Silicon-Based Reducing Agents

1
Silicon-Based Reducing Agents

Gerald L. Larson
Vice President, Research & Development
Materials for the reduction of:
Aldehydes
Ketones
Acetals
Ketals
Esters
Lactones
Thioesters
Enamines
Imines
Acids
Amides
Halides
Olens
Metal Halides
Supplement to the Gelest Catalog, Silicon, Germanium & Tin Compounds,
Metal Alkoxides and Metal Diketonates which is available on request.
127
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AZmax TEL: 035543-1630 FAX: 03-5543-0312 www.azmax.co.jp (215) 547-1015 FAX: (215) 547-2484 www.gelest.com
Gerald L. Larson
Vice President, Research & Development
2
SILICON-BASED REDUCING AGENTS
Introduction
The widely used organometallic-based reducing agents can be broadly classied as either ionic, such as lithium
aluminum hydride and sodium borohydride, or free-radical such as tri-n-butyltin hydride. The mechanistic differences
between these two classes of reducing agents very often complement one another in their ability to reduce organic substrates.
Organosilanes have been found to possess the ability to serve as both ionic and free-radical reducing agents. These reagents
and their reaction by-products are safer and more easily handled and disposed of than other reagents. Their reductive abilities
are accomplished by changes in the nature of the groups attached to silicon, which can modify the character of the Si-H bond
in the silane. For example, the combination of a triethylsilane and an acid has proven to be excellent for the reduction of
substrates that can generate a stable carbenium ion intermediate. Examples of substrates that fall into this class are olens,
alcohols, esters, lactones, aldehydes, ketones, acetals, ketals, and other like materials. On the other hand triphenylsilane and
especially tris(trimethylsilyl)silane have proven to be free-radical reducing agents that can substitute for tri-n-butyltin hydride.
The reductions with silanes can take place with acid catalysis in which the silane provides the hydride to a carbenium ion
intermediate. This is often the situation in the reduction of carbonyls, ketals, acetals and similar species. Additionally,
the silane reductions can also be carried out with uoride ion catalysis to generate a silane with more hydridic character.
Some of the key reductions possible with silanes are summarized in Table 1.
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General Considerations
Hydridosilanes are readily produced on an industrial scale through the use of Grignard chemistry starting with
trichlorosilane, methyldichlorosilane, and dimethylchlorosilane, among others, as key raw materials. Alternatively, the
Si-X (X = primarily Cl or OR) bond can be reduced to Si-H.
The organosilanes are basically hydrocarbon-like in that they are stable to water, are, in general, ammable and are
lipophilic. In contrast to hydrocarbons, the low molecular weight silanes such as monosilane, methylsilane, and dichlorosilane
are pyrophoric. The silanes will react with base or, more slowly, with acid to give the corresponding siloxane with the evolution
of hydrogen gas. They show a strong, characteristic, carbonyl-like absorption in the infrared at about 2200 cm
-1
.
1
The metallic nature of silicon and its low electronegativity relative to hydrogen - 1.8 versus 2.1 on the Pauling scale
- lead to polarization of the Si-H bond such that the hydrogen is hydridic in nature. This provides an ionic, hydridic reducing
agent that is milder than the usual aluminum-, boron-, and other metal-based hydrides. Thus, triethylsilane, among others,
has been used to provide the hydride in Lewis acid-catalyzed reductions of various carbenium ion precursors. In addition, the
Si-H bond can be employed in various radical reductions wherein the silane provides the hydrogen radical.
Table 2 shows the Si-H bond strengths for several silanes. From these data the rather wide variation in the Si-H bond
strengths from tris(trimethylsilyl)silane on the low-energy end to triuorosilane on the high-energy end can be noted. This
is yet another example of the extraordinary effect that groups attached to silicon can have on the chemistry of the silane and
that these effects can go beyond the simple steric effects that have been so successfully applied with the silicon-based blocking
agents.
2-4
TABLE 2 BOND STRENGTHS OF VARIOUS HYDRIDOSILANES
Compound Product Code Bond Strength Reference
kJ mol
-1
kcal mol
-1
F
3
Si-H SIT8373.0 419 100 5
Et
3
Si-H SIT8330.0 398 95 6
Me
3
Si-H SIT8570.0 398 95 7
H
3
Si-H SIS6950.0 384 92 6
Cl
3
Si-H SIT8155.0 382 91 5
PhMeHSi-H SIP6742.0 382 91 6
Me
3
SiSiMe
2
-H not offered 378 90 6
PhH
2
Si-H SIP6750.0 377 90 6
(MeS)
3
Si-H not offered 366 87 6
H
3
SiSiH
2
-H SID4594.0 361 86 5
(Me
3
Si)
3
Si-H SIT8724.0 351 84 6
Although triethylsilane has been the most popular of the silicon-based reducing agents, in principal any Si-H-
containing system can provide the hydride for many or most of these reductions. Considerations would include availability,
economics, and silicon-containing by-products. The silicon-containing by-products are usually the silanol or disiloxane
in the case of the trisubstituted silanes, or silicones in the case of the di- or monosubstituted silane reducing agents. Such
considerations can result in greater ease of handling and purication of the nal product.
Silicon-based reductions have been reviewed, though never in a comprehensive manner.
6,8-13
A comprehensive review
has been accepted for publication.
14
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4
Silicon-Based Radical Reductions
Griller and Chatgilialoglu
6
realized that the low bond energy of the Si-H bond in tris(trimethylsilyl)silane compared
well with that of the Sn-H bond in tri-n-butyltin hydride (322 kJmol
-1
; 77 kcal mol
-1
), and that this reagent should,
therefore, be a viable alternative for radical reductions and one that would avoid the potential problems of working with toxic
tin materials and trace tin-containing impurities in the nal product. This proved to be the case, and a number of radical
reductions with tris(trimethylsilyl)silane have been reported and reviewed.
15,16
Included among these are the reductions of
organic halides,
17-19
esters,
20
xanthates, selenides, suldes, thioethers, and isonitriles.
21
As an example of a free radical reduction, the diphenylsilane reduction of thioesters to ethers has been recently
reported.
22
This reaction uses the catalytic triphenyltin hydride as the actual reducing agent.
O
S
O
1) Ph
2
SiH
2
Ph
3
SnH cat.
Et
3
B/rt/1h
60% 2) AIBN/85-100 C
Ionic Reductions with Silanes General Considerations
As pointed out above the silanes provide a mild form of the hydride and as such can be useful in various hydridic
reductions. The general and, admittedly simplied, view of such reductions can be visualized as shown below where a
carbenium ion is reduced by a silane. In this scenario, the carbenium ion receives the hydride from the silane, and the silane
takes on the leaving group from the carbon center.
R
3
C-X + R
3
Si-H R
3
C-H + R
3
Si-X
It has been shown that in the gas phase the reaction shown below is exothermic by approximately 8 kcal/mol
indicating that the trimethylsilicenium ion is, at least in the gas phase, more stable than the tert-butyl carbenium ion.
23
Although the existence of free silicenium ions do not exist in solution under normal, unbiased conditions, it can be assumed
that the silicon center is free to take on considerable positive charge in its reactions. Reductions based on this premise include
those of olens, ketones, aldehydes, esters, organic halides, acid chlorides, acetals, ketals, alcohols as well as metal salts.
(CH
3
)
3
C
+
+ (CH
3
)
3
Si-H (CH
3
)
3
C
-
H + (CH
3
)
3
Si
+
Silane Reduction of Alcohols to Alkanes
The general equation for the silane reduction of alcohols to alkanes is illustrated below. The reaction proceeds
best when the alcohol can lead to a stabilized carbenium ion. Thus, secondary and tertiary aliphatic alcohols and benzylic
alcohols are readily reduced. Trialkyl substituted silanes are more reactive than dialkylsilanes and di- or triarylsilanes. Typical
and highly effective conditions for these reductions are treatment of the alcohol with the silane and triuoroacetic acid in
dichloromethane. Triethylsilane is often the silane of choice due to its ease of handling and high reactivity.
23,24
R
3
C-OH + R
3
Si-H
R
3
C
-
H + R
3
Si-OH and/or R
3
Si-O-SiR
3
Acid
catalyst
The reduction of secondary alcohols with a silane and a protic acid does not occur. These reductions require the use of
a strong Lewis acid such as boron triuoride or aluminum chloride.
25,26
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Primary aliphatic alcohols are not reduced with silanes.
27
Benzylic alcohols, on the other hand, are reduced under
rather mild conditions to the corresponding toluene derivative.
28
t
Bu
t
Bu
t
Bu
OH
CH
2
Cl
2
/TFA
t
Bu
t
Bu
t
Bu
Me
R
3
Si-H
The selective reduction of a benzylic alcohol in the presence of benzyl ethers, a tetrahydrofuran and an acetal has
been reported.
29
O
BnO
OBn
OEt
MeO
HO
Et
3
Si-H/TFA
CH
2
Cl
2
/ rt
O
BnO
OBn
OEt
MeO 76%
Primary alcohols can be reduced to the alkane when the reaction is catalyzed by the very strong Lews acid,
tris(pentauorophenyl)borane. The reaction requires two equivalents of the silane as the rst equivalent serves to silylate
the alcohol. It is believed that the silylated alcohol is nucleophilically displaced in these transformations.
30
On the other
hand, with boron triuoride etherate as the catalyst, the benzylic alcohol can be reduced in the presence of a primary or
secondary alcohol.
31,32
E t
3
SiH, B ( C
6
F
5
)
3
CH
2
Cl
2
, rt, 20 h
Ph OH Ph
95%
OH
OH
Ph
Ph
OH Ph
Ph
E t
3
Si H, CH
2
Cl
2
E t
2
O B F
3
, 0
o
, 0. 5 h
90%
O
O
N
OMe
MeO
H
H
OH
HO
Me
E t
3
Si H, CHCl
3
E t
2
OB F
3
O
O
N
OMe
MeO
H
H
HO
Me
92%
The reduction of an allylic alcohol in the presence of a tertiary alcohol is possible.
33
HO
OH
E t
3
Si H, L i Cl O
4
E t
2
O, rt, 16 h
OH
52%
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Silane Reduction of Alkyl Halides
As with the reduction of alcohols to alkanes, the acid-catalyzed reduction of alkyl halides to alkanes requires the
formation of a relatively stable carbenium ion intermediate that can accept the hydride from the silane. Thus, tertiary,
secondary, allylic and benzylic halides lend themselves to this type of reduction. Under certain conditions primary halides can
be reduced, but carbenium ion rearrangements are a problem.
34,35
Br
Et
3
SiD
AlCl
3
D
+
E t
3
Si H, Al Cl
3
HCl
39% 26%
B r
Cl
Et
3
SiH
AlCl
3
H
57%
Trialkylsilanes, being better hydride donors, provide less rearranged product in these reductions than their dialkyl or
monoalkyl counterparts.
35
The reduction of organic halides with pentacoordinate hydridosilanes has been reported.
36
Tertiary alkyl uorides can be reduced to the alkane in excellent yield.
37
-Chloro ethyl ethers are cleanly reduced to
the alkane.
38
An allyl chloride was reduced in the presence of an allylic tosylate.
39
O Ph
F
O
O Ph
O
E t
3
SiH, B F
3
OE t
2
CH
2
Cl
2
, 20
o
, 8 h
100%
O
O
Cl O
O
E t
3
Si H, PdCl
2
rt, 10 min
95%
SO
2
T ol
Cl
SO
2
T ol
Ph
2
Si H
2
, ZnCl
2
, Pd(PPh
3
)
4
T HF, rt, 12 h, 50 , 6 h
58%
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The reduction of -halo ketones and -halo esters has been reported to occur with the combinations of
PhSiH
3
/Mo(CO)
6
,
40
Ph
2
SiH
2
/ZnCl
2
/(PPh
3
)
4
Pd,
40
and Et
3
SiH/PdCl
2
38
with the rst of these proving to be the best.
2-Bromopropiophenone was reduced to propiophenone with polymethylhydrogensiloxane, PMHS, without reduction
of the carbonyl.
41
Br
O
O
PMHS, Pd(PPh
3
)
4
, Bn
3
N
MeCN/Me
2
SO (1:1), 110
o
, 3 h
80%
The tetramethyldisiloxane reduction of an aryl chloride in the presence of a benzophenone moiety was carried out in
high yield.
42
The high-yield reduction of an aryl triate has been reported.
43
O
Cl
HMe
2
Si OSi Me
2
H, 10% Ni /C
PPh
3
, dioxane, refl ux, 15 h
O
96%
N
N
CF
3
CF
3
OT f n-C
10
H
21
N
N
CF
3
CF
3
n-C
10
H
21
E t
3
Si H, Pd( OAc)
2
dppp, DMF, 60 , 3 d
95%
Silane Reduction of Alkynes
The reduction of p-tolylacetylene with triethylsilane gave p-ethyltoluene although in low yield.
44
E t
3
Si H, T FA
rt, 120 h
H
21%
Most of the alkyne reductions have been carried out on suitable enynes, diynes, or bromo acetylene derivatives to
produce cyclic products.
45-47
T B SO
OT MS
PMHS, Pd
2
(bpa)
3
CHCl
3
, (o-tol )
3
P
HOAc, Cl CH
2
CH
2
Cl , rt
T B SO
OT MS
90%
B r
O E t
3
Si H, Pd(PPh
3
)
4
Cs
2
CO
3
, DMF, 80 , 3 h
O
48%
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Silane Reduction of Aromatics
Furans are reduced to tetrahydrofurans with triethylsilane under suitable catalysis.
48
Thiophenes can be
similarly reduced.
49
O O
E t
3
Si H, T FA, F
3
B OE t
2
20
o
, 4 min
70%
S
O
O
E t
3
Si H, T FA, 55 , 15 h
S
OSi E t
3
O
45%
Anthracene was reduced to 9,10-dihydroanthracene in good yield with triethylsilane and boron triuoride hydrate.
50
The partial reduction of other polyaromatics was reported.
50
E t
3
Si H, F
3
B OH
2
CH
2
Cl
2
, 25
o
, 1 h
89%
The pyridine ring of quinoline was reduced in preference to the benzene ring. The isolated product was the
N-silylated derivative. Some of the dihydroreduction product was also observed.
51,52
N
PhMeSi H
2
, Cp
2
T iMe
2
80
o
, 8 h
N
Si PhMeH
N
Si PhMeH
56% 18%
+
Silane Reduction of Ethers
Trityl ethers are readily removed as triphenylmethane with triethylsilane and triethylsilyltriate as the catalyst.
53
B zO O
B zO
O
B zO
OT r
E t
3
Si H, E t
3
Si OT f
CH
2
Cl
2
, rt, 5 mi n
87%
+ Ph
3
CH
O
HO
HO
OT r
OT r
B zO O
B zO
O
B zO
OH
O
HO
HO
OH
OH
Under the inuence of the strong Lewis acid, tris(pentauorophenyl)borane, dialkyl ethers were cleaved in high yield.
54
A tertiarybutylcyclopropenyl ether was reduced to give the cyclopropene.
55
n-C
16
H
33
O
C
16
H
33
-n
E t
3
Si H, B (C
6
F
5
)
3
CH
2
Cl
2
, rt, 20 h
n-C
16
H
34
+ n-C
16
H
33
OSiE t
3
98% 98%
Ph
Ph
Ph
OB u-t
Et
3
SiH, TFA
Ph
Ph
Ph
H 45%
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9
Silane Reduction of Carboxylic Acids
Ethyldimethylsilane and a ruthenium catalyst were used to reduce aliphatic carboxylic acids to the corresponding
alcohol.
56
With tris(pentauorophenyl)borane as catalyst, triethylsilane reduces carboxylic acids to the alkane.
57,58
OH
O
OH
E tMe
2
Si H, catal yst
1, 4-di oxane, 20 , 0. 5 h
72%
R u
R u( CO)
2
(OC)
2
R u
O ( CO)
2
CO
2
H
E t
3
Si H, B (C
6
F
5
)
3
CH
2
Cl
2
, rt, 20 h
94%
Silane Reduction of Esters and Lactones
The reduction of esters and lactones has proven to be possible with the isolation of the corresponding alcohol, ether,
hemiacetal, or monosilyl acetal. Thus, an ester was reduced to the alcohol in good yield in the presence of an epoxide.
59
A
methyl ester was selectively reduced to the alcohol in the presence of a tert-butyl ester.
60
A butyrolactone was reduced to the
tetrahydrofuran,
56
as well as to a hemiacetal.
56,61,62
O
H
OE t
O
O
H
OH
PMHS, Cp
2
T i Cl
2
, n-B uL i
T HF, rt, 1 h
91%
MeO OB u-t
O O
HO OB u-t
O
87%
PMHS, Cp
2
T iCl
2
, n-B uL i
T HF, 78
o
, 1 h
O
O O
O
B nO
O
O O
OH
B nO
PMHS, Cp
2
T i (OC
6
H
4
-Cl -p)
2
T B AF/Al umi na, MeC
6
H
5
, rt
91%
Both an intermolecular
63
and an intramolecular version of the conversion of an ester to a silyl acetal have
been reported.
64,65
OMe
O
OMe
OSi E t
3
E t
3
Si H, E tI , E t
2
NH, [R uCl
2
(CO)
3
]
2
MeC
6
H
5
, 100 , 16 h
92%
SiMes
2
H
T B A F, 0
O
Mes
2
Si
OE t
dr = 98: 2
O
O
O
O
E t
E t
E t
E t
CO
2
E t
91%
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The reduction of ,-unsaturated esters can occur with 1,4-adddition to provide the silyl ketene acetal or the
-silyl ester.
66
The intermediate silyl ketene acetal can be trapped with a suitable electrophile either in an intermolecular
or intramolecular fashion.
67,68
OE t
O
OE t
OSi E t
3
E t
3
Si H, Cl R h(PPh
3
)
3
C
6
H
6
, 80 , 2 h
74%
+
OE t
OSi E t
3
6%
OE t
O
OE t
O
OE t
OSi E t
3
E t
3
Si E t
3
Si
+
E t
3
Si H, Cl R h(PPh
3
)
3
C
6
H
6
, 70 , 3 h
52% 28%
O
O
O
+
Me
3
Si H, R hCl
3
3H
2
O, 25
O
O Me
3
Si O
34%
E t
3
Si H, R hH(PPh
3
)
4
MePh, 50 , 16 h
H
O
CO
2
Pr-i
OSi E t
3
CO
2
Pr-i
OSi E t
3
CO
2
Pr-i
+
20% 40%
Silane Reduction of Aldehydes
The acid-catalyzed reduction of aldehydes with silanes works best in the presence of water.
69
In addition esters can be
formed when an organic acid is the catalyst employed.
70
H
O Et
3
SiH
TFA
O OH O
2
CCF
3
+ +
n
C
7
H
15
CHO
Et
3
SiH
(n-C
7
H
15
)
2
O + n-C
7
H
15
-OH
66% 34%
F
3
BOEt
2
PhCHO
Et
3
SiH
TFA
Et
3
SiH
H
2
O/H
2
SO
4
PhCH
2
-O-CH
2
Ph
PhCH
2
OH
80%
98%
sulfolane
An excellent alternative for the reduction of aldehydes to alcohols is through the use of triethylsilane with
uncomplexed boron triuoride in dichloromethane.
71
This method gives the corresponding alcohol in high yield and
very short reaction times.
An extremely high-yield reductive conversion of aldehydes to unsymmetrical ethers involves the reaction of the
aldehyde with a trimethylsilyl ether in the presence of a silane and a strong Lewis acid, with trimethylsilyl triate being
especially efcient.
72
Such silicon-based reductive-condensation chemistry should be applicable to combinatorial chemistry
where product isolation is a crucial issue.
n-C
4
H
9
CHO + n-C
6
H
13
OSiMe
3
Et
3
SiH/Me
3
SiI
CH
2
Cl
2
/0 C/2h
n-C
5
H
11
-O-C
6
H
13
-n
100%
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Aromatic aldehydes can be fully reduced to the corresponding toluene derivative.
71,73
OCH
3
CHO
Et
3
SiH/BF
3
CH
2
Cl
2
/0 C/10 min
OCH
3
CH
3
OCH
3
CHO
Et
3
SiH/TFA
rt/45 min
83% 100%
The conversion of aromatic aldehydes to benzylic halides has also been shown.
74-76
The best reducing agent for this
seems to be tetramethyldisiloxane.
Cl
CHO
Cl
CH
2
I
(HMe
2
Si)
2
O/Me
3
SiCl
NaI/CH
3
CN/0 C/5 min
95%
Under catalysis by uoride ion aldehydes are reduced to the corresponding silyl ether of the alcohol. Hydrolysis of
the silyl ethers provides the unprotected alcohols. Cesium uoride has been shown to be an excellent promoter for these
conversions,
77,78
as have tetra-n-butyl ammonium uoride (TBAF) and tris(diethylamino)sulfonium diuorotrimethylsilicate
(TASF).
79
This can also be used as a route to trimethylsilyl-protected alcohols from aldehydes.
2 n-C
6
H
12
CHO
Ph
2
SiH
2
CsF
(n-C
7
H
15
O)
2
SiPh
2
The reduction of aldehydes to alcohols has also been carried out with polylmethylhydrogensiloxane (PMHS) as the
hydride source. In this case, the work-up includes reaction with methanol to release the free alcohol.
80
The selective reduction of aldehydes over ketones can be realized with polymethylhydrogensiloxane as the reducing
agent with uoride ion-catalysis.
81
Ph
H
O
Ph
n
Bu
O
+
PMHS
TBAF
Ph
Ph
n
Bu
OH
+
OH 87%
< 8%
The reductive amidation of aldehydes proved possible via the acid-catalyzed triethylsilane reduction in the presence of
a nitrile or a primary amide.
82,83
PhCHO + CH
3
CN PhCH
2
NHCOMe
aq. H
2
SO
4
E t
3
Si H
80%
HO
2
C
CHO
HO
2
C
N
H
Ph
O
E t
3
Si H, T FA, PhCONH
2
MeC
6
H
5
, 120
o
, 18 h
96%
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The reduction of ,-unsaturated aldehydes can occur in a 1,2- or 1,4-fashion.
84
CHO
OH
Ph
2
Si H
2
, (Ph
3
P)
3
R hCl
0
o
, 1 h
97%
CHO CHO
E t
3
Si H, (Ph
3
P)
3
R hCl
rt, 1 h
97%
Silane Reduction of Ketones
Silanes have been used for the reduction of ketones to alcohols with excellent results.
85
The reduction of ketones or
aldehydes in the presence of acetonitrile and an acid provides an alkyl acetamide.
82
The comparable reduction of aldehydes to
alkyl acetamides is also possible.
82
O
HO
H
H
Et
3
SiH
TFA
HO
H
H
OH
: ratio = 1:4
O
Et
3
SiH/CH
3
CN
75% aq. H
2
SO
4
/rt/65h
NHCOMe
In a similar manner, the reduction of ketones and aldehydes to esters has been reported.
82
This reaction is always
accompanied with the formation of the symmetrical ether.
O
Et
3
SiH/TFA
rt/1.5h
H O
2
CCF
3
+ O
2
75% 25%
Et
3
SiH/HCOOH
rt/8h
CHO
O
2
CH O
+
The reduction of aryl ketones (acetophenone derivatives) to the methylene is readily accomplished.
86
Triethylsilane
with titanium tetrachloride works best for this transformation, though other systems also work well.
Ar R
O
Acid
Ar R
R
3
SiH
138
Gelest, Inc.
13
The selective reduction of aryl ketones to alcohols over dialkyl ketones can be carried out with phenyldimethylsilane
in the presence of cuprous chloride or cuprous acetate.
87
Cyclic ethers can be formed in the reduction of diketones or hydroxyketones.
88-90
Epoxy ketones can lead to
ethers as well.
91
O O
1. Me
3
Si H, T MSOT f, CH
2
Cl
2
0 , 4 h then rt, 2 h
2. H
2
O
O
HO
O
O
Me
3
Si H, T MSOT f
CH
2
Cl
2
, 0 , 4 h, then rt, 2 h
O O
+
42% 42%
S
O OH O
: O
S
O
:
E t
3
Si H, T MSOT f
CH
2
Cl
2
, 0 , 15 min
97%
O
O
Ph
3
Si H, catal yst, CH
2
Cl
2
78 , 6 h; 0 , 12 h
O
H H
OH
81%
The reductive halogenation of ketones has been shown. Thus, acetophenone derivatives are converted to benzylic
halides.
92,93
An ynone was converted to the propargyl chloride in good yield.
92
Cl
B r
Cl
Cl
B r
O
Me
2
Cl Si H, I n(OH)
3
CHCl
3
, rt, 4 h
99%
O I
T MDS, I
2
, CH
2
Cl
2
5
o
, 5 mi n
76%
O
Cl
Me
2
Cl Si H, I n(OH)
3
CHCl
3
, 0
o
, 0. 3 h
78%
The reduction of aliphatic ketones to the methylene is best accomplished with the
tris(pentauorophenyl)borane catalyst.
94
O
PMHS, B (C
6
F
5
)
3
, CH
2
Cl
2
rt, 5 - 20 mi n
90%
139
Gelest, Inc.
14
Dimethyl(diethylamino)silane served as the reducing agent and the amine source in the reductive amination
of acetophenone.
95
O
NE t
2
E t
2
NSi HMe
2
, T i Cl
4
CH
2
Cl
2
, 0
o
to rt, 36 h
65%
The reduction of ,-unsaturated ketones can occur in a 1,2- or 1,4-fashion.
84
O
O OH
+
E t
2
Si H
2
, ( Ph
3
)
3
R hCl
0 , 30 mi n
3% 97%
O O OH
+
E t
3
Si H, (Ph
3
)
3
R hCl
80 , 25 h
90% 6%
Some selectivity was seen in the reduction of an enone in the presence of a ketal
96
and an acid, allyl alcohol,
and halide.
97
Ph
2
Si H
2
, ZnCl
2
Pd( PPh
3
)
4
, rt, 1 h
O
O
O
O
O
O 95%
O
Cl CF
3
HO
HO
2
C
O
Cl CF
3
HO
HO
2
C E t
3
Si H, T FA, 0
o
, 1 h
rt, 48 h
82%
Silane Reduction of Other Carbonyl Systems
The reduction of amides to the amine has been shown to occur in high yields employing triethylsilane
or diphenylsilane.
98,99
N
O
N
E t
3
Si H, R e(CO)
10
, E t
2
NH
MeC
6
H
5
, 100
96%
The one-pot reduction of amides to aldehydes with diphenylsilane has been reported.
99
This provides a potentially
highly-useful, non-oxidative entry into aldehydes.
NC
NPr-i
2
O
10
NC
H
O
10
Ph
2
Si H
2
, T i(OPr-i )
4
, 20
80%
NMe
2
O
TBSO
Ph
2
SiH
2
(1.1 eq)
Ti(OPr-i)
4
(1 eq)
87%
H
O
TBSO
140
Gelest, Inc.
15
The reduction of acids and esters to alcohols with polymethylhydrogensiloxane occurs in good yields in the presence
of titanium tetraisopropoxide
100
or tetrabutylammonium uoride.
101
The reduction of esters has also been carried out with
diphenylsilane and rhodium catalysis.
102
OEt
O
OBn
PMHS
Ti(O
i
Pr)
4
/THF
OH
OBn
89%
OMe
O
8
OH
8
PMHS
TBAF
95%
The triethoxysilane reduction of esters to alcohols in high yields is possible.
103
This transformation also takes place
with PMHS as the reducing agent.
104,105
COOEt
(EtO)
3
SiH/Ti(O
i
Pr)
4
40 - 50 C
OH
The conversion of lactones to lactols was accomplished via a titanium-catalyzed reduction with PMHS.
106
O
O
Cp
2
Ti(OC
6
H
4
Cl)
2
TBAF/Al
2
O
3
PMHS/toluene
O
OH
94%
The reduction of imines to amines with trichlorosilane and dichlorosilane was reported. Dichlorosilane gave
the best results.
107
S
OMe
N
S
OMe
H
N
Silane
Cl
2
SiH
2
Cl
3
SiH
90%
61%
F
3
BOEt
2
The reduction of oximes to alkoxyamines is accomplished with phenyldimethylsilane and triuoroacetic acid.
108
N
R
2
R
1
OR
3
PhMe
2
SiH
TFA
NH
R
2
R
1
OR
3
141
Gelest, Inc.
16
Silane Reduction of Acetals, Ketals and Aminals
The silane reduction of acetals and ketals occurs readily in the presence of a variety of silanes and acid catalysts. Both
arylalkyl and dialkyl ketals can be reduced to the methylene group.
107
Ph
O O
1. E t
3
Si H, SnB r
2
-A cB r,
CH
2
Cl
2
, rt, 24 h
2. n-B u
3
SnH, A I B N,
C
6
H
6
, refl ux, 0. 5 h
Ph
77%
MeO OMe
Ph
Ph
1. E t
3
Si H, SnB r
2
-A cB r,
CH
2
Cl
2
, rt, 24 h
2. n-B u
3
SnH, A I B N,
C
6
H
6
, reflux, 0. 5 h
67%
The reduction of the acetal of benzaldehyde was carried out in good yield in the presence of an alkyl azide.
109
The
reduction of a peroxymethyl ketal occurred to give triethylmethoxysilane and keep the peroxide group as well as a primary alkyl
iodide.
110
In another similar example the peroxide functionality was lost.
110
N
3
O
O
Ph
H
PMHS, Al Cl
3
, E t
2
O, CH
2
Cl
2
rt, 12 h
69%
7
N
3
B nO
HO
7
O
O
MeO
O
O
H
E t
3
Si H, HOT f
I I
H H
56%
O
O
O
E t
3
SiH, HOT f
O
51%
Aminals and hemiaminals are reduced to amines.
111
N-Trimethylsilyloxymethylimines can be reduced to the
corresponding imine.
112
Related reactions are also possible.
113,114
N
N
HO Me
CO
2
Me
E t
3
Si H, T FA
rt, 4 h
N
N
H Me
CO
2
Me
79%
MeO
N
H
OH
O
E t
3
Si H, T FA
CHCl
3
, rt, 1- 4 h
MeO
NHMe
O
91%
O
N
MeO
2
C
OH
E t
3
Si H, T FA
CHCl
3
, rt, 20 h
O
N
MeO
2
C
Me
63%
O
N
O Fmoc
N
Me
O Fmoc
OH
E t
3
SiH, T FA
CHCl
3
, rt, 22 h
98%
142
Gelest, Inc.
17
Silane Reduction of Enamines and Enamides
The organosilane reduction of enamines has been reported.
116
The reduction of enamides can be carried out selectively
in the presence of enones.
117,118
N
H
MeO
MeO
E t
3
Si H, T FA
50 , 64 h
N
NPh
H
N
O
N
H
MeO
MeO
N
NPh
H
N
O
58%
N
CO
2
Me
Cl
O
E t
3
SiH, T FA , CH
2
Cl
2
0 , 6 h then rt, 6 h
N
CO
2
Me
Cl
O
56%
N
O
O
O
E t
3
Si H, T FA, CHCl
3
20 , 24 h
N
O
O
O
75%
Silane Reduction of Olens
Not surprisingly the ionic reduction of suitable olens, i.e. those which can generate a relatively stable carbenium ion,
can be carried out by silanes in the presence of an acid catalyst. The ability to generate the carbenium ion is essential to the
success of the reaction. For example, 1-methylcyclohexene is readily reduced to methylcyclohexane whereas cyclohexene itself
is not reduced under the same and even more forcing conditions.
118
The most common set of conditions for these reductions
is an excess of triuoroacetic acid, a strong acid with a conjugate base of low nucleophilicity, and triethylsilane.
119-123
Likewise,
terminal olens that are not styrenic in nature and 1,2-disubstituted olens are not reduced with silanes, again, due to the
inability to form a suitable carbenium ion intermediate. On the other hand, the reduction of enol ethers and similar olens
which can form good carbenium ions is possible.
122,124
+
2 Et
3
SiH/TFA
+
70% 100%
The reduction of ,-unsaturated carbonyls to their saturated counterparts is conveniently carried out with silanes in
the presence of a rhodium or copper catalyst.
125,126
O
n
C
12
H
25
O
PhMe
2
SiH
CuCl/DMI
O
n
C
12
H
25
O
95%
O
conditions
[Ph
3
PCuH]
6
5 mol %
O
Bu
3
SnH; 40 min 80%
PhSiH
3
; 8 min 86%
143
Gelest, Inc.
18
Ojima and Kogure
84
have shown that the reduction of ,-unsaturated ketones or aldehydes with triethylsilane or
ethyldimethylsilane gives 1,4-addition resulting in reduction of the double bond whereas diphenylsilane gives 1,2-addition
and straight reduction of the carbonyl.
O
silane
(Ph
3
P)
3
RhCl
OH
+
O
EtMe
2
SiH
Ph
2
SiH
2
2%
99%
98%
1%
An example of the reduction of a styrenic double bond in the presence of another double bond and a ketone is
shown below.
127
The double bond of an ,-unsaturated ketone was reduced with the triethylsilane/acid combination,
though regeneration of the ketones was necessary.
128
O
H
Et
3
SiH
TFA/CH
2
Cl
2
O
H
H
1) Et
3
SiH
TFA/CH
2
Cl
2
O
O
H
O
O
2) NaOH/H
2
O
3) [O]
The reduction of a trisubstituted olen in the presence of an ester was shown.
129
O
2
CCH
3 O
2
CCH
3
Et
3
SiH/TFA
i
PrNO
2
/LiClO
4
90%
The silane reduction of acetylenes to alkanes is not a practical approach to this transformation.
130
The reduction of
vinylcyclopropane gave ethylcyclopropane in quantitative yield.
131
Vinyl ethers are reduced to the corresponding alkyl ether.
132
E t
3
Si H
T FA, 25
o
100%
E t
3
Si H
T FA
O O
80%
144
Gelest, Inc.
19
Stereoselective Silane-Based Reductions
Doyle and West
133
demonstrated that the acid-catalyzed reduction of alkyl-substituted cyclohexanones with di-tert-
butylsilane, di-tert-butylmethylsilane and tri-tert-butylsilane proceeds with predominant formation of the less stable isomer as
the triuoroacetate. For example, 4-tert-butylcyclohexanone gives 67% of the cis-4-tert-butylcyclohexyl triuoroacetate.
O
t
Bu
2
MeSiH/CF
3
CO
2
H
O
2
CCF
3
O
Et
3
SiH OSiEt
3
CF
3
CO
2
H
The reduction of 4-tert-butylcyclohexanone with triethylsilane or dimethylphenylsilane preferentially gives the trans
product. Very high trans to cis stereoselectivity of this transformation with triethoxysilane and TBAF was reported as was the
reduction of 3-phenyl-2-butanone to anti 3-phenyl-2-butanol.
134
The stereoselective silane reduction of -hydroxy ketones with diisopropylchlorosilane has been demonstrated.
135-137
OH O
i
Pr
2
ClSiH
Et
3
N
O O
Si-H
i
Pr
i
Pr
1) SnCl
4
2) HF/H
2
O
OH OH
67% de >98%
The highly diastereoselective reduction of oximes has been reported.
108
The diastereoselectivity was much higher than
that reported for the corresponding reduction with lithium aluminum hydride in diethyl ether.
Ph
OAc
N
BnO
PhMe
2
SiH
TFA
Ph
OAc
NH
BnO
Ph
OAc
NH
BnO
+
73%
99
1
Ph
OAc
N
PhMe
2
SiH
TFA
Ph
OAc
NH
BnO
Ph
OAc
NH
BnO
+
77%
% %
OBn
82 18
The Lewis acid-catalyzed triphenylsilane reduction of hemiketals was shown to occur with high stereoselectivity.
140
O
Ph
S
S
Ph
OH
PhMe
2
SiH/TiCl
4
O
Ph
S
S
Ph
H
cis:trans = 82:1
CH
2
Cl
2
/5 min
145
Gelest, Inc.
20
Asymmetric silane reductions
A very efcient asymmetric reduction of arylalkyl ketones has been shown. The reaction, which does not work well
for prochiral dialkyl ketones, is carried out with PMHS in the presence of a chiral titanium catalyst.
138
O
"Ti"/C
6
H
6
PMHS
OH
73% yield; 73% ee
A number of asymmetric, silane-based reductions have been reported. In many cases these result in very high
enantioselectivity and offer an alternative to the asymmetric hydrogenation protocol. Enones have been reduced in a
1,2-fashion, as well as in a 1,4-manner, with high ee values.
141,142
1. PhSiH
3
, (EBTHI)Ti, MeOH,
60, pyrrolidine, MeOH, THF
2. PMHS, ketone, MeOH, 15, 4 h
O OH
90%; 84% ee
O
Ph
O
Ph
PMHS, Ph
3
PCuH, DTBM-SEGPHOS
MeC
6
H
5
, 35, 16 h
95%; 99.5% ee
The intermediate enol silyl ether from the reduction of an enone can be trapped with benzyl bromide.
143
O
O
Bn
Ph
2
SiH
2
, CuCl, NaOBu-t
(S)-p-Tol-BINAP, MeC
6
H
5
, 0, 2 - 3 h
Ph
Ph
OSiPh
2
H
Ph
95% ee
BnBr, TBAT
CH
2
Cl
2
/MeC
6
H
5
, rt
69%; dr = 94:6
146
Gelest, Inc.
21
The DTBM-SEGPHOS-catalyzed PMHS reduction of ,-unsaturated esters provides the saturated ester in high
enantiomeric excess.
144
OEt
Ph
O
OEt
Ph
O
H
PMHS, (Ph
3
P)CuH
t-BuOH, MeC
6
H
5
, 0
92%; 98% ee
O
O
Ph
O
O
H
Ph
PMHS, (Ph
3
P)CuH
t-BuOH, MeC
6
H
5
, 0
96%; 99% ee
Buchwald and coworkers
139
have reported the reduction of imines in very high enantiomeric excess through the use
of a titanium catalyst activated with phenylsilane and the reduction with polymethylhydrogen siloxane or phenylsilane. The
asymmetric reduction of imines has been reported in very high enantiomeric excesses.
139,145-147
N
Activated Ti cat.
PMHS or PhSiH
3
slow addition of 3 amine
HN
95% 98% ee
N
PhSiH
3
, catalyst
i -BuNH
2
, 65, 2.5 h
Cl
OMe
HN
Cl
OMe
E : Z = 15:1 92%, 99% ee
Reductions With Other Group 14 Hydrides
The tri-n-butyltin hydride reductions are well-known and have been reviewed.
148
A recent report shows that tri-n-
butyltin hydride can provide the hydrogen for the reductive amination of ketones and aldehydes, thus providing an alternative
to sodium cyanoborohydride for this transformation.
149
This same transformation was reported using polymethylhydrogen
siloxane, PMHS, as the reducing agent.
150
R
1
R
2
O
+ R
2
NH
2
+
ClO
4
-
Bu
3
SnH
DMF
R
1
R
2
NR
2
Triphenylgermane has been shown to reduce acid chlorides to aldehydes with palladium(0) catalysis.
151
R Cl
O
Ph
3
GeH
Pd(PPh
3
)
4
HMPA/80-100 C
R H
O
Tri-n-butylgermane has been employed in the reductive alkylation of active olens, in particular acrylonitrile.
152
CN
+ R-I
Bu
3
GeH
AIBN/80 C/8h
R
CN
+ R-H
54 - 79 % 3 - 14 %
147
Gelest, Inc.
22
TRI-SUBSTITUTED SILANE REDUCING AGENTS
TABLE 3
REDUCING AGENT STRUCTURE COMMENTS
SIT8330.0
TRIETHYLSILANE
[617-86-7]
TSCA
Si C
2
H
5
H
C
2
H
5
C
2
H
5
Used to reduce metal salts.
153
Enhances deprotection of
t-butoxycarbonyl-protected amines and tert-butylesters.
154
Used in the reductive amidation of oxazolidinones with
amino acids to provide dipeptides.
155
Converts aldehydes
to symmetrical and unsymmetrical ethers.
156
Used in the
in-situ preparation of diborane and haloboranes.
157
SIT8570.0
TRIMETHYLSILANE
[993-07-7]
TSCA
Si H
CH
3
CH
3
CH
3
Potential reducing agent that will produce low boiling
hexamethyldisiloxane by-product.
SIT8385.0
TRIISOPROPYLSILANE
[6485-79-6]
Si
CH
H
3
C CH
3
HC
H
3
C
H
3
C
CH
H
3
C CH
3
H
Very sterically-hindered silane. Used as a cation
scavenger in the deprotection of peptides.
158
SIT8665.0
TRIPHENYLSILANE
[789-25-3]
TSCA
Si H
More effective radical-based reagent for reduction of
organic halides than the trialkylsilanes.
156
Compares
well with tri-n-butyltin hydride in reduction of enones to
ketones.
63
Shows good selectivity in the reduction of cyclic
hemiacetals.
77
Converts O-acetyl furanoses and pyranoses
to deoxy sugars.
159
SIT8709.0
TRI-n-PROPYLSILANE
[998-29-8]
TSCA
Si
CH
2
CH
2
CH
3
CH
2
CH
2
CH
3
H CH
2
CH
2
CH
3
Reactivity similar to that of triethylsilane.
SIT8376.0
TRI-n-HEXYLSILANE
[2929-52-4]
TSCA
Si CH
3
(CH
2
)
5
H
(CH
2
)
5
CH
3
(CH
2
)
5
CH
3
Reactivity similar to that of triethylsilane but has higher
boiling point and produces a higher boiling by-product.
SIT8185.0
TRIETHOXYSILANE
[998-30-1] Si
OC
2
H
5
H
OC
2
H
5
OC
2
H
5
Reduces esters in the presence of zinc hydride catalyst.
52
Reduces aldehydes and ketones to alcohols via the silyl
ethers in presence of fluoride ion.
160
Gives 1,2-reduction of
enones to allyl alcohols.
161
SIT8721.0
TRIS(TRIMETHYLSILOXY)SILANE
[1873-89-8]
Si H
O
Si(CH
3
)
3
O Si(CH
3
)
3
O
Si(CH
3
)
3
Gives highly stereoselective reduction of substituted
cyclohexanones.
51
148
Gelest, Inc.
23
SIT8724.0
TRIS(TRIMETHYLSILYL)SILANE
[1873-77-4] Si
Si(CH
3
)
3
Si(CH
3
)
3
Si(CH
3
)
3
H
Undergoes exothermic decomposition at >100 C.
Radical-based reducing agent for organic halides,
selenides, xanthates and isocyanides and ketones in high
yields.
20
Can provide complementary stereoselectivity to tri-
n-butyltin hydride in the reduction of gem dihalides.
162
Mild
reducing agent in nucleoside chemistry.
163
SID3258.0
DI-tert-BUTYLMETHYLSILANE
[56310-20-4]
H
3
C
C
CH
3
H
3
C
Si
C
H
3
C
CH
3
H
3
C
H
CH
3
Used in reductive trifluoroacetolysis of ketones. Reacts
faster than di-tert-butylsilane.
72
SID3410.0
DIETHYLMETHYLSILANE
[760-32-7]
TSCA
CH
3
CH
2
Si
H
CH
3
CH
3
CH
2
Similar to triethylsilane with lower boiling point.
SID3535.0
DIISOPROPYLCHLOROSILANE
[2227-29-4]
TSCA
Si
CH
CH
H
3
C
CH
3
CH
3
H
3
C
Cl H
Used in a silylation-reduction-allylation sequence of
-hydroxy esters to homoallylic-substituted 1,3-diols.
164
Used in the silylation-hydrosilation-oxidation of allyl
alcohols to 1,3-diols.
165
Reaction carried out in
diastereoselective manner. Reduces -hydroxy ketones to
anti-1,3 diols.
166
SID4070.0
DIMETHYLCHLOROSILANE
[1066-35-9]
TSCA
Si H
CH
3
CH
3
Cl
Will form high-boiling polymeric by-products with aqueous
work-up.
SID4125.0
DIMETHYLETHOXYSILANE
[14857-34-2]
TSCA
Si H
CH
3
CH
3
OC
2
H
5
work-up.
SID4555.0
DIPHENYLMETHYLSILANE
[776-76-1]
TSCA
Si
CH
3
H
Used to reduce -alkoxy ketones to diols and -amino
ketones to aminoethanols with high stereoselectivity.
167
SIE4894.0
ETHYLDIMETHYLSILANE
[758-21-4]
TSCA
Si
CH
3
CH
2
CH
3
CH
3
H
Similar to triethylsilane with lower boiling point.
SIE4890.0
ETHYLDICHLOROSILANE
[1789-58-8]
TSCA
Si
CH
3
CH
2
Cl
Cl H
work-up.
149
Gelest, Inc.
24
Si
H
3
C
H
Cl
Cl
Si
H
3
C
H
OC
2
H
5
OC
2
H
5
CH
3
(CH
2
)
16
CH
2
Si
CH
3
CH
3
H
Si
CH
3
CH
3
H
Si
CH
3
H
Cl
SiCH
2
CH
2
Si H
CH
3
CH
3
H
CH
3
CH
3
Si
Cl
H
Cl
Cl
150
Gelest, Inc.
25
DIALKYLSILYL REDUCING AGENTS
TABLE 4
SID4230.0
DIMETHYLSILANE
[1111-74-6]
TSCA
Si H
CH
3
CH
3
H
Very low boiling point silane that is a gas at atmospheric
conditions.
SID3342.0
DI-tert-BUTYLSILANE
[30736-07-3]
H
3
C
C
CH
3
H
3
C
Si
C
H
3
C
CH
3
H
3
C
H
H
Sterically-hindered silane reducing agent.
SID3368.0
DICHLOROSILANE
[4109-96-0]
TSCA
H
Si
H
Cl
Cl
Gives improved yields in reduction of imines over that of
trichlorosilane.
56
SID3368.2
DICHLOROSILANE, 25%
in xylene
[4109-96-0]
TSCA
H
Si
H
Cl
Cl
Easier to handle form of dichlorosilane.
SID3415.0
DIETHYLSILANE
[542-91-6]
TSCA
CH
3
CH
2
Si
H
H CH
3
CH
2
Used in the in-situ preparation of diborane and haloboranes.
157
SID4559.0
DIPHENYLSILANE
[775-12-2]
TSCA
Si
H
H
Used in the preparation of silyl-substituted alkylidene
complexes of tantalum.
177
Used in the ionic reduction of
enones to saturated ketones.
178
Used in the reductive
cyclization of unsaturated ketones.
179,180
Reduces esters
in the presence of zinc hydride catalyst.
53
Reduces -halo
ketones in presence of Mo(0).
181
Reduces thio esters to
ethers.
22
Reduces esters to alcohols with Rh catalysis.
49
Employed in the asymmetric reduction of methyl ketones
114
and other ketones.
182,183
Reductively cleaves allyl acetates.
184
SIP6742.0
PHENYLMETHYLSILANE
[766-08-5]
TSCA
Si
CH
3
H
H
Used in the preparation of silyl-substituted alkylidene complexes
of tantalum.
177
151
Gelest, Inc.
MONO-SUBSTITUTED SILANE REDUCING AGENTS
TABLE 5
SIH6166.2
n-HEXYLSILANE
[1072-14-6]
TSCA
SIO6635.0
n-OCTADECYLSILANE
[18623-11-5]
TSCA
SIO6712.5
n-OCTYLSILANE
[871-92-1]
TSCA
SIP6750.0
PHENYLSILANE
[694-53-1]
TSCA
Employed in the reduction of esters to ethers.
185
Reduces ,-unsaturated ketones to saturated ketones in
the presence of tri-n-butyltin hydride.
186
Reduces tin amides
to tin hydrides.
187
Used in the tin-catalyzed reduction of
nitroalkanes to alkanes.
188
Reduces -halo ketones in
presence of Mo(0).
181
SILOXANE-BASED SILANE REDUCING AGENTS
TABLE 6
SIO6696.5
OCTAKIS(DIMETHYLSIL-
OXY)-T8-SILSESQUIOXANE
[125756-69-6]
Solid siloxane reducing agent. Offers 8 Si-H bonds.
Potential for easy removal of silicon by-products.
SIH6117.0
1,1,3,3,5,5-HEXAMETHYL-
TRISILOXANE
[1189-93-1]
TSCA
High molecular weight silane reducing agent.
SIP6718.0
PENTAMETHYLCYCLO-
PENTASILOXANE, 90%
[6166-86-5]
TSCA
SIH5844.0
HEPTAMETHYLTRISIL-
OXANE
[2895-07-0]
152
Gelest, Inc.
SIP6736.5
PHENYLHYDROCYCLOSIL-
OXANES, contains linears.
High-boiling siloxane reducing agent.
SIP6826.0
PHENYLTRIS(DIMETHYL
SILOXY)SILANE, 95%
[18027-45-7]
TSCA
SIT7274.0
1,1,3,3-TETRAISOPROPYL-
DISILOXANE
[18043-71-5]
Sterically-hindered silane reducing agent with potential for
diastereoselective reductions.
SIT7278.0
TETRAKIS(DIMETHYL-
SILOXY)SILANE
[17082-47-2]
TSCA
SIT7530.0
1,3,5,7-TETRAMETHYL-
CYCLO-TETRASILOXANE
[2370-88-9]
TSCA
SIT7546.0
1,1,3,3-TETRAMETHYL-
DISILOXANE
[30110-74-8]
TSCA
Reduces aromatic aldehydes to benzyl halides.
38
Used in
the reductive halogenation of aldehydes and epoxides.
189
SIT8721.0
TRIS(TRIMETHYLSILOXY)-
SILANE
[1873-89-8]
METHYLHYDROSILOXANE-
DIMETHYLSILOXANE CO-
POLYMERS
HMS-013 through HMS-501
having various MWs, vis-
cosities, and hydride content.
[68037-59-2]
TSCA
Potential reducing agents in the mode of HMS-991 or
HMS-992.
153
Gelest, Inc.
HMS-991 or HMS-992
POLYMETHYLHYDROSILOXANE
[63148-57-2]
TSCA
Reduces lactones to lactols.
55
Reduces aldehydes, ketones,
esters, lactones, triglycerides and epoxides to alcohols with
zinc hydride catalysis.
52
With titanium tetraisopropoxide
catalysis, carries out reductive amination of ketones
and aldehydes
82
and the reduction of acids or esters to
1 alcohols.
50
With TBAF catalysis, selectively reduces
aldehydes over ketones.
43
Used to generate tri-n-butyltin
hydride in-situ and in a one-pot hydrostannylation/Stille
coupling sequence.
190
Reduces esters to alcohols.
54
GERMANIUM AND TIN-BASED REDUCING AGENTS
TABLE 7
SNT8130
TRI-n-BUTYLTIN HYDRIDE
[688-73-3]
TSCA
Has been reviewed.
80
Catalyzes the Si-H reduction of
,-unsaturated ketones.
186
Useful in the reductive
amination of ketones and aldehydes to form 3 amines.
81
GET8100
TRI-n-BUTYLGERMANE
[998-39-0]
Reduces acid chlorides to aldehydes in presence of
Pd(0).
83
Effects free-radical reductive addition of alkyl
halides to olefins.
191
Reduces benzylic chlorides 70x faster
than silyl hydrides.
192
GET8660
TRIPHENYLGERMANE
[2816-43-5]
Readily adds to terminal acetylenes and olefins.
193
Used in
the reductive alkylation of acrylonitrile and enones.
84
GET8560
TRIMETHYLGERMANE
[1449-63-4]
Effects halogen displacement of alkyl halides with hydrogen
when exposed to UV.
194
154
Gelest, Inc.
1
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