Bromosulfonamidation of alkenes using S,S-dimethyl-N-(p-toluenesulfonyl)sulfilimine

Article abstract of DOI:10.1055/s-2001-14910

A new method for the bromosulfonamidation of olefins using a combination of S,S-dimethyl-N-(p-toluenesulfonyl)sulfilimine and N-bromosuccinimide is disclosed herein.

Full text of DOI:10.1055/s-2001-14910

LETTER
851
Bromosulfonamidation of Alkenes using S,S-Dimethyl-N-(p-toluene-
sulfonyl)sulfilimine♣
Sadagopan Raghavan,* S. Ramakrishna Reddy, K. A. Tony, Ch. Naveen Kumar, S. Nanda
Organic Division I, Indian Institute of Chemical Technology, Hyderabad 500 007, India
E mail: purush101@ yahoo.com
Received 6 April 2001
NTs
Abstract: A new method for the bromosulfonamidation of olefins
using a combination of S,S-dimethyl-N-(p-toluenesulfonyl)sulfil-
imine and N-bromosuccinimide is disclosed herein.
S
NHTs
Br
Me
Me
a.
R2
R2
R1
R1
NBS, CH2Cl2
Key words: bromosulfonamidation, sulfilimine, N-Bromosuccin-
imide
b. Aq. Satd. NaHCO3
Scheme 1
Sulfilimines 1, which have the IUPAC name "sulfimide"
remain less explored as synthetic reagents,1 as compared
with the analogous sulfoxides 2, which have found broad
use in the area of stereoselective synthesis.2 There has re-
cently been a resurgence of interest, reflected in the re-
ports regarding the synthesis of enantiomerically enriched
sulfilimines3 and their applications.4 To the best of our
knowledge, in all the chemistry of sulfilimines reported so
far, the sulfimide moiety (S=NR) does not participate in
the reaction. We disclose herein, a transformation wherein
the sulfimide moiety functions as a nucleophile in the
N-bromosuccinimide (NBS) promoted, bromosulfonami-
dation of alkenes.
The results of the study are summarized in Table. S,S-
Dimethyl-N-Ts-sulfilimine was prepared from dimethyl
sulfide and Chloramine-T by the Mann-Pope reaction.15
Dichloromethane and chloroform were found to be the
solvents of choice for the reaction.16 The reaction proba-
bly proceeds by an ionic mechanism which would explain
the observed regioselectivity; the nucleophilic attack tak-
ing place at the carbon atom (anomeric and benzylic) best
able to stabilize a partial positive charge. Triacetyl-D-glu-
cal 3, afforded product 4 as the only bromosulfonamide,
while related substrate 5, yielded sulfonamides 6 and 7 in
a 2: 1 ratio. Dihydropyran afforded isomers 9 and 10. The
structures were assigned to the products by comparing
The vicinal halo amine functionality is a structural unit of
importance in synthetic organic chemistry.5 A number of
synthetic approaches have been developed to secure this
functionality. N,N-Dihalo sulfonamides,6 N-halo carbam-
ates,7 N,N-dihalo carbamates,8 N,N-dibromo phosphora-
midate,9 halo azide,10 halogen isocyanates,11 cyanamide/
NBS,12 sulfonamide/iodonium bis-sym-collidine perchlo-
rate,13 are the reagents which effect the transformation of
alkenes to products with a halo amine moiety. These
methods are not without limitations. The reaction of diha-
lo sulfonamides is not general and straightforward. The
products resulting from dihalo sulfonamides and dihalo
carbamates have a nitrogen-halogen bond which is to be
reduced. The N-halo carbamates require stoichiometric
quantities of metal halide as promoters. The dihalo phos-
phoramidates are not readily available and the halo azides
suffer from the drawback of not being easily handled. The
utility of the sulfonamide-I+ combination has been dem-
onstrated for glycals only. The study of highly regio- and
stereoselective amino halogenation of olefins therefore
still remains important and challenging.
1
their H NMR data with literature values of known (9,
10,17 and 166a) or related compounds (4, 6, 7,13 12, 14,9
and 186a).
Stilbene afforded the product 14, resulting from trans ad-
dition of bromonium ion and sulfimide across the alkene
which is supported by its 1H NMR spectral data. The rate
of the reaction and the yield varied with the substrates.
The electron rich substrates 3, 5, 8 and 11 afforded prod-
ucts in good yield and the reaction proceeded within min-
utes at ice-salt temperature (3, 5 and 8) or in a couple of
hours at ambient temperature (11). The reaction was slow
and the yield low with stilbene and the styrenes. The reac-
tion was very sluggish with simple mono substituted alk-
enes and di substituted cyclic olefins and was not
investigated further. In general this method affords prod-
ucts in comparable or lower yields than the other ionic
methods.
The reaction probably proceeds as illustrated in Scheme 2.
The bromonium ion I, would be attacked at the benzylic
position, best able to stabilize a partial positive charge, to
afford the salt II, which on hydrolysis, would afford the
bromosulfonamide and dimethyl sulfoxide. It was found
best to introduce water only after all the starting material
was consumed (monitored by TLC examination) to ex-
clude bromohydrin formation, that could arise from the
Drawing a parallel with the reactivity of dimethyl sulfox-
ide with alkenes initiated by NBS,14 we decided to explore
the reaction of alkenes with NBS using S,S-dimethyl-N-
(p-toluenesulfonyl)sulfilimine, as the nucleophile
(Scheme 1).
Synlett 2001 No. 6, 851–853 ISSN 0936-5214 © Thieme Stuttgart · New York

852
S. Raghavan et al.
LETTER
Table Bromosulfonamide from olefins
a Yield of chromatographically purified product. b Products 6 and 7 formed in a 2:1 ratio. c Products 9 and 10 formed in a
1:2 ratio.
participation of the liberated dimethyl sulfoxide as a nu- sive and readily prepared, to access vicinally substituted
cleophile.18
haloamines which are useful to elaborate important syn-
thetic intermediates such as aziridines, vicinal diamines
and N-acylated-2-amino-2-desoxy saccharides.
In conclusion, we disclose herein a novel use for S,S-dim-
ethyl-N-(p-toluenesulfonyl)sulfilimine which is inexpen-
Synlett 2001, No. 6, 851–853 ISSN 0936-5214 © Thieme Stuttgart · New York

LETTER
Bromosulfonamidation of Alkenes
853
H
Me
Me
O
H
S
Me
Me
NTs
S
O
NHTs
N
NTs
Br
Br
Br
O
12
11
I
II
Scheme 2
Acknowledgement
(16) Typical experimental procedure: To the solution of
triacetyl-D-glucal (115 mg, 0.5 m mol) in dry dichloromethane
(2 mL) was added S,S-dimethyl-N-Ts-sulfilimine15b (138 mg,
0.6 m mol) and the mixture cooled to -15 °C. NBS (133 mg,
0.75 m mol) was added in one portion to the above solution
and the mixture let stir under nitrogen for 30 min., when TLC
examination revealed completion. A saturated aqueous
solution of sodium bi- carbonate (2 mL) was added. The
reaction mixture was diluted with more dichloromethane and
the layers separated. The organic layer was subsequently
washed with water, brine, dried over sodium sulfate and
evaporated to afford the crude mixture which was purified by
column chromatography to afford the bromosulfonamide in
75% yield. 4: 1H NMR (400 M Hz, CDCl3) 7.78 (d, J = 8.0
Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 5.58 (d, J = 10Hz, 1H), 5.25
(t, J = 10 Hz, 1H), 4.98 (m, 2H), 4.6 (d, J = 2.5 Hz, 1H), 4.0
(dd, J = 12.5, 4.0 Hz, 1H), 3.82 (dd, J = 12.5, 2.5 Hz, 1H), 3.6
(m, 1H), 2.45 (s, 3H), 2.1 (s, 3H), 2.04 (s, 3H), 12: 1H NMR
(200 M Hz, CDCl3) 7.88 (d, J = 8 Hz, 2 H), 7.41-7.12 (m, 6
H), 4.91 (dd, J = 7.2, 5.0 Hz, 1H), 4.61 (d, J = 7.2 Hz, 1H),
4.32 (m, 1H), 3.60 (dd, J = 16.3, 6.8 Hz, 1H), 3.21 (dd,
J = 16.3, 5.0 Hz, 1H), 2.50 (s, 3H). 14: 7.53-6.85 (m, 14 H),
5.25 (d, J = 8.0 Hz, 1H), 5.15 (d, J = 5.7 Hz, 1H), 4.75 (dd,
J = 8.0, 5.7 Hz, 1H), 2.32 (s, 3H).
S. R is thankful to Dr. J. S. Yadav, Head, Org. Div. I and Dr. K. V.
Raghavan, Director, I.I.C.T, for their constant support and encoura-
gement. KAT, CNK and SN are thankful to CSIR, New Delhi for
fellowship.
References and Notes
♣ IICT Communication No. 4673
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dichloromethane used was dried and distilled over calcium
hydride, the bromohydrin probably arises from salt III, formed
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Me
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Me
N
H
O
O
S
O
O
OH
Ar
H
N
I
Br
Br
O
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III
Bromohydrin
Article Identifier:
1437-2096,E;2001,0,06,0851,0853,ftx,en;S11800ST.pdf
Synlett 2001, No. 6, 851–853 ISSN 0936-5214 © Thieme Stuttgart · New York