Coordination Chemistry Reviews 306 (2016) 510532

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

From models to lignin: Transition metal catalysis for selective bond

cleavage reactions
Peter J. Deuss, Katalin Barta
Stratingh Institute for Chemistry, Rijksuniversiteit Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
1.1. Motivation and scope of this review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
1.2. Why lignin? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
1.3. Structural considerations and challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
1.4. Model compounds that mirror representative linkages in lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 512
2. Acid and base mediated depolymerization of lignin and lignin model compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 512
2.1. Base mediated depolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 512
2.2. Acid mediated depolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
3. Oxidative approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
3.1. Metal catalyzed oxidative approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
3.2. Efcient depolymerization of lignin by selective pre-oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
3.3. Photocatalytic cleavage of selectively oxidized model compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
3.4. Alternative selective oxidation methodology followed by lignin depolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
4. Reductive approaches utilizing hydrogen gas and silanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
4.1. Methods for lignin aryl-ether bond cleavage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
4.1.1. Reductive cleavage of diarylethers and aryl-alkyl ethers as lignin 4-O-5 and -O-4 model compounds . . . . . . . . . . . . . . . . . . . . . . . . 515
4.1.2. The conversion of lignin using heterogeneous catalyst based on Ni and other reductive methods for lignin conversion . . . . . . . 517
4.2. Reduction of lignin ether bond using silane reagents without transition metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
4.3. C O bond cleavage by dehydroalkoxylation with lanthanides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
5. Hydrogen neutral and hydrogen transfer approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
5.1. C O bond cleavage by dehydroaryloxylation by iridium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
5.2. Cleavage via hydrogen transfer with ruthenium catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
5.2.1. Cleavage of C2--O-4 model compounds by ruthenium catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
5.2.2. The role of the ligands in the cleavage reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
5.2.3. Ru/base promoted metal catalyzed cleavage reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
5.2.4. Related catalytic systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
5.2.5. Cleavage of C3--O-4 model compounds by ruthenium catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
6. Hydrogen transfer from alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
6.1. Copper doped porous metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
6.2. Hydrogen transfer from isopropanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530

a r t i c l e i n f o a b s t r a c t

Article history: In the coming decades major changes are expected in the chemical industry regarding the utilized raw
Received 10 December 2014 material inputs. Depleting fossil resources will gradually be replaced by renewable feedstocks wherever
Received in revised form 26 January 2015 possible. Because of this transition, new and efcient methodologies are required that enable depoly-
Accepted 6 February 2015
merization and defunctionalization of these complex, highly oxygenated biopolymers. Additionally,
Available online 17 February 2015
utilization of all components of lignocellulose is of great importance. In particular, depolymerization
of lignin into its aromatic subunits or dened aromatic platform chemicals has proven challenging.

Corresponding author. Tel.: +31 50 363 4232; fax: +31 50 363 4296.
E-mail address: k.barta@rug.nl (K. Barta).

http://dx.doi.org/10.1016/j.ccr.2015.02.004
0010-8545/ 2015 Published by Elsevier B.V.
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532
Keywords: Various approaches to overcome these difculties have been attempted and resulted in new and exciting
Aromatic chemicals developments in many elds. In this review we will give an overview of bond cleavage strategies relevant
Lignin depolymerization for lignin depolymerization using homogeneous catalysts, focusing especially on reductive and hydrogen
C O bond cleavage transfer methods.
Homogeneous catalysis
1. Introduction
1.1. Motivation and scope of this review
Devising and implementing strategies, which would enable the
production of bulk and ne chemicals [1,2] or fuels [3] from sustain-
able biomass materials, especially from agricultural or municipal
waste resources that do not compete with food supply [4], is one
of the grand challenges in sustainable chemistry [5]. To success-
fully address this challenge, a paradigm shift in chemical catalysis
is necessary. New methods are desired that allow for depolymer-
ization and defunctionalization of complex and highly oxygenated
bio-derived polymers or platform chemicals derived therein [68].
Because conventional petroleum-based chemistry primarily adds
functionality to simpler structures, novel scientic insights are of
major importance to enable such methods [9].
In order to allow for the utilization of all lignocellulose
components, particular attention has to be devoted to the depoly-
merization of lignin, which has proven particularly difcult. In this
review we will provide an overview of the different approaches
taken to tackle this problem and will primarily focus on the design
of transition metal complexes for the selective cleavage of specic
bonds in model compounds. The compatibility of these systems
with the use of real lignin will also be discussed.
1.2. Why lignin?
Lignocellulose consists of about 3050% cellulose, 2035% hemi-
cellulose and 2035% lignin [10]. While established routes exist
for the conversion of the cellulose fraction of biomass and derived
platform chemicals [1117], there is a general lack of efcient pro-
cesses for the utilization of lignin, which is the most important
renewable source of aromatics on the planet [18]. The successful
implementation of the biorenery concept in which lignocellulose
is fractionated into its main components, requires efcient chem-
ical or catalytic valorization routes for all fractions. This includes
lignin, which is currently simply burned to provide heat for other
processes [1921]. Moreover, a large volume of lignin waste is pro-
duced annually by the paper industry and this amount is expected
to increase with the introduction of second-generation bioethanol
[22,23]. Considering these factors, it has become highly desir-
able to develop efcient methods for the conversion of lignin
especially to aromatic chemicals [18,24,25]. Additionally impor-
tant is that, besides various other approaches to take care of the
increased energy demand, shale gas has emerged as an alterna-
tive to petroleum. Considering the implementation of shale gas, a
shortage of aromatic chemicals is a serious prospect [26].
A plethora of research directions have been initiated for lignin
valorization, predominantly in the past decade. Very important
are thermal approaches [27], especially pyrolysis and gasication,
which can be used for the production of syngas or pyrolysis oils
from lignocellulose or lignin [3,28,29,30]. By now lignin conver-
sion has touched a number of scientic disciplines. New methods
have emerged for enzymatic [31,32] mechanochemical [33,34]
hydrothermal [27,35] electrochemical [36] or microwave assisted
[37] lignin depolymerization. Exciting developments have taken
place in the eld of chemical catalysis [10]. Heterogeneous catalysts
511
2015 Published by Elsevier B.V.
historically developed for the petrol industry have been applied
also in lignin upgrading and new catalysts were designed [38]. A
summary of different approaches is given in a variety of excellent
reviews [3943]. Importantly, lignin depolymerization to a selected
set of desired products requires selective cleavage of specic bonds
(see also Section 1.4). This initiated new research questions and
the search for novel catalysts structures also in the eld of homo-
geneous catalysis [44]. We have recently summarized the latest
advances in this eld in a perspective, which also addressed other
biomass-derived materials such as sugars and fatty acids [45]. In the
current contribution we will focus entirely on research relevant for
lignin conversion in more depth and include a large number of new
results, which appeared in recent literature. Oxidation has already
been reviewed [10,4650] therefore this review will primarily focus
on reductive approaches using transition metal catalysts. Although
not strictly related to coordination chemistry, the discussion will
include acid and base catalysis, as well as selected examples of
heterogeneous systems where appropriate. Within this, a sepa-
rate section will address the formidable advances made in the Ford
laboratory regarding the reductive depolymerization of lignin and
lignocellulose via hydrogen transfer from supercritical methanol
[9].
1.3. Structural considerations and challenges
Due to its high aromatic content, lignin could be an ideal
source of simple aromatic or ne chemicals in the future
[8,10,11,18,41,45]. However, the selective conversion of lignin to
well dened chemicals is very challenging. This is perhaps no sur-
prise, considering that nature designed lignin to be robust, and to
provide structural stability to plants. In nature, lignin is biosyn-
thesized from three simple aromatic building blocks: coniferyl,
sinapyl and coumaryl alcohol (Fig. 1) [5154]. These monolignans
are randomly coupled via radical processes, to result in a sta-
ble, heterogeneous, 3-dimensional biopolymer that is particularly
resistant towards chemical degradation. In Fig. 1, all positions in the
corresponding monolignans that are potentially involved in bond
forming reactions are depicted. This demonstrates that a large num-
ber of variations are possible and shows why there is no generally
accepted, precise description of the lignin structure.
Nonetheless, a lignin of known origin (e.g. plant type, hardwood
vs softwood) can be described by several common characteris-
tics. These are the guaiacyl/syringyl ratio, representative structure,
aliphatic vs aromatic free OH content, the molecular weight and
the abundance of the most common linkages. Indeed, lignin chem-
istry dates back to the 3040 s when main efforts focused on
structural elucidation of the native lignin structure [5559]. The
development of new analytical procedures for structural charac-
terization of lignin and product mixtures obtained, for example by
2D NMR spectroscopy, will have great relevance for understand-
ing catalytic conversion pathways [6062]. A further difculty,
primarily caused by the amorphous structure of lignin, is its rel-
atively high molecular weight, and limited solubility in most
common organic solvents at ambient temperature. To this end,
alternative reaction media such as supercritical solvents [63,64]
or ionic liquids have emerged as an important advance [65,66].
The nature of the bond cleavage reactions desired for selective
512 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532
Fig. 1. The structure of monolignans (circles highlight most common linking sites) and the random structure of lignin.
depolymerization often necessitates elevated temperatures during
catalytic treatment, which leads to a variety of side processes and
favours the formation of intractable biochar. The undesired con-
sequences of char formation are decrease of valuable carbon yield
and catalyst deactivation [9]. Considering the insolubility of lignin,
homogeneous catalyst would have the advantage to penetrate the
three-dimensional lignin structure and reach the target linkages
more easily whereas heterogeneous catalysts might be limited by
the steric hindrance displayed by the lignin backbone and the het-
erogeneous nature of the substrate itself [45]. The advantage of
transition metal catalysis is the possibility for ne-tuning the cata-
lyst structures through precise control of metal environment [67]. A
large number of ligand variations are available. This way, after deep
insight into structure activity relationships, a very active catalyst
for specic bond cleavage reactions that operates at mild reaction
temperatures, can, in principle, be designed. Another advantage of
homogeneous catalysis is the possibility for simultaneous or tan-
dem processes. Multiple catalysts could operate in a single process,
each targeting different types of linkages present in real lignin.
1.4. Model compounds that mirror representative linkages in
lignin
Given the various difculties with the lignin starting mate-
rial and product characterization, most research in homogeneous
catalysis is focused on using model compounds that mirror
the representative linkages in lignin. These model studies use
well-dened, soluble organic substrates and enable an in-depth
understanding of the bond cleavage reactions that would be prac-
tically impossible to obtain from direct studies on lignin.
The most common linkages contain aromatic or aliphatic ether
units and a summary of these is shown in Fig. 2. In this review,
we describe the different strategies developed for cleaving these
specic bond types in lignin. However, importantly, when trans-
lating methodologies developed on model compounds to lignin,
monomer yields will heavily depend on the content of the linkage
targeted. In order for a method to produce aromatic monomers, a
subunit has to be anked by two of corresponding linkages [114].
Therefore, in order to maximize monomer yields, most research has
focused on splitting the most recurring -O-4 linkage.
New pathways for cleavage of -O-4 linkage frequently involve
the oxidative or dehydrogenative formation of the corresponding
ketone (-O-4-ketone in Fig. 2) [68]. This is in line with recent
theoretical studies, which systematically calculated the bond dis-
sociation energies of the most representative lignin linkages [69].
According to these studies, the less abundant -O-4 linkage would
be most readily cleaved with a calculated bond dissociation energy
(BDE) of 55 kcal mol1 . As a comparison, the calculated BDE of the
-O-4 linkage was found between 105 and 115 kcal mol1 . Con-
sidering the above-mentioned strategy, which proceeds through
the -O-4-ketone linkage, the calculated BDE is decreased to below
60 kcal mol1 , rendering this motif far more susceptible to cleav-
age.
In this review, we will attempt to give a detailed overview of new
and exciting strategies developed for lignin depolymerization, in
which often model compounds that mirror lignin linkages are used
(Fig. 2). Although not strictly coordination chemistry, given their
historical relevance, acid and base catalysis will be briey intro-
duced in Section 2. These concepts are important also because acids
or bases are repeatedly used in parallel with transition metal catal-
ysis. Then, a concise Section 3 related to oxidation chemistry will
follow, highlighting the most recent, very promising studies espe-
cially regarding lignin depolymerization. This includes methods
that apply selective oxidation methodologies followed by different
cleavage strategies. The focus of this review will be the develop-
ment of the reductive strategies detailed in Sections 46. In Section
4 reductive approaches employing hydrogen gas are described.
Hydrogen neutral approaches are summarized in Section 5. Studies
on lignin and lignocellulose disassembly using hydrogen transfer
processes from alcohols are shown in Section 6 focused around
highlights from the Ford laboratory.
2. Acid and base mediated depolymerization of lignin and
lignin model compounds
2.1. Base mediated depolymerization
In the upcoming sections various examples will be described,
where the addition of organic and inorganic bases appears to facili-
tate the cleavage of lignin model compounds and models that have
been modied using other methodology (Sections 5.2.3 and 5.2.4).
In these cases the base either catalyzes the cleavage of the organic
substrates, or is required to aid the transition metal catalyzed pro-
cesses. This is also highlighted in some recent examples combining
hydrogenolysis promoted by bases [70,71]. Base catalyzed depoly-
merization of lignin has also been extensively used in combination
with supercritical uids (see also Section 6.1) [72,73]. Lercher and
coworkers investigated the depolymerization of lignin catalyzed
by NaOH in aqueous media [74]. The types of aromatic molecules
obtained are depicted in Fig. 3a. Mechanistic details of the phenyl
ether cleavage were also elucidated using a C2--O-4 bond model
compound, whereby a six-membered transition state involving a
hydroxide ion and sodium cation was proposed, leading to C2-
fragments (Fig. 3b). The nature of recondensation processes was
also investigated. It was found, that recondensation upon cleavage
causes the formation of products with a wide molecular weight
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532 513

Fig. 2. Typical linkages found in lignin, which serve as models for the development of cleavage methodologies for selective depolymerization. Types of reactions discussed
in this review and the corresponding sections (see Fig. 6 and Tables 4 and 5 for an overview of terminology for the different model compounds used and a comprehensive
overview of all methodologies described in this review).

range, often even larger than the initial lignin itself. The impor-
tance of suppressing these side reactions, in this case by capping
with boric acid [74] was later also conrmed in other studies [75].
2.2. Acid mediated depolymerization
Depolymerization under acidic conditions is perhaps one of the
most classical methods in lignin chemistry. Historically this eld
has developed in the context of wood pulping and fractionation of
lignocellulose to its main components. In these early studies, elab-
orate methodologies were described for the isolation of lignin of
different type and origin with main focus at that time being struc-
tural elucidation [56,7678]. During these studies changes in the
lignin structure were also observed and this lead to novel mech-
anistic ndings regarding lignin reactivity under these conditions.
Several pathways have been elucidated. These main ndings are
summarized in Fig. 4.
The main products of acidolysis of lignin have been identied
several decades ago and were used to determine the composi-
tion and structure of the lignin polymer (examples provided in
Fig. 4a) [79,80]. Later studies have indicated how these compounds
are formed after prolonged exposure of lignin to acidic condi-
tions, mainly by cleavage of the most abundant -O-4 linkage
(Fig. 4b) [81]. Detailed investigation of these pathways is ongo-
ing to this date and recently comprehensive studies and reviews
were published [8285]. In the widely accepted proposed reaction
mechanism, the main cleavage pathway is through dehydration to
provide carbocation I1 as main reactive intermediate. The cleavage
is proposed to occur through a set of rearrangements to inter-
mediates like I2 and I3 that can cleave following rehydration to

Fig. 3. (a) Aromatic monomeric product obtained from lignin depolymerization with 25 wt% NaOH in water at 300 C and 250 bar. (b) Proposed NaOH catalyzed cleavage
mechanism of the -O-4 bond involving sodium cations [74].
514 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532

Fig. 4. (a) Identied monomeric aromatic products from acidolysis of birch and spruce lignin with 1,4-dioxane:H2 O 9:1 0.2 M HCl [80] (in bold Hibbert ketones [83]). (b)
Proposed mechanism for the formation of the major products from cleavage (bold arrows) of the -O-4 linkage in lignin and condensation reactions (dashed arrows) leading
to higher molecular weight products [8084].

give ketone products K1 and K2. These ketones then rearrange
via an allylic-shift to give mixture of observed monomeric aro-
matic compounds that are typically referred to as the Hibbert
ketones (K1K5) [77]. A parallel cleavage pathway is the loss of
formaldehyde leading to C2-fragment I4 that upon cleavage leads
to aldehyde K6 [80,8284]. This aldehyde is known to undergo
self-condensation reactions [86]. In our group we have show-
cased different methodologies to prevent condensation of such
aldehyde intermediate leading to interesting aromatic products
[87].
Like the use of bases, the application of acids alone with the
goal of producing monomeric compounds is considered rather
ineffective due to competing repolymerization and condensation
reactions of the cleaved lignin fragments. Therefore, acid mediated
depolymerization of lignin is usually considered in combination
with other methodologies (see Sections 4.1.2 and 6.2).
3. Oxidative approaches
3.1. Metal catalyzed oxidative approaches
Oxidative degradation of lignin is the prime methodology
used by nature [88]. Fungi and bacteria typically employ specic
manganese containing peroxidases [89] as enzymes to achieve
decomposition of woody or lignocellulosic residues. Inspired by
nature, research groups have explored many well-dened metal
complexes for the oxidative deconstruction of lignin, and these
approaches have been extensively reviewed [10,45,46,48,49]. The
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532
use of oxidants such as manganese, iron and chromium reagents
was also reported to facilitate the removal of lignin from cellulose
for paper production via cleavage of the -O-4 motif [47,90,91].
Exhaustive oxidation of aromatics is also highly relevant in other
bleaching applications and these aspects were summarized in
a review by Hage [46]. Oxidation is also the only methodology
currently employed at commercial scale to obtain an aromatic
chemical, vanilin, from lignin. This is done from lignin obtained
as waste stream by the paper industry via oxidative copper catal-
ysis [92]. Elegant in depth studies using vanadium [9399] copper
[94,96,100,101] and cobalt [102,103] complexes have shown high
control for the regioselectivity of the cleavage of the -O-4 bond
in model compounds. Importantly, some of these approaches
have been applied on lignin itself [95,103,104]. Here, generally,
vanillin, vanillic acid and related compounds corresponding to
syringyl and phenolic subunits in lignin are obtained as major
compounds. Methyltrioxo rhenium (MTO) was used in combina-
tion with hydrogen peroxide to cleavage lignin model compounds
[105,106]. Interestingly, a recent report by Khn et al. demon-
strated the cleavage of a C2--O-4 model compound catalyzed by
in situ generated methyldioxo rhenium (MDO) providing aldehyde
products that relate to those generated under acidic conditions
[107]. Recently, highly selective oxidation of lignin and lignin model
compounds to dicarboxylic acid was reported using chalcopyrite
(CuFeS2 ) and H2 O2 [108]. High yield was explained by the demon-
stration that also linkage can be oxidatively cleaved under the
employed conditions (60 C, pH 4, 5 h).
3.2. Efcient depolymerization of lignin by selective pre-oxidation
Oxidative cleavage is typically reported to lead to complicated
product mixtures containing highly oxygenated aromatic products
that are challenging to analyze. Several recent reports, however,
demonstrated the unique benets of the selective oxidation of the
secondary alcohol in the common -O-4 motif as this leads to the
formation of the more labile -O-4-ketone [68]. This strategy also
relates to the other cleavage methodologies presented later on in
Sections 3.3 and 3.4.
Relying on their own selective oxidation strategy, Stahl and
coworkers reported a very effective approach to lignin depolymer-
ization into monomeric aromatic products (Scheme 1) [109]. In
earlier work the group had established the selective oxidation of
the secondary alcohol in the -O-4 motif by a specic methodology
that uses catalytic 4-acetamido-TEMPO/HNO3 /HCl under aerobic
conditions [101,110]. The used model compounds were converted
to the earlier described -O-4-ketone (see Section 1.4, Fig. 2). The
product of lignin oxidation was referred to as oxidized lignin.
However, further oxidative cleavage of -O-4-ketone containing
model compounds and lignin was not yet at a desired level due to
instability of the formed products under these oxidative conditions.
In the recent work, a highly effective cleavage of oxidized lignin
to low molecular weight aromatic products with excess sodium
formate in aqueous formic acid (8590 wt%) at 110 C in 24 h was
reported [109]. For oxidized aspen lignin, this resulted in around
50% monomeric aromatic products providing the product mixture
outlined in Scheme 1. These results correspond well to the -O-
4 content (90%) in the applied source of lignin calculated from
2D-HSQC NMR of which 90% was reported to be oxidized to the
corresponding ketone using this selective oxidation methodology
[101].
3.3. Photocatalytic cleavage of selectively oxidized model
compounds
Photocatalytic cleavage of the -O-4-ketone by visible light,
relying on own previously reported iridium mediated C O bond
515
cleavage methodology [111] was reported by Stephenson et al.
[112]. Interestingly, this protocol was also successfully applied on a
-O-4 model in which the -hydroxyl-group was ethylated and the
-hydroxyl-group was replaced by an aldehyde. The aldehyde func-
tionality in this position was shown by calculations to destabilize
the -O-4 bond to a similar extent as the ketone in the -position
[69]. In a batch to ow reactor setup -O-4 model compounds were
cleaved at room temperature by initial oxidation using a slightly
modied TEMPO based oxidation protocol in the presence of (but
not on) lignin itself [101,113]. Very low iridium loadings were used
(Scheme 2).
3.4. Alternative selective oxidation methodology followed by
lignin depolymerization
Very recently, the group of Westwood presented a new
approach to achieve selective oxidation of lignin and lignin -O-
4 model compounds (Scheme 3) [114]. Also this methodology uses
molecular oxygen as the oxidant, promoted by catalytic amounts of
2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tert-butyl
nitrite (tBuONO). With this catalytic system the -O-4-ketone was
formed selectively at room temperature for model compounds.
Additionally, the same selective oxidation reaction could be per-
formed using lignin at 80 C in 14 h. The oxidation step was followed
by a reductive cleavage protocol using Zn/NH4 Cl at 80 C inspired by
previous work with simple ketones [115]. Model compounds were
successfully cleaved within 15 min, and oxidized lignin was depoly-
merized within an hour using this methodology. The oxidation and
cleavage protocols were successfully applied in a sequential/one
pot fashion to depolymerize birch lignin into aromatic monomers
shown in Scheme 3. In this case, the overall yield was calculated to
correspond to about 43% based on the -O-4 content of the used
lignin source. DDQ was also applied by the same group to modify
the robust linkage in lignin pioneering a new path for selec-
tive cleavage of this linkage [116]. Another alternative non-metal
based oxidation was reported using nitrogen-containing graphene
material in the presence of tert-butyl hydroperoxide [117].
4. Reductive approaches utilizing hydrogen gas and silanes
4.1. Methods for lignin aryl-ether bond cleavage
4.1.1. Reductive cleavage of diarylethers and aryl-alkyl ethers as
lignin 4-O-5 and -O-4 model compounds
In 2011, Hartwig and co-workers reported the very effective
cleavage of diarylethers using Ni(cod)2 and a NHC ligand in the
presence of base under mild conditions (1 bar of hydrogen, 120 C,
Scheme 4) [118]. The corresponding arene and phenol products
were obtained in excellent yield. The catalyst system originates
from the extensive research on nickel catalyzed cross-coupling
reactions via C O bond activation [119124]. However, PCy3 , a
typical ligand for nickel catalyzed cross-coupling reactions was
reported to decompose under cleavage condition used. Therefore,
in situ generated NHC ligands were tested that lacked labile P C
bonds. With the more donating NHC1, the reaction proved to
be highly effective and selective for aromatic products without
showing signicant amounts ring hydrogenation towards satu-
rated hydrocarbons.
Different hydride donors could also be applied, and in these
cases a variety of NHC ligands or Ni(acac) as nickel precursor could
be used, albeit less efciently compared to NHC1 in combination
with Ni(cod)2 (Table 1) [118]. It was also demonstrated that
either with silane reducing agents, aluminium hydride donors or
hydrogen gas with the addition of AlMe3 also aryl-alkyl ethers and
benzylic ethers were successfully cleaved. The catalytic system
516 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532

Scheme 1. Lignin depolymerization procedure via selective oxidation and subsequent formic acid/sodium formate mediated cleavage of the formed -O-4-ketone [101,109].

was more active for aryl substrates with electron withdrawing
substituents. For asymmetric diphenyl ethers, the ether bond
was preferably cleaved at the side of the least electron rich aryl.
Interestingly, both the activity and selectivity pattern could be
reversed by using a ligandless nickel system using either Ni(cod)2
or Ni(CH2 TMS)2 (TMEDA) and base [125]. This system is more
relevant to lignin in which the aromatic rings contain electron
donating hydroxy and methoxy substituents. In this case, forma-
tion of heterogeneous nickel clusters or particles were suggested
as the active species. Similarly, metal particles were suggested to
be the active catalysts in the cleavage of various diaryl ethers and
aryl-alkyl ethers with Co(acac)2 or Fe(acac)3 in the presence of 2.5
eq. of NaOtBu and LiAlH4 at 140 C [126,127].
The studies by Hartwig included several model compounds
for 4-O-5 and the -O-4 linkage found in lignin (Scheme 5). The
methodology was successful at cleaving these linkages effectively
with high product yields. However, a C3--O-4 model compound
was cleaved by base alone at elevated temperatures without the
presence of nickel to give a mixture of products.
The group of Agapie studied the mechanism of the nickel cat-
alyzed aryl-alkyl ether cleavage reaction [128]. Using labelled
aromatic ethers 2-D3 C-O-naphthalene and 2-(CD2 (CH2 )4 CH3 )-O-
naphthalene, over 90% deuterium incorporation into the product
naphthalene (2-D-naphthalene) even under hydrogen atmosphere
was shown (Scheme 6a). Further elegant studies using aryl-ether
with pendant phosphines helped to propose a mechanism for the
nickel-catalyzed cleavage of aryl-alkyl ether bonds (Scheme 6b).
Several intermediates were isolated and characterized using
NMR and single-crystal X-ray diffraction. The mechanism was pro-
posed to proceed through coordination of a nickel(0) species to the
arene followed by insertion into the C O bond. In computational
studies for nickel catalyzed cross-coupling reaction this sequence
of steps has also been previously proposed [129]. Cleavage occurs
via -hydride elimination forming a formyl-group and reductive

Scheme 2. Photocatalytic cleavage of a selectively oxidized lignin -O-4 model compound [112].

10 wt% DDQ/tBuONO
2-methoxyethal:DME (2:3) O O O
80 C, 14 hours, O2 MeO MeO
birch lign OH + OH +
After 14 hours: HO HO HO
0.5 wt% 5 wt% 0.5 wt%
Zn/NH4Cl, H2O OMe OMe OMe
80 C, 1 hour

Scheme 3. Selective oxidation with DDQ/tBuONO and cleavage with Zn/NH4 Cl of birch lignin into monomeric aromatic products [114].
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532 517

Scheme 4. Nickel catalyzed diarylether hydrogenolysis [118].

Table 1
Nickel catalyzed cleavage of diphenylether (R1 = R2 = H, in Scheme 4).a Data adapted from supplementary information [118].

Entry [Ni] L H T ( C) Conv. (%) Benzene (%) Phenol (%)

1 Ni(cod)2 NHC1HCl H2 b 120 100 99 99

2 Ni(cod)2 NHC1HCl H2 b 100 75 69 75
3 Ni(cod)2 PCy3 H2 b 120 4 0 0
4 Ni(cod)2 NHC1HCl DIBALH 60 100 99 99
5c Ni(cod)2 NHC2HCl DIBALH 60 87 87 60
6c Ni(acac)2 NHC1HCl DIBALH 60 35 37 10
7c Ni(cod)2 d NHC1HCle Et3 SiH 100 65 42 65
8c Ni(cod)2 d NHC2HCle Et3 SiH 100 58 38 54
9c Ni(cod)2 d NHC3HCle Et3 SiH 100 20 20 16
10c Ni(cod)2 d NHC4HCle Et3 SiH 100 46 44 44
11c Ni(cod)2 d NHC5HCle Et3 SiH 100 52 48 52
a
Conditions: 20 mol% [Ni] 40 mol% L, m-xylene, 2.5 eq. H, 2.5 eq. NaOtBu, 16 h.
b
1 bar.
c
Toluene as solvent.
d
10 mol%.
e
20 mol%.

elimination of the arene from the formed nickel hydride species.
The role of the hydrogen is the reduction of the formyl group to
the corresponding alcohol and formation of the catalytically active
nickel species. The formyl group was also able to act as hydrogen
source to form carbon monoxide, which remained coordinated. The
ability of the strongly donating bulky NHC ligand to stabilize the
nickel(II) intermediate and promote the reductive elimination step
is likely the reason for its success. A recent report showed evidence
for aryl-alkyl ether cleavage by Ni(cod)2 /PCy3 in the presence of
silanes in which case however, the Ni(0)/Ni(II) mechanism does
not operate in the cleavage of C OMe [130]. Here, Ni(I)-SiR3 was
suggested as a key intermediate. Additionally, a crucial role was
ascribed to the alkene (e.g. cod), originating from the precursor, as
stabilizing agent for the catalyst in its resting state.
4.1.2. The conversion of lignin using heterogeneous catalyst
based on Ni and other reductive methods for lignin conversion
As demonstrated by the examples detailed above, nickel chem-
istry appears to be highly suitable for the cleavage of lignin derived
model compounds. Earlier, heterogeneous Ni/SiO2 catalysts were
reported for the cleavage of simple diaryl ethers and aryl-alkyl
ethers at 120 C and added hydrogen pressure to obtain phenols
and arenes [131]. In addition to the relatively low temperature at
which this heterogeneous catalyst operated, the reaction worked
remarkably well in water as solvent. Additionally, no base was
added. In this system ring hydrogenation products were also
detected. Later, many different studies using heterogeneous Ni cat-
alysts for the conversion of lignin were described. For example,
the hydrogenolysis of lignin to propylguaiacol and propyl syringol
products in good selectivity without signicant over-reduction was
reported [132,133]. Furthermore, Ni doped HZSM-5 was used as a
catalyst to obtain alkyl-phenols in up to 15% yield [134]. Later,
a series of NiM (M = Ru, Rh, Pd) catalysts were reported for lignin
depolymerization to aromatic chemicals in water under mild con-
ditions (130 C, 1 h) [135]. A Ni/Au bimetallic catalyst was used
for the production of phenol from lignin [71,136]. Other coopera-
tive bimetallic palladium/zinc catalysts were effective for efcient
lignin hydrogenolysis to aromatic products [137]. Among other
reductive methods an early two-step procedure described the con-
version of lignin to alkanes by Kou et al. [138]. Perhaps the earliest
example of lignin and wood hydrogenolysis was carried out under
relatively forcing conditions over CuCr catalysts [139]. Hetero-
geneous approaches, also including high temperature strategies,
are detailed in several reviews [10,29,39,42,43]. Surprisingly, only
limited number of homogeneous catalysts were described to be
effective in lignin depolymerization using hydrogen gas or other
hydrogen sources. Combinations of ruthenium and rhodium, pre-
cursors and phosphine and nitrogen ligands were tested in the
518 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532

Scheme 5. Lignin model compounds successfully cleaved during studies on nickel catalyzed ether cleavage [118,125].

degradation of ethanol organsolv lignin with added hydrogen gas
[140].
4.2. Reduction of lignin ether bond using silane reagents without
transition metals
The group of Grubbs recently reported a transition metal free
system to successfully cleave diaryl and aryl-alkyl ethers to obtain
the corresponding phenols and arenes. In this study Et3 SiH was
used in the presence of strong bases like KOtBu at temperatures
ranging from 75 to 165 C [141]. The reaction also led to preferen-
tial formation of ortho-silylated aromatics depending on reaction
conditions (type of base and solvent).
Earlier reports had already described the cleavage of aryl
and alkyl ether bonds using Et3 SiH in the presence of catalytic
B(C6 F4 )3 [142,143]. Cantat and coworkers recently exploited this
hydrosilylation methodology for the cleavage of aryl-ether bonds
resembling those found in lignin [144]. Simple model compounds

Scheme 6. Mechanistic studies on the nickel catalyzed aryl-alkyl ether cleavage (a) Showing deuterium labeling studies. (b) Showing studies using aryl-ether with pendant
phosphines [128].
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532
Scheme 7. Mild cleavage of (a) lignin -O-4 and (b) -O-4 model compounds under
organocatalyzed hydrosilylation conditions [144].
without additional hydroxyl functionalities, mirroring the -O-
4 bond and -O-4 linkages were readily cleaved to provide
a phenoxysilane and the corresponding alkylaromatic products
in good yields at mild reaction conditions (Scheme 7a) [144].
The cleavage was highly selective for the O-alkyl bond whereas
O-aryl cleavage products were not observed. Additionally, aro-
matic O-Me bonds were also cleaved to give the corresponding
aryl-O-silanes and methane. The formation of alkylated phenoxy
silanes was a side reaction that was observed under the con-
ditions applied. More realistic lignin -O-4 model compounds
were also efciently cleaved (Scheme 7b). However, interest-
ingly, the formation of the silane derivative of 2-phenyl-ethanol
was observed as second cleavage product in addition to the cor-
responding phenoxysilane. Computational and isotope labelling
studies concluded a mechanism that involves an aryl shift from
the to the carbon, following the initial dehydrogenative sily-
lation of the benzylic alcohol. Importantly, triethylsilane could be
exchanged for cheap silanes (Me3 Si(OSiMeH)n OSiMe3 = PMHS and
Me2 SiHOSiHMe2 = TMDS) that can be potentially provided by the
silicone industry.
Brook et al. later published a related methodology in which
PMDS (Me3 SiOSiMe2 H) was used to cleave a range of aryl-alkyl
ether containing lignin model compounds to obtain silylated prod-
ucts [145]. Interestingly, they demonstrated that diarylethers are
unaffected by this methodology. The methodology was further
extended to wood-lignin samples. Hard- and softwood samples
in toluene were exposed to silane reagents with B(C6 F4 )3 as
catalyst under the inuence of sonication. For softwood only
Et3 SiH and MePh2 SiH showed solubilization of the lignin (<30%).
Changes to the characteristics of the insoluble fraction did indi-
cate silylation of the lignin, however depolymerization was found
inefcient. Hardwood on the other hand was very efciently sol-
ubilized by PMDS (>95%) with 10 wt% B(C6 F4 )3 . The molecular
weight range was decreased from over 3600 g/mol in the original
lignin to smaller oligomeric fragments of <600 g/mol upon reduc-
tion/depolymerization using this method.
519
4.3. C O bond cleavage by dehydroalkoxylation with lanthanides
Hydroalkoxylation is a well-known method for the function-
alization of alkynes, alkenes, allenes and a variety of catalytic
systems have already been described [146148]. In an elegant study
Marks and coworkers showed that the reverse reaction can be
applied for the cleavage of aryl-alkyl ethers and for which several
lanthanide/hydrogenation catalyst systems are discussed in the
section below [149]. The linkages targeted with this methodology
resemble many of the aryl-ether bonds found in lignin.
Lanthanide triates catalyze a range of chemical transfor-
mations that have great promise for application in biomass
depolymerization and defunctionalization [150152]. The group
of Marks reported the cleavage of aryl-alkyl and dialkyl ethers
using lanthanide triates combined with palladium nanoparticles
under hydrogen atmosphere in ionic liquid [149]. The reported sub-
strate scope included models with aryl-alkyl ether C O bonds that
relate to -5 and -O-4 linkages in lignin (Scheme 8a). The key
step of this cooperative catalyst system is the lanthanide-mediated
dehydroalkoxylation, which is the microscopic reverse of the previ-
ously reported hydroalkoxylation catalyzed by lanthanide triates
[153,154]. The mechanism was proposed to involve transfer of a
proton in the -position relative to the ether to the etheric oxygen
(Scheme 8b). The proposed catalytic cycles was supported by DFT-
calculations [155], which found that lanthanides with smaller ionic
radii and thus enhanced electrophilicity gave faster reactions due to
a lower activation barrier for the etheric C O bond cleavage. Over-
all, reactivity decreased in the order Yb(OTf)3 > Sm(OTf)3 > La(OTf)3 .
Palladium nanoparticles deposited on alumina were necessary
to ensure continued hydrogenation activity under the reported
reaction conditions, as these were found sufciently resistant to
thermal sintering in contrast to Pd/BaSO4 . A later study showed
that in the case of dialkylether cleavage the same reaction could
be combined with dehydration of the formed alcohol followed
by hydrogenation to yield defunctionalized alkane products [156].
Various transition metal triates could be used of which Hf(OTf)3
showed the best performance.
5. Hydrogen neutral and hydrogen transfer approaches
5.1. C O bond cleavage by dehydroaryloxylation by iridium
complexes
Recently, the group of Goldman reported, based on earlier sto-
ichiometric work [157,158] the catalytic dehydroaryloxylation of
aryl-alkyl ethers (Scheme 9a, Table 2) [159]. These new results
are relevant for lignin depolymerization but importantly provide
a new and atom economic method for the deprotection of the rel-
atively unreactive aryl-alkyl ethers by direct scission of the ether
bond catalyzed by a single iridium complex. Hydroaryloxylation of
olens with phenols for the formation of the C O bond has been
previously established with iridium pincer complexes [160,161].
The same and similar pincer complexes comprising sterically less
congested phosphines are capable of catalyzing the reverse reac-
tion. The applied iridium phosphine(pincer) complexes used for
this C O bond cleavage are depicted in Scheme 9a and the main
results are summarized in Table 2 [159].
Of the pincer complexes applied, a lower steric bulk around
the phosphines was found benecial (Table 2 entries 13). For
substrates containing an additional Ar OMe group, the methoxy
group was not cleaved. This revealed the importance of available
-hydrogens (entry 8) for a successful cleavage reaction. The pro-
posed mechanism, depicted in Scheme 9b, proceeds via a cyclic
six-coordinate iridium intermediate, in which the oxygen and the
-carbon are coordinated to the metal. This complex was proposed
520 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532

Scheme 8. (a) Cleavage of etheric C O bonds via lanthanide catalyzed dehydroalkoxylation coupled to in situ hydrogenation with palladium nanoparticles on alumina [149].
(b) Proposed catalytic cycle of the lanthanide mediated C O bond hydrogenolysis [155].

Scheme 9. (a) Iridium catalyzed dehydroaryloxylation of aryl-alkylethers and (b) proposed mechanism [159].

Table 2
Iridium catalyzed dehydroaryloxylation of aryl-alkyl ethers shown in Scheme 9 [159].a

Entry [cat] Ar R1 R2 T ( C) Time (h) Conv. (%)

1 Ir(pin)1 3,5-Me2 C6 H3 Me H 150 16 4

2 Ir(pin)2 3,5-Me2 C6 H3 Me H 150 16 88
3 Ir(pin)3 3,5-Me2 C6 H3 Me H 150 16 92
4 Ir(pin)3 3,5-Me2 C6 H3 Me H 150 48 97
5 Ir(pin)3 3,5-Me2 C6 H3 Me Me 150 240 99
6 Ir(pin)3 4-Me-C6 H4 Me H 150 48 90
7 Ir(pin)3 Ph Me H 150 48 78
8 Ir(pin)3 4-OMe-C6 H4 Me H 150 44 62
9 Ir(pin)3 3,5-Me2 C6 H3 Me H 200 1 97
10 Ir(pin)3 3,5-Me2 C6 H3 Me Me 200 16 96
11 Ir(pin)2 3,5-Me2 C6 H3 H Hex 200 240 72
12 Ir(pin)3 3,5-Me2 C6 H3 H Hex 200 240 68
a
Conditions see Scheme 9, 500 mM substrate and 10 mM catalyst, in sealed ampule under vacuum (0.01 Torr).
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532 521

OH R3 O R3
2 RuH2(CO)(PPh3)3 1-5 mol%
R O R2 HO
Xantphos 1-5 mol%
+
R1 R4 Toluene, 135 C R1 R4
2-4 hours
R = H or OMe R = H or OMe

dehydrogenation

hydrogenolysis
[H2RuL]

[RuL]

[Ru]
O O O OAr
[Ru]
O O [Ru]
Ar Ar Ar Ar Ar
ruthenium insertion into the arylether bond

Scheme 10. Ruthenium catalyzed dehydrogenation/hydrogenolyis of C2--O-4 model compounds and proposed reaction steps [162].

to undergo aryloxide migration to give the cleaved products coor- rate was observed with a more pronounced drop in activity for the
dinating the iridium complex. From this complex the products are in situ system.
released via sequential alkene dissociation and phenol elimination. Later, Ru(cod)(methallyl)2 in combination with the triden-
tate bis(2-diphenyl phoshinoethyl) phenyl phosphine (below
referred to as triphos) was reported as a unique alterna-
tive for achieving the same dehydrogenation/hydrogenolysis
5.2. Cleavage via hydrogen transfer with ruthenium catalysts sequence [164]. Interestingly, another triphosphine (1,1,1-
tris(diphenylphosphineomethyl)ethane), which forms a very
5.2.1. Cleavage of C2--O-4 model compounds by ruthenium potent catalyst in combinations with Ru(cod)(methallyl)2 for
catalysts the hydrogenation of esters, CO2 to methanol [165] and other
In principle lignin contains a plethora of aliphatic alcohol moi- challenging substrates [166] showed only moderate activity.
eties that can act as hydrogen source to provide the reducing
equivalents for bond cleavage reactions. This would potentially
5.2.2. The role of the ligands in the cleavage reactions
provide methodology in which no external hydrogen is needed
The particularities regarding the above described ruthenium-
to achieve lignin depolymerization. Ellman, Bergman and cowork-
phosphine combinations can be explained by the requirement that
ers reported in a seminal publication the selective cleavage
an active catalyst should allow for both effective dehydrogenation
of C2--O-4 model compounds by such a hydrogen neutral
and subsequent hydrogenolysis via insertion of the metal hydride
ruthenium catalyzed dehydrogenation/hydrogenolysis reaction
into the arylether bond. Both Ru/xantphos and Ru/triphos systems
(Scheme 10) [162]. Full conversion was reached within 2 h and
are known to enable dehydrogenation coupled to secondary reac-
the transformation was perfectly selective towards phenolic and
tion steps [167,168] that reintroduce the formed hydrogen into the
functionalized acetophenone products. Similarly to the selective
nal product. However, C O bond hydrogenolyis via metal C O
oxidation described in Section 3, this methodology relies on in situ
bond insertion with such catalysts is relatively less established and
formation of a -O-4-ketone compound, which facilitates cleavage
typically requires strong electron withdrawing groups or directing
of the -O-4 ether bond.
groups [169]. Applying the corresponding ketones as substrates,
The ruthenium catalyst required for effective cleavage was
combined with an external hydrogen source, showed that the sec-
formed in situ by mixing the diphosphine ligand xantphos with
ond hydrogenolysis step is indeed ruthenium catalyzed [162,163].
RuH2 (CO)(PPh3 )3 . Remarkably, many other mono- and bidentate
Additionally, kinetic measurements of the cleavage reaction sup-
phosphine ligands were completely unreactive (Table 3 entries
ported by DFT calculations using a simple model compound and
18). Additionally, the ruthenium precursor, appeared to be inex-
Ru/xantphos as catalyst supported the tentative mechanism pro-
changable, with only RuH2 (PPh3 )4 showing signicant activity
posed by Bergman et al. [170].
(Table 3 entries 915). This hinted on subtle effects that are impor-
Leitner et al. determined that triphos and Ru(cod)(methallyl)2
tant for achieving the required hydrogen shuttling and subsequent
initially react to form a Ru(methallyl)2 -diphosphine com-
bond cleavage reaction by a single Ru-phosphine complex.
plex that upon further heating is converted into the active
James et al. conducted further studies on the Ru/xantphos sys-
Ru(methallyl)(triphos) complex in which all three phosphorous
tem by using preformed RuH2 (CO)(PPh3 )(xantphos) [163]. These
atoms of the phosphine are coordinated (Scheme 11) [164]. In
showed little difference between the preformed and the in situ
parallel, further details were revealed regarding the coordination
formed catalysts for the cleavage of simple C2--O-4 model com-
of xantphos by studies performed by James (Scheme 12) [163].
pounds and when the C2--O-4-ketone intermediate was used as
substrate under the addition of hydrogen gas. These results con-
rmed the tentative mechanism proposed earlier and indicated
the involvement of a ruthenium dihydride species in the second
hydrogenolysis reaction. A small difference between the preformed
and the in situ generated catalytic systems was found when C2--
O-4 model compounds with additional aromatic ring substituents
were applied as substrate. Here, in general, a lower hydrogenolysis Scheme 11. Formation of the active Ru(methallyl)(triphos) complex [164].
522 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532

Table 3
Ruthenium-phosphine ligand combination for the cleavage of C2--O-4 model compounds [162].a

Entry Sub.b [Ru] L Ketone (%) Phenol (%)

1 1 RuH2 (CO)(PPh3 )3 5 6
2 1 RuH2 (CO)(PPh3 )3 PPh3 <1 6
3 1 RuH2 (CO)(PPh3 )3 PCy3 4 5
4 1 RuH2 (CO)(PPh3 )3 dppm 0 0
5 1 RuH2 (CO)(PPh3 )3 dppp 0 <1
6 1 RuH2 (CO)(PPh3 )3 dppbz 0 0
7 1 RuH2 (CO)(PPh3 )3 dppf 5 6
8 1 RuH2 (CO)(PPh3 )3 xantphos >99 >99
9 2 RuH2 (CO)(PPh3 )3 xantphos >99 >99
10 2 RuHCl(CO)(PPh3 )3 xantphos 0 0
11 2 Ru(CF3 CO2 )2 (CO)(PPh3 )3 xantphos 0 0
12 2 RuH(CF3 CO2 )(CO)(PPh3 )3 xantphos 0 0
13 2 RuH2 (PPh3 )4 xantphos 36 38
14 2 Ru3 (CO)12 xantphos 0 0
15 2 Ru(methallyl)2 (cod) xantphos 13 10
a
Conditions: 5 mol% Ru, 5 mol% ligand (10 mol% in case of monophosphines), 0.2 mmol substrate 0.4 M in toluene, 135 C, 1.75 h, yields determined by GC/MS relative to
internal standard.
b
Substrate 1: R1 = R2 = R3 = R4 = H; Substrate 2: R1 = R2 = R4 = H, R3 = OMe (Scheme 10).

Evidence for intermediates with tridentate ligand coordination
was obtained based on NMR studies as well as crystal structures of
isolated inactive complexes. In one such catechol complex, shown
in Scheme 12a, the xantphos ligand is coordinated in a tridentate,
facial fashion which might be enabled by the wider bite angle of
this ligand [171]. This suggests comparable coordination modes for
both xantphos and triphos ligands in the catalytically active species.
For Ru/xantphos the proposed mechanism postulated the loss of
PPh3 and H2 from the formed RuH2 (CO)(PPh3 )(xantphos) [167]
complex leading to a catalytically active species (Scheme 12b).
Under reaction conditions it was suggested that the catalytic cycle
is more likely initiated by OH insertion of the substrate, which is
in equilibrium via substrate loss to give the same active species.
Overall, the possible hemi-lability of both xanthphos and triphos
ligands appear to be vital characteristics of these catalytic systems
and possibly important to stabilize key 16 electron intermediates
proposed by DFT calculations [170].
5.2.3. Ru/base promoted metal catalyzed cleavage reactions
Subsequent reports described ruthenium catalyzed cleavage
of C2--O-4 models compounds with several simpler commer-
cially available ruthenium precursors, including RuH2 (CO)(PPh3 )3 ,
in the presence of a base. Plietker et al. achieved the cleavage
reaction with RuCl2 (CO)(PPh3 )3 and potassium amylate, while the
obtained product subsequently underwent -alkylation with alco-
hols catalyzed by KOH [172]. Jameel et al. studied the cleavage
reaction of C2--O-4 models compounds using RuH2 (CO)(PPh3 )3
and RuHCl(CO)(PPh3 )3 in the presence of 50 mol% KOH [173]. A
two-fold role for the base was suggested. Firstly, it facilitates ruthe-
nium catalyzed alcohol dehydrogenation by converting inactive
ruthenium halide species into active hydride species [174,175].
Secondly, it aids the cleavage reaction itself through the mecha-
nism shown in Scheme 13. Indeed, small amounts of direct cleavage
products (ketone, phenol and 2-phenylethanol) were found when
the reaction was carried out solely in the presence of KOH [173].
Base catalyzed hydrolysis of lignin was discussed in the previous
Section 2.1.
A related, non-precious metal system was reported by Wang
et al. The use of simple iron salts such as Fe(acac)3 , 2.5 eq. of NaOtBu
and 1 bar hydrogen at 135 C was effective for the cleavage of C2-
-O-4 model compounds and initial formation of dehydrogenated
intermediates was also suggested [127]. Good yields of phenolic
products were obtained although the corresponding acetophenone
products were converted into a mixture of other organic com-
pounds under these reaction conditions. The formation of an active
heterogeneous catalyst was proposed in which the nature of the
iron precursor as well as the added ligand played a role.
5.2.4. Related catalytic systems
The relative position of the aryl ether and the secondary alco-
hol function in these C2--O-4 model compounds was essential
for enabling the cleavage reaction. DFT calculations conrmed this
and found a concerted ve membered transition state in which both
oxygens of the -O-4 linkage participate [170]. A parallel study that

Scheme 12. (a) Isolated catechol complex showing a tricoordinate xantphos ligand. (b) Proposed active complex for the Ru/xantphos system [163].
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532
Scheme 13. Base assisted ruthenium catalyzed hydrogen neutral dehydrogenation/hydrogenolysis of C2--O-4 model compounds [173].
also exemplied how the position of the distant chelating groups is
important for alkyl ether bond cleavage was reported by Hong et al.
using [RuCl2 (benzene)]2 and a NHC ligands [176]. Here the pres-
ence of a hydroxyl group at the C3 position of a benzyl-alkyl ether
led to cleavage and dehydrogenative coupling of amines, while
a hydroxyl groups in the C2, C4 and C5 position did not lead to
cleavage. Coordinating groups in close proximity to the ether are
in general important for the ability of ruthenium to insert into C O
bonds [169,177]. Interestingly, RuH2 (CO)(PPh3 )3 is a frequently
applied ruthenium precursor for insertion into Ar OMe bonds cou-
pled to C X bond formation reactions, although these systems
typically comprise cleavage of the O Ar bond instead of the O-
alk bond [169,177]. Cleavage of Ar OMe is in this case a minor
side reaction but also one of the catalysts deactivation pathways as
demonstrated by the inactive catechol complex described above in
Section 5.2.2, providing an indication why model compounds with
substituted aromatic rings show lower overall conversion using this
catalytic system. Related dialkylether cleavage has been reported
with iridium pincer complex via a dehydroaryloxylation mecha-
nism (Section 5.1) [159]. If a similar mechanism would be in oper-
ation for the cleavage of the C2--O-4 with ruthenium complexes,
this would yield upon cleavage an enol-ether that is a tautomer
of the observed acetone product. No evidence has thus far been
found that indicated any role of such a pathway towards the ketone
products in ruthenium catalyzed cleavage of lignin -O-4 model
compounds. Kochi et al. did report ruthenium catalyzed cleavage
of the ether linkage in 2-(2-methyoxyethyl)pyridine and analogous
compounds, followed by alkylation with triarylboroxines, suppos-
edly via a dehydroalkoxylation mechanism [178]. Here the dehy-
droalkoxylation pathway was suggested based on the observation
of small amounts of vinyl pyridine by NMR spectroscopy. Never-
theless, the properties of the catalyst applied in this case, obtained
by in situ mixing of [RuCl2 (p-cymene)]2 and triphenylphosphite
are expected to be signicantly different from the systems used for
cleavage of C2--O-4 model compounds described above.
5.2.5. Cleavage of C3--O-4 model compounds by ruthenium
catalysts
Enhancing the complexity of the lignin model compounds
allows addressing the functional group tolerance and compat-
ibility of the designed catalyst systems with more oxygenated
substrates and ultimately lignin itself. The rst report of Bergman
did include the depolymerization of a synthetic polymer [162] that
comprised phenyl-ether bonds, but lacked other crucial charac-
teristics of a lignin structure. In separate studies the reactivity in
523
the presence of additional primary alcohol moieties was described
[163]. In contrast to the cleavage of C2--O-4 model compounds
described in Section 5.2.1 the cleavage of C3--O-4 model
compounds was found challenging with ruthenium/phosphine
catalysts. The group of James attempted the cleavage of M1 using
RuH2 (CO)(PPh3 )(xantphos) but only found small amounts of
guaiacol as cleavage product (Scheme 14). Addition of external
hydrogen did not show any improvement.
Cleave of a related model compound was also described in the
presence of 1 equivalent of KOH and in situ formed Ru/xantphos
[173]. In this case, signicant amounts of guaiacol (53%) were
reported, but only traces of the corresponding ketone cleavage
products were detected. When M2 was subjected to hydrogenoly-
sis using RuH2 (CO)(PPh3 )(xantphos) also no signicant amounts of
cleavage products were obtained [163].
Systematic studies were carried out to explain the lack of
cleavage activity of RuH2 (CO)(PPh3 )(xantphos) in reactions using
C3--O-4 model compounds that in addition contain an extra
-OH functional group [163]. After cleavage reactions, various
ruthenium-substrate complexes were isolated (Scheme 14). Com-
plexes C1 and C2 were obtained from the attempted cleavage
reaction of M2. Complex C2 was isolated from the reaction mixture
initially containing M1 and RuH2 (CO)(PPh3 )(xantphos). Crystal
structures and NMR characterization of these complexes were pro-
vided. These revealed, that the substrate is dehydrogenated at both
secondary and primary alcohol positions, thus there is no dis-
crimination between primary or secondary alcohol moieties of the
substrate, both undergoing dehydrogenation. In addition, C2 dis-
plays an already cleaved substrate, which could explain the small
amount of guaiacol observed in these reactions. Similarly to the
catechol complex described in Section 5.2.2 for the simpler model
substrate, coordination of the xantphos oxygen is observed. The
structures of complexes C1 and C2 reveal likely catalyst deactiva-
tion pathways, and these species were found to be further inactive
as dehydrogenation as well as hydrogenolysis catalysts. Thus, it was
concluded by the authors that the presence of the additional -
OH inhibits the applied ruthenium catalysis. This also explains the
lack of signicant depolymerization found with lignin as substrate,
obtained from different sources [163,179].
Given the inactivity of model substrate M1 in cleavage reac-
tions due to the additional primary alcohol functionality, further
studies were performed in the James group using model com-
pound M3, which comprises a ketone in the -position instead of a
secondary alcohol, and an acetyl-protected hydroxyl group in the
-position [180]. Indeed, 27% of the corresponding ketone and 42%
524 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532
Scheme 14. The ineffective cleavage of C3--O-4 model compound M1 using RuH2 (CO)(PPh3 )(xantphos) and inactive complexes isolated from further studies [163].
Scheme 15. Cleavage of an acetylated C3--O-4 model compound [180].
guaiacol were obtained as main cleavage products (Scheme 15).
Interestingly, also a good amount of acetophenone (19%) was
observed indicating a loss of -carbon at a certain stage of the
reaction. Attempts to transfer this methodology to acetylated
lignin were unsuccessful, although this was ascribed to the low
solubility of the used lignins in toluene and the ineffective catal-
ysis in DMF, which does solubilize lignin. Nonetheless, these
systematic studies provided valuable insight into the prospect
of lignin depolymerization using well-dened ruthenium com-
plexes.
6. Hydrogen transfer from alcohols
6.1. Copper doped porous metal oxides
Reductive bond cleavage in complex biopolymers via hydro-
gen transfer from alcohol solvents is a highly attractive method,
especially considering that methanol or ethanol can be poten-
tially derived from lignocellulose or other renewable resources
[9]. In 2009, the Ford group described hydrogen transfer from
supercritical methanol for the selective cleavage of the aromatic
ether bond in a simple lignin model compound dihydrobenzofuran
(DHBF) [181]. The catalyst used in the study was a copper doped
porous metal oxide, derived from calcination of a synthetic hydro-
talcite, which was obtained from inexpensive and earth abundant
materials. The role of this multifunctional catalyst was to pro-
mote reforming of the methanol solvent to CO and H2 that thereby
serves as liquid syngas; and to catalyze diverse hydrogenolysis
and hydrogenation processes, the latter consuming the produced
hydrogen equivalents. Hydrogenolysis of DHBF to ethyl-phenol
was observed, together with subsequent aromatic ring hydrogena-
tion to deliver 2-ethyl-cyclohexanol as the main reaction product
(Fig. 5a) [182]. Later, analogously to DHBF, poplar wood organo-
solv lignin was converted to very clean mixtures of substituted
cyclohexanols under similar reaction conditions (300 C, 200 bar,
Fig. 5b). Importantly, lignin was fully depolymerized and markedly
deoxygenated. Another advantage of this system is that water
formed by deoxygenation processes reacts with the CO to provide
more hydrogen equivalents through the water gas shift reaction.
Indeed, gas phase analysis of a reaction mixture conrmed the pres-
ence of mainly hydrogen, carbon-monoxide, carbon dioxide and
methane. A series of reaction steps describing prospective lignin
disassembly have been proposed and supported with numerical
values. These theoretical and 1 H NMR based experimental indexes
helped the rapid and holistic evaluation of the complex product
mixtures obtained. Full depolymerization of the lignin starting
material (3000 g/mol) to monomers was conrmed with gel per-
meation chromatography (GPC) and GCMS analysis. A key nding
after careful gravimetric analysis of the reaction solids was the
absence of char formation. Interestingly, the formation of these
undesired intractable side products could also be prevented when
crude lignocellulose (various wood chips) was fully solubilized in
this UCSB process [9,183]. Here a detailed GC-FID analysis estab-
lished that a mixture of cellulose derived C2-C6 aliphatic alcohols
and lignin derived C9 alcohols were obtained. The supercritical sol-
vent together with the in situ produced hydrogen was uniquely
suited for disconnection of the main lignocellulose components.
Such complete and rapid conversion of lignocellulose via hydro-
gen transfer from supercritical methanol without the formation of
char and the resulting relatively uniform product mixtures were a
surprising discovery.
Interesting is the fate of cellulose under these reaction condi-
tions, which is fully converted to aliphatic alcohols. Hydrogenolysis
processes of polyols over copper based catalysts were previously
known and have been summarized in a detailed review [184]. The
conversion pathways of cellulose in aqueous media were studied in
detail using commercially available methanol reforming catalysts
[185].
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532
Fig. 5. Copper doped porous metal oxides in the catalytic conversion of biomass. (a) Reactivity of the dihydrobenzofuran (DHBF) model compound [182]. (b) Reactivity
of organosolv lignin, cellulose and lignocellulose in supercritical methanol [182,183]. (c) Aromatic products from lignin in high yield at 140160 C. P3 isolated as pure
compound upon column chromatography [186].
Of course, while the advantage of supercritical solvents is appar-
ent in the conversion of wood sawdusts, much milder reaction
conditions can be used with biomass derived platform chemi-
cals or organosolv lignin if controlled hydrogenolysis is desired.
Depolymerization of extracted and fractionated organosolv can-
dlenut lignin to well dened aromatic chemicals in high yield was
carried out at 140180 C with 50 bar H2 (Fig. 5c) [186]. Single
aromatic compounds were isolated by column chromatography
in high yields. Given the Cu20PMO activity in dehydrogenation
of alcohols, this makes a dehydrogenation step, similar to those
reported in Sections 3.2, 3.4 and 5.2, likely prior to cleavage. Mech-
anistic investigation using model compounds in the presence of
similar supported copper based catalysts conrm hydrogenolysis
processes under these conditions [187]. Later, the group of Hensen
used similar Cu-doped porous metal oxides for the conversion of
lignin in supercritical ethanol without added hydrogen to obtain
complex mixture of aromatic compounds. Different catalyst to sub-
strate ratios and lignin were used [188]. Supercritical ethanol in
combination with molybdenum catalysts was used in the depoly-
merization of Kraft lignin [189].
Hydrogen transfer from alcohols over basic copper catalysts
under supercritical or milder conditions is an attractive approach
that was pioneered in the Ford group and the concepts laid out in
these early studies are being further developed by many groups.
An especially interesting concept is the prospect of transferring
hydrogen equivalents from the cellulose fraction of lignocellulose
onto lignin [190]. The copper-doped basic heterogeneous catalysts
are well suited for the conversion of both lignin derived [191]
525
as well as cellulose derived substrates and platform molecules
[192,193]. Main advantages are the absence of pathways observed
under acidic conditions and the low tendency for the formation
of humins. Sintering of copper and catalyst stability especially for
work in aqueous media needs to be addressed [194].
6.2. Hydrogen transfer from isopropanol
In 2013, an elegant dehydroxylation method was reported by
Rinaldi using isopropanol as hydrogen donor [195]. The method
used a combination of Raney Ni and solid acid catalysts to pro-
mote a distinct set of reaction steps, which ultimately lead to
complete deoxygenation of phenol to benzene. The unique advan-
tage of this method is that it allows for highly desired simple
aromatics under low severity conditions and high selectivity. Under
optimized conditions up to 82% benzene yields were obtained start-
ing from phenol as substrate. Simple aryl and alkyl ethers were
very efciently cleaved at 160 C. The method was successfully
extended to realistic substrates such as bio-oils and organosolv
lignin. For organosolv lignin an additional processing step at 240 C
was needed to achieve cleavage of the aromatic ether bonds and
substantial deoxygenation to simpler arenes and alkanes. These
transformations were conrmed by 2D-GC and NMR methods.
7. Conclusions
To provide a general overview of the used methodologies and
types of products obtained mainly from the model compound
526 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532

Table 4
Overview of the products formed and conditions used in studies with lignin model compounds, focused on those described in this work (highlighted entries have been
studied on lignin, see Table 5).

Typea Categoryb Catalyst/reagents Conditions Products Ref.

C2--O-4 models D 15 mol% RuH2 (CO)(PPh3 ) 135 C [162]

15 mol% xantphos 24 h

D 5 mol% Ru(cod)(methallyl)2 135 C [164]

5 mol% bis(2-Diphenyl phoshinoethyl) 2h
Phenyl phosphine
Or 1 mol% preformed complex

D 5 mol% RuH2 (CO)(PPh3 )(xantphos) 135 C [163]

20 h

D 2.5 mol% RuHCl(CO)(PPh3 )3 125 C [173]

50 mol% KOH 1248 h

D 5 mol% RuCl2 (CO)(PPh3 )3 140 C [172]

25 mol% Ktamylate 18 h
25 mol% Ethylacetate

C 20 mol% Fe(acac)3 140 C [127]

1 atm H2 24 h
2.5 eq. NaOtBu

D 5 mol% RuCl2 (CO)(PPh3 )3 140 C [172]

25 mol% Ktamylate 16 h
25 mol% Ethylacetate + addition of 1 eq.
KOH and 1 eq. RCH2 OH after 8 h

C 25 eq. Et3 SiH rt [144]

2 mol% B(C6 F5 )3 2h

C 25 eq. Et3 SiH rt [144]

10 mol% B(C6 F5 )3 16 h

C 10 eq. PDMS 50 C [145]

0.3 mol% B(C6 F5 )3 3h

A 0.2 M H2 SO4 150 C [82]

20 h

A 0.2 M HBr 85 C [84]

6h

B 5 mol% MeReO3 135155 C [107]

10 h

B (1) 1.05 eq. 4-AcNH-TEMPO]BF4 1) rt, [112]

(2) 1 mol% [Ir(ppy)2 (dtbbpy)]PF6 15 h
3 eq. DIPEA, 3 eq. HCO2 H 2) rt
Visible light 16 h

B 2 wt% LCN 80 C [117]

5 eq. TBHP 12 h

p-OH B 5 mol% Co-Schiff-base rt [102]

O2 (50 psi) 16 h

C2--O-4 models C 10 mol% Yb(OTf)3 110 C [149]

No OH functionalities 2 mol% Pd-NPs 22 h
600 psi H2

E H-BEA-35/Raney Ni 0.083 160 C [195]

3 eq. iPrOH 4h
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532 527

Table 4 (Continued)

Typea Categoryb Catalyst/reagents Conditions Products Ref.

D 2 mol% Ir(pincer) 150200 C [159]

0.01 Torr 1240 h

Hydrobenzofuran C 10 mol% Yb(OTf)3 110 C [149]

2 mol% Pd-NPs 22 h
600 psi H2

E Cu20-PMO 320 C [181]

sc-MeOH 13 h

C3--O-4 models D 2.5 mol% RuHCl(CO)(PPh3 )3 125 C [173]

100 mol% KOH 48 h

A 2.5 eq. NaOtBu 100 C [118]

2h

C 3 eq. Et3 SiH rt [144]

2 mol% B(C6 F5 )3 16 h

C 5 eq. TMDS rt [144]

2 mol% B(C6 F5 )3 16 h

C 800 eq. PDMS 50 C [145]

7 mol% B(C6 F5 )3 3h

A 0.2 M H2 SO4 150 C [82]

220 h

A 0.2 M H2 SO4 150 C [82]

220 h

A 0.2 M HBr 85 C [85]

6h

B (1) 5 mol% DDQ 1) 80 C [114]

10 mol% tBuONO 14 h
O2 2) 80 C
(2) Zn/NH4 Cl 15 min

B (1) 1.05 eq. 4-AcNH-TEMPO]BF4 1) rt, [112]

(2) 1 mol% [Ir(ppy)2 (dtbbpy)]PF6 15 h
3 eq. DIPEA, 3 eq. HCO2 H 2) rt
Visible light 16 h

B (1) 5 mol% AcNH-TEMPO 1) 45 C [109]

10 mol% HNO3 , 10 mol% HCl 24 h
1 atm O2 2) 110 C
(2) HCO2 H:H2 1215 h
HCO2 Na

B 5 mol% MeReO3 110 C [107]

4h

B 10 mol% V-Schiff-base 80 C [95,98]

Air 24 h

B CuOTf/TEMPO 100 C [99,100]

2,6-Lutidine 1840 h
O2

p-OH B 5 mol% Co-Schiff-base rt [102]

O2 (50 psi) 1648 h
528 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532

Table 4 (Continued)

Typea Categoryb Catalyst/reagents Conditions Products Ref.

p-OH B 10 mol% V-8-quinolinate 80 C [97]

Air 48 h

-OAc D 5 mol% RuH2 (CO)(PPh3 )(xantphos) 135 C [180]

20 h

C1--O-4 models C 5 mol% Ni(cod)2 80 C [118]

10 mol% NHC1HCl 16 h
2.5 eq. NaOtBu
1 bar H2

C 0.25 mol% [Ni(CH2 TMS)2 (TMEDA)] 120 C [125]

2.5 eq. NaOtBu 48 h
1 bar H2

C 1 eq. Et3 SiH rt [144]

2 mol% B(C6 F5 )3 2h

C 2 eq. PDMS rt [145]

0.6 mol% B(C6 F5 )3 2h

B 2 wt% LCN 80 C [117]

5 eq. TBHP 12 h

4-O-5 models C 20 mol% Ni(cod)2 120 C [118]

40 mol% NHC1HCl 1648 h
2.5 eq. NaOtBu
1 bar H2
C 0.510 mol% [Ni(CH2 TMS)2 (TMEDA)] 120 C [125]
2.5 eq. NaOtBu 4896 h
1 bar H2
C 3 eq. Et3 SiH 75165 C [141]
3 eq. KOtBu 2040 h
C 15 mol% Co(acac)2 140 C [126]
2.5 eq. LiAlH4 24 h
2.5 eq. NaOtBu
C 20 mol% Fe(acac)3 140 C [127]
2.5 eq. LiAlH4 24 h
2.5 eq. NaOtBu

model B 5 wt% CuFeS2 60 C [108]

H2 O2 1h
Acetate buffer pH 4
a
See Fig. 6 for general model compound structures.
b
Categorized as in this review A = Section 2, B = Section 3, C = Section 4, D = Section 5, E = Section 6.

studies and from lignin, we summarized the corresponding refer-
ences in Table 4 for which the corresponding terminology for the
different linkages is shown in Fig. 6.
Additionally, the most recent methodologies that have been also
tried on lignin itself have been summarized in Table 5. Important
here is that monomer yields from different methodologies should
only be compared with caution due to the important inuence of
the lignin source has on these yields. As described in Section 1.4
successful cleavage reactions targeting a specic lignin motif that
provide monomers require that monomer subunit to be anked by
two of these motifs inside the polymeric structure. Because, the
actual recurrence of linkages varies depending on the source and
isolation procedure used results would best compared using the
same lignin source and often even the same batch of lignin. For this
reason several groups have made an effort to calculate theoretical
maximum yields based on the experimentally determined occur-
rence of the linkage targeted [114,133]. This situation of course
completely changes if a methodology effects many of the different
linking motifs in lignin.
From the above summaries it becomes evident, that a large
number of creative solutions have emerged over the past 5 years
alone. The quest for new catalyst structures for lignin depolymer-
ization led to a number of new insights and resulted in many
original solutions. Given the difculty of lignin depolymerization,
these methods have mainly concentrated on enabling bond cleav-
age in aromatic ethers. Consequently, the diversity of products
 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532 529

Table 5
Examples of methodologies developed on model compounds applied on lignin.

Lignin source Catalyst Conditions Results/monomeric products Ref.

Alkali (Aldrich)/pyrolytic (Univ. of BC)/DCM 5 mol% 135 C No effective depolymerization only some effect was [163,180]
soluble (Univ. of BC)/Indulin AT kraft RuH2 (CO)(PPh3 )(xantphos) 20 h found for acetylated kraft
(MeadWestvaco Crop)/Lignol Energy Corp
(Lignol Energy Corp)/acetylated kraft

Hardwood kraft (FPInnovations Lignoforce 800 eq. PDMS 50 C Softwood: 30% solubilization [145]
Technology)/softwood (Weyerhaeuser) 610 wt% B(C6 F5 )3 3h Hardwood: 95% reduction/degradation into lower
molecular weight fragments (38mers)

Organosolv tulip poplar/organosolv switchgrass 10 mol% Co-Schiff-base rt Combined yield up to 3.5 wt% [102,103]
O2 (50 psi) 72 h (Q1:Q2:Q3:Q4 = 1:13:5:10)

Organosolv poplar H-BEA-35/Raney Ni 0.083 160 C 40 wt% oil containing 39:9:2 arens:alkenes:phenols [195]
3 eq. iPrOH 2h
Then 240 C
2h

Organosolv poplar Cu20-PMO 300 C Full conversion to aliphatics without char formation [182]
sc-MeOH 24 h

Organosolv candlenut Cu20-PMO 140180 C [186]

40 bar H2 1420 h

180 C, 14 h; up to 54.8 wt% P14 (36.1 wt% P3 isolated)

140 C, 20 h; up to 63.7 wt% P14 (43.3 wt% P3 isolated)

Organosolv birch (1) 10 wt% DDQ/ 1) 80 C About 43% of theoretical maximum yield of monomers [114]
10 wt% tBuONO 14 h based on -O-4 content
O2 2) 80 C
(2) Zn/NH4 Cl 1h

Cellulolytic enzyme aspen (1) 5 mol% AcNH-TEMPO (1) 65 C [109]

10 mol% HNO3 , 10 mol% HCl 48 h
2 atm O2 (2) 110 C
(2) HCO2 H:H2 (10:1) 24 h
3 eq. HCO2 Na

Organosolv Miscanthus giganteus 10 mol% V-Schiff-base 80 C [98]

air 24 h

Diluted acid corn stover/steam exploded spuce 10 wt% CuFeS2 60 C [108]

H2 O2 5h
Acetate buffer pH 4

Organosolv birch (1) 2 wt% LCN (1) 80 C Low molecular weight products (mw < 400) [117]
5 eq. TBHP 12 h
(2) HCl (H2 O/EtOH) (2) 150 C
5h
530 P.J. Deuss, K. Barta / Coordination Chemistry Reviews 306 (2016) 510532

Fig. 6. Overview of model compounds used in lignin depolymerization studies.

derived from these methodologies is not particularly large. In most References

studies similar model compounds were used, which are gener-
ally split to phenols or substituted phenols, and acetophenone or [1]
propyl-aromatics. When translating these model studies to lignin,
the analogous products of lignin disassembly are propyl-phenolics,
acetophenone derivatives (Table 5). These products would still be
somewhat specialized to be considered for drop-in strategies [196],
and additional processing and deoxygenation or C C bond cleavage
steps are desired. In addition, for most of the presented methods,
compatibility with real lignin feeds has not yet been demonstrated.
Although some of the methods mentioned show much promise,
more research is needed to evaluate different methodologies and
to establish efcient routes, including product separation strategies
to obtain well-dened aromatic chemicals from lignin. Compared [11]
to cellulose, to obtain well dened platform chemicals from lignin [12]
is expected to be much more difcult, naturally due to the inher-
ent complexity of the lignin structure and the variety of different
linkages and sub-units depending on plant type. Comprehensive
studies regarding the understanding of the different types of cleav-
age processes will have a profound impact on valorization of
realistic lignin streams. Besides functional group compatibility, and
robustness of the new catalyst structures, these should be prefer-
ably derived from earth abundant, sustainable materials, since large
amounts of substrate will have to be processed.
The implementation of lignin as a renewable, sustainable source
of aromatic chemicals for the chemical industry is a highly desired
prospect. As evident from this review, incredible research advances
have been made in the past 5 years in many elds, including
homogeneous catalysis. Although, overall, many of the presented
systems are not yet ready for a direct industrial implementation,
these fundamental studies, especially related to efcient cleavage [24]
methodologies, are very important. The new catalysts and insights
developed in these early studies will denitely inspire the catalytic [25]
systems of the future.
Acknowledgements
The authors gratefully acknowledge nancial support from the
European Commission (SuBiCat Initial Training Network, Call FP7-
PEOPLE-2013-ITN, Grant No. 607044).
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