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JOURNAL OF THE
Iranian
Chemical Society
D
a
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran
b
Department of Chemistry, Faculty of Science, Ilam University, Ilam, Iran
c
Department of Phytochemistry, Medicinal Plants and Drugs Research Institute,
SI
Shahid Beheshti University, Evin, Tehran, Iran
d
Department of Chemistry, Faculty of Science, Guilan University, Rasht, Iran
compounds, acylation of alcohols, phenols, amines or thiols, epoxidation of alkenes, aziridination and etc. The main purpose of
writing this review is encouraging of active researchers interested to this field for the synthesis of new N-halo reagents specially
with different halogens and applications of these new N-halo reagents in organic reactions or finding more and more applications
of existing N-halo reagents in organic synthesis.
ch
Keywords: N-Halo reagents, N-Halo imides, N-Halo amines, N-Halo sulfonamides, N-Halo amides, N-Halo sulfonimides
Ar
This article is dedicated to Professor Seyyed Ahmad Banihashemi one of the founders of polymer chemistry in Iran on the
occasion of his 75th birthday.
www.SID.ir
Kolvari et al.
Depending on the conditions, a number of highly reactive few hours under mild conditions [13].
intermediates can be formed including halogen radicals, The enantioselective epoxidation of chalcones was carried
halogen cations, halogen anions, N-radicals, N-cations, N- out using TCCA as oxidant in the presence of a chiral
anions, etc. Consequently, N-halo reagents have the potential quaternary ammonium salt as a phase transfer catalyst in good
to promote important reactions such as halogenation, yields with moderate enantiomeric excesses (Scheme 1) [14].
oxidation, and protection as well as formation of C-X, C-O,
and C=O bonds. In addition to the numerous organic and
inorganic halogenating agents, N-halo reagents play an R1 H
D
H N
compounds. Some of the N-halo reagents which are presented
in Tables 1-4 are reviewed in this article.
OR2
SI
TRICHLOROISOCYANURIC ACID O 10 mol% O O
R R' R R'
Trichloroisocyanuric acid (TCCA, 1), 1,3,5-trichloro- Toluene, TCCA, 50% KOH
1,3,5-triazine-2,4,6-(1H, 3H, 5H)-trione, was first synthesised R = Ar, R' = Alkyl or Aryl
in 1902 from the reaction of the potassium salt of cyauric acid
of
with chlorine gas [9]. TCCA was commonly named as
Scheme 1
Symclosene, ACL-85 and Chloral [10,11].
TCCA was used in the presence of base as an efficient
ive
O
oxidant for the epoxidation of enones and tandem oxidation-
Cl Cl epoxidation of allylic alcohols in a water suspension system in
N N
the presence of a surfactant (Scheme 2) [15].
O N O
Cl
ch
1
O O O
TCCA
1
R1 R2 R R2
Surfactant, KOH(aq)
Oxidation Reactions R1 R1 OH R1 O
TCCA KOH
Oxidations by TCCA are mainly categorized into two Surfactant, KOH(aq) Cl R2 R3
R2 R3 R2 R3 Et2O, Pentane, r.t.
sections, transfer of oxygen and dehydrogenation. An
R1 = Aryl or Alkyl, R2, R3 = H or Alkyl
interesting application of TCCA is the conversion of α,β-
unsaturated carbonyl compounds to their corresponding
epoxides. TCCA has been used for the oxidation of enones in Scheme 3
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127
Application of N-Halo Reagents in Organic Synthesis
N-Bromosuccinimide NBS N Br
O
O
Br Br
D
N N
Tribromoisocyanuric acid TBCA
O N O
Br
SI
O
Br
N N
Sodium monobromo isocyanurate SMBI
O N O- Na+
H
of
O
N-Bromophthalimide NBPI N Br
O
ch
O Br
N-Bromo-p-toluenesulfonamide sodium salt
- H3C S N
(Bromoamine T) -
+
O Na
O
Ar
N-Bromosaccharin NBSa N Br
S
O
O
H3C
N,N'-Dibromo-N,N'-1,2-ethanediyl -bis (p-
BNBTS SO2NCH2 )
toluenesulfonamide) 2
Br
H3C SO2
N-Bromo bis(p-toluenesulfonyl)amine NBBTA N Br
H3C SO2
128 www.SID.ir
Kolvari et al.
Table 1. Continued
O O O O
O O
1,3-Dibromo-5,5-diethylbarbituric acid - N N
Br Br
D
O
SI
Table 2. The Name and Structure of N-Chloro Reagents
O
of
N -Chlorosuccinimide NCS
N Cl
O
O
ive
Cl Cl
N N
Trichloroisocyanuric acid TCCA
O N O
Cl
O
ch
Cl
N N
Sodium dichloroisocyanurate SDCI
O N O- Na+
Cl
Ar
N -Chlorophthalimide NCPI N Cl
O
O Cl
N-Chloro-p-toluenesulfonamide
- H3C S N-
sodium salt (Chloramine T) Na+
O
O
N -Chlorosaccharin NCSac N Cl
S
O
O
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129
Application of N-Halo Reagents in Organic Synthesis
Table 2. Continued
NHCl
Trichloromelamine TCM N N
ClHN N NHCl
D
Cl
N
2,6-Dichloropyridazin-3(2H)-one - N
SI
Cl
O
Cl Cl
N,N,2,3,4,5,6-Heptachloroaniline N
Cl Cl
-
Cl Cl
of
Cl
(CH-CH2)
n
Poly[4-vinyl-N,N'-dichlorobenzenesulfonamide]
-
ive
SO2NCl2
5
R1 N R
F X-
R
N
1-Alkyl-4-fluro-1,4-diazabicyclo
-
[2,2,2]octane N
F (X)
2
N-Fluoroquinuclidinium
- N
tetrafluoroborate
BF4
F
O
O
N-Fluoro-3-cyclohexyl-3-methyl-2,3- S
dihydrobenzo[1,2-d]isothiazole-1,1- CMIT-F NF
dioxide Me
130 www.SID.ir
Kolvari et al.
Table 3. Continued
O O
S
N-Fluoro-3-ethyl-3-methyl-1,1-dioxo-2,3- NF
- Me
dihydro-1λ6-benzo[e]1,2-thiazin-4-one
Et
O
R
R
N-Fluorocamphorsultam -
N
D
O S F
O
O O
S
N-Fluoro-o-benzenedisulfonimide NFOBS N F
SI
S
O O
CH2Cl
N
1-(Chloromethyl)-4-fluoro-1,4-diazabicyclo
F-TEDA-BF4
[2,2,2]octane bis(tetrafluoroborate)
of
N
F
O O
Ph S
N-Fluorobenzensulfonimide NFSi N F
ive
Ph S
O O
NO2
N
N-Flouro-2,4-dinitroimidazole NF-2,4-DNI N F
O2N
O
ch
O
F3C S
N-Flouro bis[(trifluoromethyl)sulfonyl]imide - N F
F3C S
O O
O O
Ar
S
N
N-t-Butyl-N-flurobenzensulfonamide -
F
N-Iodosuccinimide NIS N I
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131
Application of N-Halo Reagents in Organic Synthesis
Table 4. Continued
N-Iodophthalimide NIPI N I
O
O
N-Iodosaccharin NISac N I
S
O
D
O
H 3C
N,N'-Dibromo-N,N'-1,2-ethanediylbis(p-
BNITS SO2NCH2 )
toluenesulfonamide)
SI
2
I
of
O R3 OH R3
Cl Cl R2 R2
N N N N
+ AcOH, NaOAc +
O N O R 4
N R 1 CH3CN, CH2Cl2, H2O HO N OH R4 N R1
Cl O
ive
Scheme 4
ch
Oxygen transfer to nitrogen was also achieved by TCCA. TCCA was successfully used for the synthesis of Fipronil
Pyridine and its derivatives were readily oxidized to their N- 2 (a highly efficient insecticide) from the corresponding
Ar
oxides with a solution of TCCA, acetic acid, sodium acetate sulfide (Scheme 6) [19].
and water in acetonitrile and dichloromethane with 78-90%
O
yields (Scheme 4) [17]. CH3 CH3
F3C S F3C S
Acetylenic sulfides were oxidized to acetylenic sulfoxides
N N
by a solution of pyridine, water, benzoic acid and TCCA in H2N
N
H2N
N
TCCA
acetonitrile and dichloromethane (Scheme 5) [18].
CH3CN, CH2Cl2, H2O
1h, 70%
O CF3 CF3
TCCA, Py
R1 C C S R2 1
R C C S R2 2
CH3CN, CH2Cl2, H2O
82-94% Scheme 6
R1 =Ph, n-C3H7, n-C4H9, n-C6H13, n-C5H11, -CH2OCH3
R2 = Ph, 4-MeC6H4
The second oxidation mechanism by TCCA involves
Scheme 5 dehydrogenation. This behavior may be applied for the
132 www.SID.ir
Kolvari et al.
aromatization of cyclic compounds or oxidation of alcohols, TCCA was used for the oxidation of urazoles and bis-
primary amines and hydrazines. TCCA was used for the urazoles to their triazolinediones under both heterogeneous
oxidation of 1,3,5-trisubstituted pyrazolines to their and also solvent-free conditions with excellent yields at room
corresponding pyrazoles under either heterogeneous or temperature (Scheme 10) [24].
solvent-free conditions in good yields at room temperature
(Scheme 7) [20].
R1 H
N N TCCA N N
CH2Cl2, r.t.
R2 N 1 O N O or solvent- free O N O
N R R2 N R1
TCCA N 2 2
D
R R
CCl4, r.t. 1 2
R 3
or solvent-free R = H or Na, R = Alkyl or Aryl
R3
R1, R2, R3 = Aryl
SI
Scheme 10
Scheme 7
R CH3CN, -15 °C, 3 min R R1, R2= Methyl, Ethyl, n-Propyl, or R1=R2= -(CH2)4-, -(CH2)5-
N N
H H
R= Alkyl or Aryl Scheme 11
Ar
Scheme 8
An interesting application of TCCA was reported by
Chen and his co-workers reported the oxidation of primary Hieagl, et al. in the conversion of α-aminoacids into nitriles
amines into nitriles by TCCA in the presence of a catalytic by oxidative decarboxylation in water or methanol in the
amount of TEMPO under mild reaction conditions (Scheme 9) presence of pyridine [26]. For example L-isoleucine was
[23]. Optimization of the reaction condition showed that the converted to (S)-(+)-2-methylbutyronitrile in 88% yield after
best results were obtained in dichloromethane at 10 ºC and the 3.5 h with no considerable loss of its optical purity (Scheme
use of 1 mol% of the catalyst. 12).
Scheme 9 Scheme 12
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133
Application of N-Halo Reagents in Organic Synthesis
TCCA takes part in dehydrogenation of primary and procedure and the total absence of any transition metal make
secondary alcohols for their conversion to aldehydes and the reaction suitable for safe laboratory use (Scheme 15). A
ketones, respectively. Chemoselective oxidation of benzylic mechanism was proposed for these reactions (Scheme 16).
and secondary alcohols was achieved by the use of TCCA and
Boc Boc
wet SiO2 in the presence of a catalytic amount of KBr under
N N
heterogeneous conditions at room temperature (Scheme 13)
TCCA
[27]. TEMPO(cat.), NaBr
N acetone, NaHCO3 N CO2H
Boc OH r.t., 24 h, 100% Boc
O
O H2O Cl Cl
D
N N
R1 R2
HOCl Scheme 15
O N O
Br O Cl
H H
SI
N N
O N O
Br TCCA
H
N N
OH
O O Cl
Cl + OH R OH
R1 R2
of
O
Cl
1 2
R , R = Aryl and Alkyl N NH
O N O N
Cl
Scheme 13 O O
O
Cl Cl H R
H2O N N H
ive
other sensitive functional groups such as vinyl and ketals Fluorinated alcohols were also oxidized to aldehydes by
(Scheme 14). the use of TCCA in the presence of TEMPO [30]. TCCA was
used for the conversion of primary alcohols and diols to
O
O methyl esters and lactones, respectively, by refluxing in
O
O O dichloromethane (Scheme 17) [31].
OH O
O
TCCA
n-Bu4NBr, K2CO3 O O O
O O
CH3CN/H2O
52% OH TCCA OMe
CH3OH, CH2Cl2
Scheme 14 24 h, 99.6%
O
Efficient oxidation of primary alcohols to the OH TCCA
corresponding carboxylic acids was carried out at room O
OH Py, CH2Cl2
5 h, 97%
temperature and in acetone/water, using TCCA in the presence
of a catalytic amount of TEMPO [29]. The mild conditions of Scheme 17
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Kolvari et al.
D
18) [32]. Scheme 21
TCCA
RNH2 RNCl2
SI
CH2Cl2, 15 °C
Regioselective chlorination of isatin at the 5-position and
R NH2
TCCA RCN
also deactivated aromatic compounds, such as nitrobenzene
Et3N, DMF was carried out by TCCA in H2SO4 [37]. An interesting
15 °C
CO2H example of application of TCCA as a chlorinating agent was
TCCA
of
RCN described in the synthesis of some cyclic dichloroimines
R NH2 NaOH, H2O
5 °C (Scheme 22) [38].
R= Aryl or Alkyl
Scheme 18 R R
ive
N
N-Chlorination of various amides, lactams and carbamates TCCA N
Br CHCl3/CH3CN
were proceeded efficiently by TCCA under very mild Cl Br
reflux
condition at room temperature [33]. An interesting example Cl
R= H or Cl
that demonstrates the chemoselectivity of the method is shown
ch
Scheme 22
in Scheme 19.
HO HO
TCCA The preparation of diverse β-chloroethers, β-chloroacetates
Ar
Boc Boc
N CO2Me CH2Cl2, r.t. N CO2Me and chlorohydrins was achieved by the reaction of alkenes
H 3 h, 99% Cl with TCCA in alcohols (MeOH, EtOH, i-PrOH and t-BuOH),
acetic acid or aqueous acetone, respectively (Scheme 23) [39].
Scheme 19
Hiegel et al. reported a procedure for the conversion of R2 R1 R4OH, r.t. R4O R1
alcohols to alkyl chlorides using TCCA in the presence of R1= Ph, Alkyl R3= H, Methyl
triphenylphosphine (Scheme 20) [35]. R2= H, Alkyl R4 = H, Alkyl, Ac
CH3(CH2)8CH2OH
TCCA, Ph3P
CH3(CH2)8CH2Cl
Scheme 23
CH3CN, 60 °C
2 h, 74%
TCCA was reacted with alkynes in the presence of water in
Scheme 20 acetone or acetonitrile to form α,α-dichloro ketones and in
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135
Application of N-Halo Reagents in Organic Synthesis
methanol to form α,α-dichlorodimethyl ketals (Scheme 24) They have also reported an easy and general method for
[40]. deprotection of thioacetals to their corresponding carbonyl
compounds using TCCA/silica gel in the presence of water
O
[45]. Similar reactions were also carried out in non-aqueous
TCCA conditions (CHCl3 and DMSO) at room temperature [46]. The
H2O, acetone Cl Cl
59% same group took advantage of TCCA in catalytic preparation
and cleavage of THP-ethers of various hydroxy functional
H3CO OCH3
groups with high yields (Scheme 27) [47]. A mechanism was
TCCA
Cl Cl
CH3OH
D
62%
TCCA (cat.), DHP
60-80 °C
Scheme 24 ROH
TCCA (cat.), MeOH, r.t. RO O
SI
Carboxylic acids were chlorinated in the α-position by R = 1°, 2°, 3°, Allylic, Propargylic, Benzylic
O O
RO TCCA RO RO O
ive
P H P Cl
RO CH3CN, r.t. RO
10-15 min O
RO O
Cl
R= Phenyl, Benzyl, or Alkyl ROH + N H
ROH
Scheme 25
ch
O
Treatment of styrene-butadiene rubber with TCCA was OR
Cl + N
reported to chlorinated the rubber and improved its adhesion H
H
properties [43,44]. O
Ar
O O S OH OAc
TCCA TCCA
R R R
HS(CH2)nSH n-2 R 1
R 2 Ac2O, CH2Cl2 1
R R2
O O S
CH2Cl2, r.t. r.t.
n = 2, 3
R1, R2 = Alkyl, Aryl
R= Substituted Phenyl, Cinnamyl
Scheme26 Scheme 29
136 www.SID.ir
Kolvari et al.
A novel and efficient trimethylsilylation of various TCCA and triphenylphosphine in the presence of carboxylic
alcohols and phenols was efficiently carried out with acids resulted in the in situ formation of the corresponding
hexamethyldisilazane (HMDS) in the presence of catalytic acid chlorides [53]. Subsequent addition of amines or alcohols,
amounts of TCCA in good to excellent yields in in the presence of a tertiary amine, afforded the corresponding
dichloromethane at room temperature (Scheme 30) [49]. amides, or esters, in good to excellent yields. The method was
interestingly applied to the synthesis of a protected dipeptide
(Scheme 33).
TCCA (0.06-0.1 mmol),
HMDS (0.8 mmol)
ROH ROSiMe3
CH2Cl2, r.t.
D
BnO
O O O
R = 1°, 2°, 3°, Benzylic, Naphtyl 1) TCCA, Ph3P, CH2Cl2
0 °C to r.t., 45 min
OH N
Scheme 30 NHBoc NHBoc
SI
2) O
N , Et3N, 2 h
85%
H H OBn
Cl
Miscellaneous Reactions
A combination of TCCA and sodium nitrite in the presence Scheme 33
of
of wet SiO2 has been used for the nitrosation of N,N-dialkyl
amines under mild and heterogeneous conditions [50]. For
example 2-methylpiperidine was converted to its N-nitroso Alcohols were converted into alkyl nitrates, nitrites or
derivative in short time with quantitative yield (Scheme 31). thiocyanates by the action of TCCA and triphenylphosphine
along with silver nitrate, silver nitrite, or sodium thiocyanate,
ive
Scheme 31
TCCA, Ph3P R-ONO
ROH
CH3CN, AgNO2
TCCA, Ph3P
The same reagent system was used for the mononitration ROH R-SCN
Ar
CH3CN, NaSCN
of p-substituted phenols at room temperature in good yields
R= Nonyl, Octyl, Cyclohexyl, Benzyl
(Scheme 32) [51].
Scheme 34
OH OH
NO2
TCCA, NaNO2 Amides were chlorinated on nitrogen using TCCA and the
CH2Cl2, wet SiO2 produced N-chloroamides were then rearranged to the
r.t.
X X corresponding methyl-N-substituted carbamates by sodium
X = F, Cl, CN, CH3, OCH3, COCH3, CHO, CH2Ph, NHOAc, CO2H
methoxide in methanol [55]. Isocyanates were suggested as
the intermediates (Scheme 35).
Scheme 32 TCCA was used efficiently for the synthesis of 3,4-
dihydropyridine-2(1H)-ones through the three-component
Dinitrophenols were also obtained in a similar way but Biginelli reaction of a β-ketoester, an aldehyde and urea
under solid-phase reaction conditions [52]. The reaction of (Scheme 36) [56]. TCCA has been used as an initator for the
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137
Application of N-Halo Reagents in Organic Synthesis
O O
O
TCCA NaOCH3
R NH2 R N C O R N OCH3
CH3OH R NHCl CH3OH H
Scheme 35
O R1
O O O R 2O NH
R1CHO + + TCCA
OR2 H 2N NH2 O
Solvent-free, 90 °C N
H
D
2h
R1= Alkyl or Aryl, R2= Methyl or Ethyl
Yield: 75-90%
SI
Scheme 36
metal-catalyzed living radical polymerization of methyl An efficient and highly regioselective bromination of
methacrylate [57]. activated aromatic rings promoted by TBCA through in situ
generation of Br+ has been developed by de Almeida et al.
of
TRIBROMOISOCYANURIC ACID AND [58a]. For example, monobromination of 2-methoxy-
SODIUM MONOBROMOISOCYANURATE naphtalene was carried out in excellent yield after a short
reaction time (Scheme 37). Also, Niknam et al. have reported
There are few reports on the application of
ive
O O
Br Br Br Na
N N N N Scheme 37
O N O O N O
nitration of phenols, silylation of alcohols and oxidation
H
Ar
Br
3 4
Br O
N
O H
CF3CO2H
N
H O
O
SMBI O
O
O Br
N
H
H2SO4
5
O
O
Scheme 38
138 www.SID.ir
Kolvari et al.
D
diethyl ether. An interesting example was selective economic advantages, DBH has found widespread
bromination of compound 5 by changing the solvent (Scheme applications in industrial processes such as swimming-pool
38). sanitizer, brominating agent for ethylene propylene diene
SI
Bromination of some azulene derivatives were achieved by monomer rubber (EPDM) to improve ozone resistance,
SMBI. Bromination in dichloromethane gave the products in additive in plastics to promote photodegradation and as a
low yields, while the reactions in dichloromethane-water gave fungicide to preserve fresh fruits [61-68].
good yields of the desired compounds (Scheme 39) [60]. The
following mechanism was suggested for these reactions
of
Br
O N O
R R
Me N
Me Br
SMBI
ive
CH2Cl2-H2O
6
Br
R = Et, n-Pr, Ac2O Among the methods, which were reported for the
preparation of DBH [69-72], the bromination of 5,5-
ch
O
Ar
O
Br
N NH Br Br
HN N
O H O
O N O
O N O H H
Na+ H2O
Na+
Br
H Br
Br
O H-OH2
H
Scheme 40
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139
Application of N-Halo Reagents in Organic Synthesis
CO2H CO2H
NaHCO3 was studied with precision (Scheme 41) [73]. It was
D
reported that the mechanism of the reaction consists of two
bromination steps (Scheme 42). Studies cleared that the rate of the bromination of various
aromatic derivatives substituted with electron donating groups,
SI
with DBH, considerably enhanced in the presence of
H H trimethylsilyltrifluoromethanesulfonate (TMSOTf) [75]
O N O O N O (Scheme 44).
Step 1: N + NaOH Me N
Me
of
H Na
Me Me
OMe OMe
2NaOH + Br2 NaOBr + NaBr + H2O OMe
DBH(0.5 eq)
H Br
N
TMSOTf (0.5 eq)
O O
ive
O N O r.t., 2 h, 50-86%
Br
Me N + NaOBr N + NaOH Scheme 44
Na Me
Me Na
Me
Br Br
intermediate (Scheme 45).
O N O N
O O
Me N + HOBr N + NaOH
Me Br Br
Ar
Na H
Me Me Br
O N O O N OSiMe3 O N O
TMSOTf
NaOH + HBr NaBr + H2O + TfOH
N Me N NH
Me Me
Me Br Me Me
ArBr
Scheme 42 DMH
+ BrOTf
ArH
The application of DBH in organic reactions mainly can be
studied in the following sections. TMSOTf
DMH
Halogenation Reactions
DBH BrOTf ArBr
Bromination reactions. In 1993, Auerbach and co-
workers reported that DBH in aqueous NaOH can be used as
TfOH Ar
an efficient reagent for the bromination of activated benzoic
acids [74]. They also showed that DBH gave better yields than
Scheme 45
NBS (Scheme 43).
140 www.SID.ir
Kolvari et al.
Similarly, Eguchi and co-workers used DBH in the pyrogallol derivatives by DBH, which gave single
presence of organic and inorganic acids with pKa values less monobromides in 1.5 h at room temperature (Scheme 48) [78].
than -2 to get the monobromide in excellent yields [76]. Very
good yields were obtained even for aromatics having electron-
COOMe COOMe
withdrawing substituents. In some cases, catalytic amounts of
Br
acids were sufficient (Scheme 46). DBH (0.53 eq)
r.t., 1.5 h, 77%
O OH O OH
O O
R R Me Me
Me Me
D
DBH/acid (0.5/(0.1-1.0 eq)) Scheme 48
r.t. or reflux, 5 min-24 h,
62.4-99.5% Br
SI
Treatment of 5,13-di-tert-butyl-8,16-dimethyl [2.2]
R H2SO4 CF3SO3H
metacyclophane 7 with DBH (0.55 eq.) in CH2Cl2 at room
NO2 75% 87%
temperature led to the introduction of bromine on the bridged
CF3 81% 86% methylene group for the first time (Scheme 49) [79]. The
of
OMe 97% 97% reaction was accompanied by the formation of two by
CO2Me 71% 76% products 9 and 10. The yields of 9 and 10 depended on the
Scheme 46 amounts of DBH, so in the presence of 3.1 eq. of DBH only
compound 10 was obtained in 98% yield.
ive
Me Bu-t Me Bu-t
COOMe COOMe
Ar
Br 7 8
DBH (0.5-0.55 eq)
CHCl3, r.t., 88-99%
R1O OH R1O OH t-Bu t-Bu
OR2 OR2
R1 = Bn, Me; R2 = Me, OH
Br Br
COOMe COOMe
Me Me Me Me
Br
DBH (0.5-0.55 eq) + Br Br
CHCl3, r.t., 80-99%
O OH O OH
1 O O t-Bu
R R1 t-Bu
R2 R1, R2 = H, Me, Ph R2
9 10
Scheme 49
Scheme 47
In 2006, Azarifar et al. reported an efficient method for
They also studied the regioselective bromination of
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141
Application of N-Halo Reagents in Organic Synthesis
the conversion of various N-arylglycines to sydnones using Flourination reactions. Hiyana et al. reported the
DBH in the presence of NaNO2/Ac2O under mild and neutral oxidative desulfurization-fluorination of methyl xanthates with
conditions (Scheme 50) [80]. The following mechanism was (HF)9/pyridine and DBH (Scheme 53) [81]. Under the reaction
conditions, trifluoromethyl ethers (R-OCF3) were produced
through R-OCF2SMe intermediates.
Ar
DBH (0.8 eq) N
ArNHCH2CO2H N
NaNO2 (1.25 mmol)/Ac2O (1.5 mmol) O
O
0-5 °C, CH2Cl2, 10-16 h, 80-94% S
R (HF)9/Py (2mL, 8.8 mmol of F-)
[R-OCF2SMe]
Scheme 50 O SMe
DBH (3 mmol), CH2Cl2
D
0 ° C, 1 h, 48-80%
proposed for these transformations (Scheme 51). R= Substituted Phenyl, Benzyl, n-C10H21 R-OCF3
Scheme 53
SI
Br
O N O O N O
They also showed that β-hydroxy orthothioesters 11
N + NaNO2 N Na + BrNO2 derived from both aromatic and aliphatic aldehydes were
Me Me
Me Br Br
Me successfully converted into their corresponding
of
difluoro(methyl thio)methyl ketones 12 using n-Bu4NH2F3 and
BrNO2 NO + BrO
DBH. Reactions were performed in CH2Cl2 at room
temperature (Scheme 54) [82].
+ NO
ArNH2CH2CO2H HOBr + ArN(NO)CH2CO2H
ive
+ BrO
OH O
Ac2O + HOBr AcOBr SMe n-Bu4NH2F3 (5 mmol) SMe
R DBH (4 mmol)
SMe R F
SMe CH2Cl2, 10 min, r.t.
28-95% F
AcOBr
Ar H
ch
O 11 12
N R= Aryl or Alkyl
Ar OAc
N OH N
-AcOH O OH
+ BrO Scheme 54
N
O
Correspondingly, when orthothioesters were selected as
Ar
Ar H Ar H
N N
OAc BrO
+ HOAc + HOBr
the substrate the monobromo- difluorinated compounds were
N N + O
O OH O obtained as the main products (Scheme 55) [83]. A
Scheme 51
Br
SMe n-Bu4NH2F3 (3 mmol) SMe
They also showed that DBH is able to promote the R DBH (3 mmol) R
SMe F
bromination of sydnones to their 4-bromo-substituted SMe CH2Cl2, 20 min, 0 °C to r.t.
F
52-87%
congeners in excellent yields in DMF at room temperature
Scheme 55
(Scheme 52).
Ar H Ar Br
N
DBH (2 mmol) N mechanism which initiated by the electrophilic attack of Br+ at
N + N +
O
O DMF, r.t., 2.0-2.6 h
O
O the sulfur atom of the substrate has been suggested (Scheme
94-99%
56).
Scheme 52
142 www.SID.ir
Kolvari et al.
D
H Br Scheme 58
H Br
SMe
SMe R F
R
F product can be rationalized by the following mechanism
SI
F
F
(Scheme 59). On the basis of the proposed mechanism,
electrophilic attack of Br+ to organic sulfide produces a
Scheme 56 sulfonium ion 14, which is attacked by the fluoride ion to give
the final product. The reaction of RCH(SMe)CF2SMe, under
of
They also found that when RCH(OAc)C(SMe)3 was used
H R1 H R1 R1
instead of RCH2C(SMe)3, the corresponding difluoro acetate Br+ + -HBr +
RS-C RS-C 2 RS=C 2
was obtained as the main product (Scheme 57) . R2 R R
Br
ive
13 14
F R1
H OAc H OAc F
SMe n-Bu4NH2F3 (5.2 mmol) F RS-C 2
R DBH (4.4 mmol) R R
SMe F
SMe CH2Cl2, 10 min, 0 °C, SMe Scheme 59
Argon atmosphere
ch
53-70%
R = 1-Naphtyl, 2- Naphtyl, n-C11H23 the same conditions, ended up with the formation of
Scheme 57 trifluorosulfides, [RCF(SMe)CF2SMe], as the main products
(Scheme 60).
Ar
Furuta et al. reported that various organic sulfides, on Shimizu et al. reported an efficient method for the
H SMe F SMe
n-Bu4NH2F3 (3.5 mmol)
CF2SMe DBH (2.5 mmol) CF2SMe
CH2Cl2, r.t., 20 min
68%
Scheme 60
Scheme 61
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143
Application of N-Halo Reagents in Organic Synthesis
conversion of gem-disulfides to the corresponding gem- They have also reported a mild method for the preparation
difluorinated compounds by a combination of of trifluoromethyl ethers (R-OCF3). The reaction was carried
hexafluoropropene-dimethylamine and DBH (Scheme 61) out by the reaction of dithiocarbonates (R-OCS2Me) with a
[86]. reagent system consisting of 70% HF/Pyridine and DBH
Using this method, 1,3-dithiolanes derived from ketones (Scheme 65) [88]. When the reaction was applied to
gave better results than those from aldehydes. The probable ROCS2Me wherein R = secondary alkyl, tertiary alkyl or
mechanism of the reaction is shown in Scheme 62. benzylic group, fluorination was leading to corresponding
alkyl fluorides (R-F) (Scheme 66).
D
BrS S 70% HF/Py (40 mmol)
BrS
F DBH (3 mmol)
S SBr PhCH2CH2CH2-O-C-SMe PhCH2CH2CH2-O-CF3
S BrF S S
S F CH2Cl2, -78 °Cto 0 °C, 1 h
75%
SI
BrS
Scheme 65
Br
BrF S F F F F
trifluoromethyl and 3,3,3-trifluoropropenyl substituted Due to their stability and stereoselectivity on the glycoside
aromatic compounds were obtained in acceptable yields synthesis, the glycosyl fluorides have recently received
(Schemes 63 and 64) [87]. considerable attention [89]. Among different methods reported
for the preparation of glycosyl fluorides, bromofluorination of
ch
Scheme 64
OR
OR OR
OR
RO SiF4(gas), DBH (1.1 mmol) Br
RO O H2O (1.0 mmol), HMPA (0-5 mmol) RO RO
RO O RO O RO
+ + RO O
1,4-dioxane (4 mmol) F
0 or 50 °C, 1h Br
F F Br
144 www.SID.ir
Kolvari et al.
absence of HMPA, formation of the α-fluorides predominated DBH has also been used for the efficient oxidation of
with ratio of 74:26, and the addition of HMPA improved the mono and bis-urazoles to their corresponding triazolinediones
selectivity in favor of the α-isomers. The best stereoselectivity both in solution and under solvent-free conditions (Scheme
was obtained when the reaction was carried out in the presence 71) [94].
of 3.0 eq. of HMPA, in which the α- vs. β-isomer ratio was
92:8.
H O O H O O
Hiyama et al. has also reported that when alkene was N N
N N
A or B
treated with KHF2/HF/n-Bu4NF/DBH reagent system, the N R2 N N R2 N
related bromofluorinated product was obtained in good to high N N N N
R1 O O R1 O O
D
yields (Scheme 68) [91]. The stereochemistry of the addition
of F and Br was anti for all of the olefins. A: DBH (2 mmol), 4h, 99-100%, CH2Cl2, r.t.
B: DBH (2 mmol), 4h, 33%, Solvent-free, r.t.
SI
O F O R1 = H, Na, R2 = -(CH2)6- , -C6H4-CH2-C6H4-
n-Bu4NH2F3 (1.5 mmol)
DBH (1.5 mmol) Br
OMe OMe
CH2Cl2, r.t., 13 h, 85 % Scheme 71
R3 R3 Scheme 72
A: DBH (1-4.25 mmol), 0.3-1.75 h, 70-98%, CCl4, r.t.
B: DBH (2-18 mmol), 0.3-4.5 h, 63-92%, Solvent-free, r.t.
A mechanism was proposed for this reaction (Scheme 73).
R1 = Ph, Acetyl, R2 = Aryl, R3 = Substituted Phenyl
Ar
Scheme 69 O
Br O
N
The same group has also shown that when the reaction was 2RSH + N Br 2 R S Br N
N
carried out in the presence of silica gel under microwave H
O
irradiation, the products were obtained during very short II O
I
reaction times (Scheme 70) [93].
O
DBH (2.5-4 mmol) H
R1 N R1 N N
N Ph Silica gel (20-32 mg)
N Ph 2 RSBr + N H
II
MW, 1-5 min, 74-90%
R2 R2 O
III
R1 = Aryl, R2 =Substituted Phenyl
2 RSBr RSSR + Br2
Scheme 70
Scheme 73
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145
Application of N-Halo Reagents in Organic Synthesis
The same subject has also been investigated by another DBH (1.2 mmol)
R1 N N R3 R1 N N R3
group in 2005 [96]. DBH in accompanying with NaNO2 was 1-15 min, 63-89%
R2 H
used as a co-catalyst for the acceleration of the aerobic R2 Br
1
R = Substituted Benzyl and Phenyl,
oxidation of benzylic alcohols in water catalyzed by TEMPO R2 = H, Substituted Phenyl,Methyl, R3= Substituted Benzyl
(Scheme 74) [97]. All reactions were performed at 80 ºC and
the products were obtained in good to high yields. Scheme 76
D
H2O (3 ml), oil bath (80 °C), (benzoyl peroxide) or a radical inhibitor (butylated hydroxy
1.5-6 h, 88-98%
R1, R2 = Alkyl and Aryl
toluene, BHT), an ionic mechanism, which involved
bromination of imidazolidine`s nitrogen, followed by
Scheme 74
SI
deprotonation and displacement of a bromide ion, was
proposed for the reaction (Scheme 77).
Recently, Rievera et al. reported a suitable method for the
synthesis of 5-substituted-2-amino-1,3,4-oxadiazoles, as
Miscellaneous Reactions
biologically active important molecules, via oxidative
Walters et al. studied the use of DBH for the oxidation of
of
cyclization of thiosemicarbazides using DBH in the presence
hydroxylamines to gem-halonitro compounds in the presence
of potassium iodide (Scheme 75) [98]. The main advantage of
of ozone (Scheme 78) [100]. The bromo derivatives were
this method is its applicability for the large scale synthesis of
obtained in 44-73% yields.
the hydroxyl oxadiazoles.
ive
Scheme 78
N NH2
Ar N i-PrOH (8 mL) N N
H
S NaOH (5N, 1.54 mL)
1h, 10 °C, 53-97%
Scheme 75
O O
Br
Br
Br N
N R1 N N R3 N
N Br 1 3 +
R N N R
+ R2 H
R2 H O
O
O
H
R1 N N R3 + N
N H
R2 Br
O
Scheme 77
146 www.SID.ir
Kolvari et al.
F F
When 1,3-dithiolanes bearing a phenyl or substituted
aromatic group and a methyl (or methylene) group attached to Me
Me
MeO O MeO
C-2 were treated with DBH in the presence of HF/pyridine, a O
Me
Me DBH
rearrangement took place instead of gem-difluorination HF/Pyridine
(Scheme 79) [101]. A mechanism was proposed for this S S Me
MeO O
rearrangement, which is shown in Scheme 80. Me
DBH was also applied for the synthesis of S
diglicodeoxynucleotides containing 2′-O-(trifluoromethyl) S
adenosine in the presence of HF/pyridine (Scheme 81) [102]. Scheme 79
D
Using this method, products were obtained in relatively
acceptable yields under mild reaction conditions. glycosyl S,S-acetals to their corresponding O,O-acetals using
Madhusudan et al. reported the facile conversion of DBH under mild and neutral conditions (Scheme 82) [103].
S S
Br
S
SI S Br S S Br
H
- H+
of
Me Me Me
MeO O MeO O MeO O
Me Me Me
ive
S S
S S Br H S
S
H
Me - H+ Me
Me
MeO O MeO O
MeO O Me Me
Me
ch
Scheme 80
N N N
N N N
N N N N
N N
HF/Py (5 mL)
O O DBH (3.75 mmol) HO HO
O O
TIPDS -78 °C - 0 °C, CH2Cl2 +
O OH OH OCF3 O O
F F
TIPDS = tetraisopropyldisiloxane-1,3-diyl
Scheme 81
OAc OAc
CH(SEt)2 DBH (1 mmol) CH(OMe)2
AcO AcO
30 min, 86%,
OAc OAc r.t. OAc OAc
Scheme 82
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147
Application of N-Halo Reagents in Organic Synthesis
The proposed mechanism of this reaction is illustrated in under the same conditions, glycofuranosides were obtained in
(Scheme 83). When glyclic glycosyl S,S-acetals were reacted good to high yields (Scheme 84). In the case of
Br Br
H SEt
OAc H SEt H H SEt
OAc OAc OAc
OAc H SEt
OAc H SEt -EtSBr OAc H SEt Br OAc H OMe
DBH
H OAc
H OAc H OAc H OAc
MeOH
OAc
OAc OAc OAc
D
AcO
AcO AcO AcO
SI
H H OMe
OAc OAc
-EtSBr OAc H OMe MeOH OAc H OMe
H OAc H OAc
of
OAc OAc
AcO AcO
Scheme 83
ive
OH
AcO O
CH(SEt)2 DBH (1 mmol) OAc OMe
HO 30 min, 86%,
OH OH r.t.
OAc
ch
Scheme 84
Br
H SEt
OH H SEt H H
Ar
OH H SEt OH OH O
DMF OH H SEt OH H SEt OH H SEt
H OH
H OH H OH H OH
OH
OH OH OH
HO
HO HO HO
H H H
O O O
OH H SEt OH OH H OR
H ROH
Br
H OH H OH H OH
OH OH OH
HO HO HO
Scheme 85
148 www.SID.ir
Kolvari et al.
glycofuranoside formation, the authors proposed that product Recently, DBH/NaNO2/wet SiO2 has been used as an
was formed by intramolecular nucleophilic attack from the efficient reagent system for the direct nitration of phenols
hydroxyl group at C-4 following by a nuclophilic attack of the (Scheme 87) [106]. All reactions were performed at room
alcohol at C-1 (Scheme 85). temperature and under completely heterogeneous conditions.
Because of the unstability of α-aminoaldehydes, which are
reckoned as extremely valuable chiral building blocks in
OH OH
asymmetric synthesis [104], the preparation of N-protected
DBH (1mmol) NO2
derivatives of these compounds is attracted the attention of NaNO2 (1mmol)
many organic chemists. Davis et al. reported that the wet SiO2(50% w/w, 0.4 g)
30 min, 90%
D
hydrolysis of sulfimine derived N-sulfinyl-α-amino-1,3- Cl Cl
dithianes with aqueous DBH affords the corresponding N- Scheme 87
tosyl-α-aminoaldehydes in good yields and high enantiomeric
SI
purities (Scheme 86) [105].
The reaction did not proceed in the absence of wet SiO2. The
following mechanism was proposed for the description of the
O
S
reaction pathway (Scheme 88).
Tosyl
of
p-Tolyl NH 1) DBH (2 eq.) NH
2) Na2SO3
In the same manner, when N,N-dialkylamines were treated
H H
R S R with DBH/NaNO2/wet SiO2 reagent system, their
S O corresponding N-nitrosated derivatives were obtained in good
to excellent yields (Scheme 89) [107]. The reaction conditions
R = Ph, i-Pr, t-Bu
ive
O O
Br H
ch
N N
N Br N H
+ 2H2O (wet SiO2) + 2HOBr
O O
HOBr + NO2 HNO2
Ar
HNO2 + 2H NO + H3O
N2O3 NO + NO2
2NO2 N2O4
OH OH O OH
NO2
+ NO +H NO2
-NO
-H
Cl Cl Cl Cl
Scheme 88
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149
Application of N-Halo Reagents in Organic Synthesis
Scheme 89
A or B
ROH ROY
Recently, an efficient and high yielding method for the
acylation of alcohols with acetic anhydride using DBH has A: DBH (0.015 mmol), HMDS (7.0 mmol), CH3CN, r.t.,
immediately-15 min, 80-95%
been reported (Scheme 90) [108]. The proposed mechanism, B: DBH (0.5 mmol), DHP (1.4 mmol), n-Hexane, r.t.,
D
Y: TMS, THP
R= Aryl or Alkyl ( 21 substrates)
OH DBH (0.05 mmol)
OAc
Scheme 92
SI
Ac2O (2mmol)
R1 R2 1
R R2
CH2Cl2, r.t., 1-38 h,
80-95%
R1, R2 = Alkyl or Aryl selective trimethylsilylation or tetra-hydropyranylation of
various types of alcohols in the presence of tertiary alcohols
of
Scheme 90 (Scheme 93). The mechanism which has been reported for the
above mentioned method is the same as that reported for the
tetrahydropyranylation of alcohols in the presence of TCCA
which was based on activation of Ac2O by the in situ (Scheme 28).
generated H+, is shown in Scheme 91.
ive
O
O O O
Br
N Br
+ Ac2O N + O
Ar
O O O
H
+ ROH ROAc + N
N
O O O
O
H Br +
N + Br N OH
O
Scheme 91
DHP, DBH
n-Hexane
Me3COH + OH OTHP + Me3COTHP
r.t., 30 min
95% 0%
Scheme 93
150 www.SID.ir
Kolvari et al.
O
Ar
1-BROMO-5,5-DIETHYLBARBITURIC ACID
N Ar
DBH, AcO2 N AND 1,3-DIBROMO-5,5-DIETHYLBARBI-
N N
O
O Reflux
O
O TURIC ACID
Scheme 94 1-Bromo-5,5-diethylbarbituric acid 16 and its 1,3-dibromo
analogue 17 were prepared in 1991 but found little attention of
1,3-DICHLORO-5,5-DIMETHYLHYDANTOIN organic chemsits [115]. They have been used for the oxidative
D
applications and only few reports are available on its uses in
N N N N
Br Br
organic synthesis. These reports are included α-chlorination of H Br
acetophenones (Scheme 95) [111], oxidative cleavage of O O
SI
oximes [112,113] and oxidation of urazoles [114]. 16 17
O
cleavage of different kinds of trimethylsilyl ethers in good
Cl N
N yields at room temperature (Scheme 96) [116]. The conversion
of
Cl
of benzyl trimethylsilyl ether to benzaldehyde in the presence
O
of both 16 and 17 was conducted in different solvents. The
15
results showed that the efficiency and the yield of the reaction
ive
O O
O O
Cl H
N N
p-TsOH +
R + 1/2 R 1/2 N
N CH3OH/30-35 °C Cl O
O H
ch
Cl
R = H, p-CH3, p-OCH3, p-Cl, p-NO2, p-Br, m-NO2, o-NO2
Scheme 95
Ar
OSi(Me)3 O
A or B
CH2Cl2
Scheme 96
OH
OH
HO OH
17 (Cat., 20% eq) / HMDS (1.5 eq) TMSO OTMS
r.t./ neat/ 85%
Br
Br
Scheme 97
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151
Application of N-Halo Reagents in Organic Synthesis
X
in dichloromethane was better than in other solvents. THP-
Cl
ethers remained intact under the reaction conditions.
Silylation of alcohols and polyols is one of the most N
O N
commonly used methods for their protection. H H
Cl
Cl Cl
Trimethylsilylation is a classic way to produce volatile R1 C R or R1 C H R1 C R or R1 C Cl
Base or Acid
derivatives of alcohols and polyols. The application of 17 as a R2 R2 R2 R2
D
protection of alcohols over phenols (Scheme 97) [117]. Scheme 98
SI
METHOXYPYRIDAZIN-3(2H)-ONE catalyst in organic transformations. The application of some
N-halo sulfonamides such as N,N-dihalo sulfonamides was
2,4,5-Trichloro- and 2,4-dichloro-5-methoxypyridazin- reviewed by Koval [119,120]. Herein, application of a broad
3(2H)-one were synthesised by Park et al. as two novel range of N-halo sulfonamides is reviewed.
reagents in 2005 [118]. α-Chlorination of active
of
methylene/methine compounds with these reagents in the Halogenation Reactions
presence of either Lewis or protic acids in dichloromethane Khazaei et al. have reported a novel compound that was
(for Lewis acid) or water (for protic acid) at room temperature synthesized via bromination of methyl methacrylate with high
gave also α-monochlorides and/or α,α-dichlorides selectively yield. This brominated compound is suitable for
ive
in good to excellent yields (Scheme 98). polymerization as an adhesive (Scheme 99) [121].
Carbanionic substrates were subjected to chlorination with
N-HALO SULFONAMIDES poly[4-vinyl-N,N-dichlorobenzenesulfonamide]. Chlorinated
products were obtained in good yield and short reaction time
ch
N-halo sulfonamides have been widely used in organic under mild condition (Scheme 100) [122].
CH3
CH3 CO2Me
Ar
CO2Me CCl4
CH2 C +
CH2 C + 10 h, 87% H3C SO2NCH2
H3C CH2Br
CH3 SO2NCH2
2 H
Br
CH3 CH2Br
CO2Me CO2Me H2
heat
CH2 C + CH2 C C C C C
CH3 CH2Br H2
CH3 CH3
Scheme 99
152 www.SID.ir
Kolvari et al.
D
bromobenzene-1,3-sulfonamide (PBBS). These new reagents
Recently some new N-halo sulfonamides have been
have been used for bromination of activated aromatic
reported as chemoselective brominating agents for a broad
compounds in good yields (Scheme 103) [129].
SI
CH3
H3C
SO2NCH2 )
of
2
Br SO2NBr2 SO2NCl2
I II III
H3C SO2
ive
Br2N NBr2
N Br SO2NCH2 ) S S
2
H3C SO2 Br O O O O
IV V VI
ch
H 3C
Br Br
( H2C N N
S S CH2) n
SO2NCH2 )
O O O O 2
Ar
I
VII VIII
Scheme 101
CH3 CH3
CCl4
+ Alkene Bromoalkene +
H3C (PhCO2)2 H3C
SO2NCH2 ) SO2NCH2 )
2 2
Br H
Scheme 102
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153
Application of N-Halo Reagents in Organic Synthesis
R R
and characterization of carbonyl compounds. To achieve this
PBBS or TBBDA aim N-halo compounds have been used widely as versatile
CH2Cl2 reagents. Recently a broad range of N-halosulfonamides
25-40 °C (NHSs) has been reported for regeneration of carbonyl
30-180 min Br
79-98% compounds from oximes (Scheme 105) [130,131,135-139].
R= -NHCOCH3, -OCH3, -NEt2 N,N´-Dibromo-N,N´-1,2-ethanediyl bis(p-toluenesulfon-
amide) (BNBTS) has catalytically been applied for
Scheme 103
tetrahydropyranylation of a various range of alcohols and
phenols in dichloromethane and tetrahydropyranylation of
D
these compounds has been also carried out in methanol at
N,N'-Diiodo-N,N'-ethanediylbis(p-toluenesulfonamide)
room temperature (Scheme 106) [140].
(BNITS) as a novel iodinating agent has been used for
SI
iodination of some aromatic compounds in high yields
(Scheme 104) [132].
BNBTS, CH2Cl2, r.t.
ROH +
O BNBTS, MeOH, r.t.
O O
R R R= 1°, 2°, 3°, Alkyl and Aryl R
of
2 Cat. TFAA + BNHTS
+ BNITS 2
CH3CN, 81 °C Scheme 106
3-5 h, 90-93%
I
Scheme 104 Conversion of 1,1-diacetates to aldehydes has been
ive
The protection of carbonyl compounds is very important in good yields with BNBTS under microwave irradiation
multistep synthesis. Protected carbonyl compounds such as (Scheme 108) [142].
oximes, semicarbazones, phenylhydrazone derivatives, BNBTS has been used for deprotection of aliphatic and
diacetals, dithianes and etc. are easily prepared and are highly aromatic 1,3-dithianes to their corresponding carbonyl
Ar
stable compounds used extensively for protection, purification compounds under mild condition (Scheme 109) [143].
NOH NHS O
1 2 1
R R R R2
O Br
O H3C (CH-CH2)
S N Br n
NHS : O O S N
O Br SO2NCH2 )
2
Br
SO2NCl2
Scheme 105
154 www.SID.ir
Kolvari et al.
OAc O
solid state, H2O, r.t. + BNHTS + 2AcOBr
+ BNBTS H
R OAc R
1.5 to 4 min
90-98%
R = Alky or Aryl
Scheme 107
R1 R1 TBBDA or PBBS
BNBTS HMDS
N NH NO2 O RXH RXSiMe3
CH2Cl2, MW CH2Cl2 or solvent free, r.t.
R2 R2
D
30-60 min
O2N
89 -95% X = S or O
R1, R2 = Alky or Aryl R= Aryl, Alkyl
SI
Scheme 108 Scheme 111
n
O Oxidation Reactions
BNBTS, AgNO3
S S Another important application of N-halo reagents in
of
80% aq. CH3CN, r.t. R1 R2
80-90% organic chemistry is the oxidation of different functional
R1 R2
15-30 min groups through the release of halonium ions. TBBDA and
R1, R2 = Alkyl, Ary, H TCM were used as effective oxidizing agent for the
conversion of urazoles and bis-urazoles to the corresponding
ive
n = 1, 2
Scheme 109 triazolinediones under mild and heterogenous condition at
room temperature with good to excellent yields (Scheme 112)
Deprotection of 1,3-oxathiolanes to carbonyl compounds [146].
has been carried out with BNBTS in good yields under mild
ch
Cl
conditions (Scheme 110) [144]. HN
Br2N NBr2 N Cl
S S N NH
n O O O O O N
BNBTS Cl NH
O S
Ar
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155
Application of N-Halo Reagents in Organic Synthesis
BNBTS OH OCOCH3
R-SH RS-SR
CH2Cl2, r.t. Ac2O, Catalysts
1.5-3.8 h 90-95% R1 R2 R1 R2
CH2Cl2, r.t., 1-48 h
R = Alkyl or Aryl 90-98 %
N,N,N',N'-tetrabromobenzene-1,3-disulfonamide (TBBDA),
Catalysts: X= Br or Cl
BNBTS and PBBS were used as efficient reagents for the
oxidation of 1,3,5-trisubstituted pyrazolines to their SO2NX2
corresponding pyrazoles in solvent-free conditions both under
Scheme 116
D
microwave irradiation or at room temperature (Scheme 114)
[148-151].
A combination of equal amount of Ph3P and BNBTS has
SI
been used for the conversion of carboxylic acids into esters
and amides in the presence of alcohols and amines,
R1 R2 R1 R2
BNBTS or TBBDA respectively (Scheme 117) [155]. Authors have suggested that
N N N N
MW, Solvent-Free
Ph or CCl4, r.t. Ph
or Solid Phase, r.t.
of
R1, R2 = Aryl 1) BNBTS, Ph3P 1) BNBTS, Ph3P
CH2Cl2, 0 °C CH2Cl2, 0 °C
R2R3NCOR RCO2H RCO2R1
Scheme114 2) or R2R3NH, Py, r.t. 2) R1OH, Py, r.t.
O
R1 R2 R 1
R2
CH2Cl2
0 C
31-95 %
CH2Cl2
R1, R2= H, Alkyl or Aryl 2Ph3P + SO2NCH2 SO2NCH2
2 2
Br Ph3PBr
Scheme 115 RCO2H - Sulfonamide
R1OH R2R3NH2
Miscellaneous Reactions
N-halo reagents have been also applied as catalyst in
[Ph3P-OCOR]Br
esterification reactions. N,N-dibromo(p-toluenesulfonamide)
and N,N-dichloro(p-toluenesulfonamide) catalyze acetylation
RCO2R1 R2R3NCOR
of structurally drivers alcohols by the reaction of acetic Reaction intermediate
anhydride in chloroform at room temperature (Scheme 116)
[153-154]. Scheme 118
156 www.SID.ir
Kolvari et al.
Me Me
O I O H
N Na2CO3 N
2R + S CH2 2 S CH2
H O 2 R OMe + O 2
O MeOH, dark O
2.5-42 h
65-90%
R = Alky or Aryl
Scheme 119
D
(BNIBTS) has converted aldehydes to methyl esters in the The corresponding diamine derivatives were stereoselectively
presence of methanol in good yields at room temperature obtained with good yields (Scheme 122) [159].
(Scheme 119) [156].
SI
NHAc
N-Bromosulfonamides 18 and 19 reacted with several
COOR 1) 2-NsNCl2/MeCN COOR
types of arenes in the presence of KSCN at 0 or 25 ºC to Ar Ar
2) Na2SO3(aq)
afford aryl thiocyanates (Scheme 120) [157]. NHNs-2
61-74%
SCN R = Me or Et
of
18 or 19
KSCN Scheme 122
0 or 25 C
R 2-4 h
70-98% R
CHLORAMINE T
ive
CH3 CH3
CH3 Br CH3 Br
chemical. Chloramine T acts both as a source of ‘halonium
18 19
ion’ as well as a ‘nitrogen anion’. As a result, it reacts with a
Scheme 120
wide range of functional groups, leading to an array of
molecular transformations. Chloramine T has been used in
Ar
CH3
Cl
1) o-NsNClNa
COOR CuOTf (10 mol %) COOR
Ar Ar
2) Na2SO3(aq)
NH(o-Ns)
63-76% SO2NClNa
R = Me, Et or i-Pr
20
Scheme 121
Tandem diamination of cynamic esters have been Wang and Li carried out oxidation of hydrocarbons to their
successfully carried out with N,N-di-chloro-2-nitrobenzene- corresponding ketones using the Fe(TPP)Cl/Chloramin T/O2
www.SID.ir
157
Application of N-Halo Reagents in Organic Synthesis
not found S
Chloramine T Chloramine T
O CHO
Fe(TPP)Cl MeOH, H2O
CH3CN S
24h
83 % Scheme 126
D
Aziridine, an important three-membered heterocyclic ring
system, is a useful precursor for the synthesis of several
SI
NH N biologically important compounds such as amino acids, amino
TPP: sugars and alkaloids. For this purpose Chloramine T has been
N HN
used in the presence of various catalysts (Scheme 127) [166-
172].
of
Scheme 123 R1 R3
Ts
Chloramine T, Cat. R1 N R3
Solvent or
Chloramine T was used for the conversion of some amines R2 R4 solvent-free, r.t. R2 R4
ive
N NH2
Scheme 127
ch
Chloramine T
Ru Complex
N H3O+ NH2
H
TsNClNa + NBS
Synthesis of chlorolactones by reaction of unsaturated
carboxylic acids with Chloroamine T has been reported TsNClNa
158 www.SID.ir
Kolvari et al.
2-Pyrazoline and 2-isoxazolines have been prepared by the (Scheme 130) [174]. Minakata et al. reported a new synthetic
reaction of araldehyde hydrazones and aldoximes with procedure for the amino chlorination of a variety of olefins
bifunctional olefins in the presence of Chloramine T. The and conjugated dienes to obtain vicinal chloramine derivatives
generated 2-pyrazolines were also oxidized to the with a combination of Chloramine T and carbon dioxide
corresponding pyrazoles in the course of the reaction (Scheme (Scheme 131) [175].
129) [173].
Reaction of araldoximes with 4 eq. of Chloramine T in
refluxing methanol in the presence of 1,5-diphenyl-1,4- BROMAMINE T
pentadien-3-one, produced N-(p-tolyl)-N-(p-tosyl)-benzamide
D
via addition of 2 eq. Chloramine T to the intermediate Bromamine T is the brominated analogue of Chloramine
followed by extrusion of sulfur dioxide. The 1,5-diphenyl-1,4- T. It has been used for aziridination of olefins in the presence
pentadien-3-one remained intact in the course of reaction of palladium (Scheme 132) [176]. The proposed mechanism is
SI
Ar'' N Ph
Chloramine T N
ArCOCH=CHSO2Ar' + Ar''CH=NNHPh
MeOH
ArCO SO2Ar'
of
Scheme 129
ive
OH
H N O O N SO2NH2
SO2
+ Chloramine T
MeOH
ch
+
Ph Ph
Cl Cl
Scheme 130
Ar
Cl NHTs
1) CO2 (10 atm)
Ts PhH, r.t., 6 h
+ Cl N +
R Na 2) Na2SO3 NHTs Cl
R R
21 22
Yield (%)
Entry R
21 22
1 NO2 (21a) 71 (22a) 0
2 Cl (21b) 74 (22b) 0
3 Me (21c) 54 (22c) 9
4 MeO (21d) 0 (22d) 76
Scheme 131
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159
Application of N-Halo Reagents in Organic Synthesis
shown in Scheme 133. are prepared easily starting from saccharin [179].
R1 X R1 X R1 X O
TsNBrNa, Pd (II) R2
+
R2 MeCN, rt R2 N TsHN Br N X
Ts S
2.5-81% 7-19% O
O
Ts : CH3C6H4SO2
R1, R2 = Alkyl or Aryl, X: COOMe, CONMe2, CN, X= Cl, Br, I
COMe, CO(CH3)2, SOPh, Ph, or CH2OH.
23
D
Scheme 132
NCSac has been shown to undergo electrophilic-Ritter
SI
type reaction with alkenes in acetonitrile. These reactions have
Br
NMe2
Ts N NMe2
been carried out at -42 ºC up to room temperature and two
TsNBrNa Cl Pd different products have been obtained (imidazoline or
Cl Pd O -NaCl O
Cl aziridine) (Scheme 135) [180].
O
Ts
of
N SO2Ar
NMe2
1.1 eq. NCSac N
Ts N Pd Cl -PdClBr MeCN, -42 °C
NMe2 N N-SO2Ar
Br O R +
then KOEt R
Scheme 133 EtOH,-42 °C to r.t.
R
ive
Ar = 2-EtO2CC6H4- R = Aryl
Both Fe(ІІ) and Mn-porphyrin complexes are effective
catalysts for aziridination of alkenes using Bromamine T, the Scheme 135
reaction proceeded with moderate to low stereospecificity
(Scheme 134) [177,178]. N-halosaccharines have been used for regioselective
ch
R2 MeCN, r.t.
R2 O NXSac (1.2/1.2) X= Br, Cl, I
PhO PhOCH2CH(OH)CH2X
r.t., 1% aq. CH3CN, 3-40 Min
Catalyst = Fe(Por)Cl or Mn Complex
15-95%
R1, R2, R3 = Alkyl or Aryl
NXSac (2.5/2.5)
PhOCH2CHXCH2X
Scheme 134 O reflux, CH3CN
X= Br, Cl,
PhO (75-90%)
X'= Br, Cl, I
NXSac (1.2/1.2)
PhOCH2CHX'CH2X
NX'Sac (2.5/2.5), reflux, CH3CN
N-HALOSACCHARINES
Scheme136
N-halosaccharines proved to be useful and alternative
reagents for diverse organic transformations, such as
halogenation of aromatic compounds, co-halogenation of Chlorinated and brominated aromatic compounds were
alkenes, oxidation of alcohols, halogenation of benzylic and α- prepared selectively by reaction of electron-rich aromatic
carbonylic positions, etc. N-Chloro-, N-bromo- and N- compounds with NCSac or NBSac in good yields at room
iodosaccharin, 23 (NCSac, NBSac, and NISac, respectively) temperature (Scheme 137) [182].
160 www.SID.ir
Kolvari et al.
G G
Sanchez and Fumarola reported an efficient method for
NXSac benzylic and α-carbonylic bromination using NBSac under
MeCN, rt
X mild conditions (Scheme 139) [184].
X= Br or Cl
Scheme 137
CH3 CH2Br
D
out at room temperature under neutral condition in good yields Scheme 139
and short reaction times [183].
NBSac has successfully been used for chemoselective
SI
OAc O oxidation of thiols to their corresponding disulfides in
R1 NISac R1 dichloromathane under microwave irradiation in high yields
R3 R3
15 min to 6 h I
R2
R 2 (Scheme 140) [185]. Two mechanisms were proposed for
70-90%
these reactions that both are shown in scheme 141.
R1, R2 , R3 = Alkyl or Aryl
of
O O NBSac
O O R-SH RS-SR
NISac CH2Cl2, MW
R1 R2 R1 R2 3-10 min
15 min to 6 h
I 86-94%
70-90%
ive
R= Aryl or Alkyl
R1, R2 , R3 = Alkyl or Aryl
Scheme 140
Scheme 138
Ionic mechanism:
ch
O O
R-SH + N Br N R S Br
S S
O O H
O O
Ar
I II
O
II NH + R S Br
S
O
O
2R S Br RS-SR + Br2
Radically mechanism:
O O
N Br NH
R-SH + + R S Br
S S
O O
O O
Scheme 141
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161
Application of N-Halo Reagents in Organic Synthesis
NBSac was applied as an efficient reagent for the oxidative The reactions of NCSac and NBSac with alkenes
cleavage of oximes to the corresponding aldehydes and (cyclohexene, styrene, α-methylstyrene, and 1-hexene) gave
ketones under microwave irradiation with reasonable yields the corresponding halohydrins in H2O and acetone as solvent
[186]. The same group has reported the above transformation (Scheme 144) [188].
with NBSac in water and acetone as solvent at room
temperature or by conventional heating or microwave
irradiation (Scheme 142) [187]. R1 R1
NXSac X
2 3 H2O/Me2CO HO
R R R2 R3
10-45 min
71-93%
D
NOH O X = Cl or Br
NBSac
R 1
R acetone, H2O R1
2
R2 R1 = n-Bu, Ph
r.t, reflux or MW R2 = H
R3 = H, Me
SI
R1, R2= Alkyl or Aryl
Scheme 144
Scheme 142
r.t., 24 h,CH2Cl2
OH Br
G G OH
product ratio : 66% (6-Bromo)/34% (other isomers)
NBSac Scheme 145
ch
MeCN, r.t.
5-10 min
60-77%
Br Aloui and Fairbanks have reported glycosylation reactions
by NISac in the presence of acetone and methanol for
G G
stereoselective production of acetal-linked α-glycosides
Ar
Scheme 143
BnO BnO
BnO O O
NISac, MeOH (3 eq), acetone BnO
SPh
BnO -78 to 0 °C, 2.5 h, 76% BnO
OBn
OBn O OMe
Scheme 146
162 www.SID.ir
Kolvari et al.
NOH O
took place at room temperature, mostly within short reaction NBP
1
R R2
acetone, H2O 1
R2
times and with high anti stereoselectivity. R
r.t.
R1, R2= Alkyl or Aryl
Scheme 148
OR OR
Y NBSac or NISac Y
Ph Y
Ph solvent, ROH or Ph An interesting example of the chemoselectivity of these
41-97% Br I reactions includes deoximation in the presence of primary
Y = COMe, COPh, CO2H, CO2Me, CN benzylic alcohols (Scheme 149).
R = H, Me, Et,
solvent : CH3CN or acetone/H2O Similar reactions were also carried out under microwave
D
irradiation in very short times [193]. NBP has been used for
Scheme 147
the oxidation of various organic compounds in the presence of
mercuric acetate as well as in acetic acid medium. Among
SI
them, kinetic studies were carried out for the oxidation of
N-HALOPHTHALIMIDES
glycylglycine [194], aromatic aldehydes [195,196],
acetophenone derivatives [197,198], aliphatic amines [199], α-
N-Halophthalimides (NXP) have been used in organic
hydroxy acids [200], and aspirin [201]. NBP was used for the
synthetic methodology especially in the oxidation and
of
facile oxidation of thiols to symmetrical disulfides in a
bromination reactions. In most cases these reagents are
mixture of acetone-water under microwave irradiation [202].
converted to phthalimide in the end of reactions, as a nontoxic
Both aromatic and aliphatic thiols were selectively oxidized in
chemical.
good to excellent yields (Scheme 150).
ive
N-Bromophthalimide NBP
RSH RS-SR
N-Bromophthalimide (NBP) has been found to be an acetone, H2O
MW
efficient and selective reagent for the mild oxidative cleavage
R = Aroamtic, Aliphatic
of oximes to yield the corresponding carbonyl compounds in
ch
NOH O
OH OH
+ NBP
+
Ar
acetone, H2O
r.t.
91% 99%
Unchanged alcohol
Scheme 149
R O R O
Et2O
+ N Br + NH
r.t.
72-90%
O O
Br
Scheme 151
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163
Application of N-Halo Reagents in Organic Synthesis
Reaction of substituted benzene rings with NBP, under NCP was successfully used in the first step of the ring
neutral conditions, gave the corresponding bromo derivatives expansion of peniciline V sulfoxide p-nitrobenzyl ester 24 to
with a preference for the formation of para over the ortho 3-exomethylene cephalosporin V sulfoxide p-nitrobenzyl ester
isomers (Scheme 151) [203]. NBP has also been used for the 25 (Scheme 153) [206].
bromination of some deoxyhexoses [204].
N-FLUORO REAGENTS
N-Chlorophthalimide
The photoinitiated free radical chlorination of The development of mild and selective methods for
hydrocarbons with N-chloro-phthalimide (NCP) has been introduction of fluorine into organic substrates is an important
D
reported [205]. Some evidence led authors for the suggestion objective because this element exerts unique influences upon
of the chlorination mechanism (Scheme 152). physical, chemical, and biological properties. Until quite
recently, however, the selective electrophilic fluorination of
SI
O O enolates and carbanions was difficult because most procedures
hν employed highly reactive, corrosive and toxic materials such
N Cl N + Cl
as F2, FC1O3, or MeC(O)CF3 . To overcome these limitations,
O O a range of N-fluoro reagents with different reactivities, that
O were safe and easy to handle without special equipment, was
of
O
developed [207]. These reagents are easy to handle but have
RH + N NH + R
low reactivity [208]. Recently, fluorous biphasic and triphasic
O O systems has been developed so that catalysts which has
perfluoroalkyl groups as tags are soluble in perfluoro solvents
ive
O
O H H
H H
Ar
V SCl
V S
CH3 NCP, toluene
N
N CH3 Polyvinylpyridinedivinylbenzene O CH3
O
CO2PNB CO2PNB
24
O
H
V S
1) SnCl4
N
O
2) MeOH
CO2PNB
25
V= PhOCH2CONH
PNB= p -Nitrobenzyl
Scheme 153
164 www.SID.ir
Kolvari et al.
F
N-fluoro reagents are reviewed. Sniekus et al. have reported F
flouroniation of aromatic compounds by N- [F+]
+
fluorobenzensulfonimide (NFSi) and N-fluoro-o-
F
benzenesulfonamide (NFOBS) via direct ortho metallation
Scheme 156
(Scheme 154) [214].
R R R
SO2NHMe SO2NHMe F
Br Br F F Br
F
2 eq n-BuLi 1) n-BuLi, -78 °C +
THF/ -40 °C 2) NFSi
D
N N N
NFOBS
Me Me 20-78% 4-24%
71% O
SI
R = -OCH2OCH3,
Scheme 154 O
F
Li
H3CO NMe2 NMe2
Ar
H3CO NMe2
H3CO
t-BuLi/pentane NFSi/THF
N -78 °C to 0 °C 0 °C, 2 h N
N
TIPS 40% TIPS
TIPS
TIPS = triisopropylsilylgramine
Scheme 155
NO2 F
N F reflux, 3 day F
+ +
C2H4Cl2, 20 mL
O2N
23%
9:1
Scheme 158
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165
Application of N-Halo Reagents in Organic Synthesis
Cl
N N
R R n
Cl N Cl N
F S S O n
BF4 F CF3SO2
F + +
R1 R2 CH2Cl2/ THF/ H2O R1 R2 S S N
H F
R = -NO2, -Cl, -OMe 1 2
R , R = Alkyl or Aryl
Scheme 159
Scheme 162
N-fluoro reagents is shown in Scheme 160.
D
groups [238-239] to achieve a broad range of α-fluorinated
Modified nucleosides have become useful agents for the
organic compounds such as α-fluorosulfonamides, α-
treatment of cancer and viral diseases due to their good
fluorolactams, α-fluoroketones, etc. Various N-alkylimines
SI
antitumor and antiviral activity. In particular, several
derived from acetophenones were successfully
nucleosides with substituents at 4'-position are good
monofluorinated using NFSi in a mixture of acetonitrile and
candidates as antiviral agents. 4'-Fluoro nucleoside is one of
DMF at 0 ºC. Alternatively, the same procedure in the absence
these moieties that have strong activity including anti-HIV
of DMF gave rise to diflourinated imines when performed at
activity. Jung and Toyota have synthesized 4'-
room temperature. The obtained α-fluoro and α,α-difluoro-
of
fluorothymidines using NFSi as fluorinating agent (Scheme
imines were subsequently reduced to give the corresponding
161) [223].
β-flouro and β,β-diflouroamines (Scheme 163) [237].
O O
ive
NH NH i-Pr
O N
N O N O
3.4-4 eq. i-PrNH2 1.2 eq. NFSI
ButO2C 5.5 eq LDA 0.6 eq. TiCl4 2.0eq. K2CO3
O 4.5 eq t-BuLi F O
Et2O, r.t., 15 h
NFSi ButO2C
OH
ch
O O O O F
F-L
+ +
F
F
Scheme 160
166 www.SID.ir
Kolvari et al.
chloronium ion because the 1,3,5-triazine ring has strong Et2O room temp.
Cl Cl Cl Cl
Cl Cl
D
electron-withdrawing character. However, there are few Cl Cl Cl Cl
papers concerning the utilization of TCM in organic synthesis 27 28
[240-241].
Scheme 165
SI
NHCl
N N
N-HALOSUCCINIMIDE
ClHN N NHCl
of
26
Some specific properties of N-halosuccinimides (NBS,
NCS and NIS) cause their wide application in organic
Kondo et al. have reported a simple and selective method synthesis. The scope of the application of N-halosuccinimides
for the oxidation of alcohols to the corresponding carbonyl is so wide that needs a special review for covering their
ive
compounds and oxidative lactonization of diols with TCM in chemistry. The recent application of NBS as a catalyst,
methylene chloride at room temperature under mild conditions oxidant, selective brominating reagent and the initiator in the
(Scheme 164) [242]. polymerization has been reviewed [245]. Although two
excellent review articles have been published on this subject
[1,245] we think that publishing a new review for covering the
ch
HOCH2(CH2)nCH2OH TCM
(CH2) n O new applications of these compounds in organic synthesis is
CH2Cl2, r.t.
O
necessary. N-Hallosuccinimides are commercially available
R1 R1
and extensively had been used in many fields of fine organic
TCM
Ar
O
N,N,2,3,4,5,6-Heptachloroaniline 27 and N-chloro-
2,3,4,4,5,6-hexachlorocyclohexa-2,5-dienylideneamine 28 N X
(Scheme165) can be used as chlorinating agents. Compound
28 was used as a new mild and highly regioselective O
chlorinating reagent in the chlorination of phenol and o-cresol NBS: X=Br
NCS: X=Cl
in CCl4, DMF and CH3CN. The effects of C2H5OH, C5H5N, NIS: X=I
www.SID.ir
167
Application of N-Halo Reagents in Organic Synthesis
O
O
X Y O O
N N X Y
N N S N (CH2)n N S
O N O R'
R O X Y O
Z O
X≠Y R=R' or R≠R'
X≠Y≠Z X≠Y X= Br, Cl, I
X=Y≠Z X= Cl, Br or I Y= Br, Cl, I
X≠Y=Z Y= Cl, Br or I
X= Cl, Br or I
Y= Cl, Br or I
Z= Cl, Br or I
Scheme 166
D
CONCLUSIONS Kaishi 11 (2000) 749.
SI
[5] T. Umemoto, S. Fukami, G. Tomizawa, K. Harasawa,
It should be noted that a correct and updat citation and K. Kawada, K. Tomita, J. Am. Chem. Soc. 112 (1990)
literature survey is very important for researchers to find 8563.
relevant information, pioneer ideas, and progress of any [6] G.R. Dake, M.D.B. Fenster, P.B. Hurley, B.O. Patrick,
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of
reagents indicate a wide synthetic potential of the described [7] X.L. Armesto, M. Canle, M.V. Garcia, J.A. Santaballa,
reagents and a great interest of researchers in these Chem. Soc. Rev. 27 (1998) 453.
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synthesizing various classes of organic compounds, including Org. Lett. 2 (2000) 3699.
ive
organic functional group transformation have been developed [9] F.D. Chattaway, J.M. Wadmore, J. Chem. Soc. 81
on the basis of N-halo reagents. We think that the present (1902) 191.
review article may be bringing a basic to advance information [10] Merck Index; Merck & Co Whitehouse Station, NJ,
to this very important subject and to encourage active 1996.
ch
researchers in this field for the synthesis of new N-halo [11] Y. Ura, G. Sakata, Ullmans, Encyclopedia of Industrial
reagents with different halogens such as those given in Chemistry, 6th ed., Wiley-VCH, Weinheim, 2001.
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Ar
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