Synthesis of Functionalized N-Arylsulfonyl Aziridines from α,β-Unsaturated Esters, Amides, Ketones, and Nitriles Using N,N-Dichloroarylsulfonamides as Nitrogen Source

Article abstract of DOI:10.1081/SCC-120030324

A convenient and general aziridination process has been developed for the synthesis of functionalized N-arylsulfonylaziridines bearing an alkoxycarbonyl, acyl, cyano, and carboxamide group at C₂. The two-step sequence involves addition of N,N-dichloroarylsulfonamide to the appropriate olefin in the presence of Cu(acac)₂, treatment of the resultant chlorosulfonamide with Na₂SO₃, followed by cyclization with NaOH to give the appropriate aziridine in good yields. The reaction is found to be an anti-stereoselective.

Full text of DOI:10.1081/SCC-120030324

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Synthesis of Functionalized N‐Arylsulfonyl Aziridines
from α,β‐Unsaturated Esters, Amides, Ketones,
and Nitriles Using N,N‐Dichloroarylsulfonamides as
Nitrogen Source
Upender K. Nadir a & Anamika Singh a
a Chemistry Department, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi,
110016, India
Version of record first published: 21 Aug 2006.
To cite this article: Upender K. Nadir & Anamika Singh (2004): Synthesis of Functionalized N‐Arylsulfonyl Aziridines from
α,β‐Unsaturated Esters, Amides, Ketones, and Nitriles Using N,N‐Dichloroarylsulfonamides as Nitrogen Source, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 34:7, 1337-1347
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 7, pp. 1337–1347, 2004
Synthesis of Functionalized N-Arylsulfonyl
Aziridines from a,b-Unsaturated Esters,
Amides, Ketones, and Nitriles Using
N,N-Dichloroarylsulfonamides
as Nitrogen Source
*
Upender K. Nadir and Anamika Singh
Chemistry Department, Indian Institute of Technology, New Delhi, India
ABSTRACT
A convenient and general aziridination process has been developed for the
synthesis of functionalized N-arylsulfonylaziridines bearing an alkoxycar-
bonyl, acyl, cyano, and carboxamide group at C2. The two-step sequence
involves addition of N,N-dichloroarylsulfonamide to the appropriate olefin in
the presence of Cu(acac)2, treatment of the resultant chlorosulfonamide with
Na2SO3, followed by cyclization with NaOH to give the appropriate aziridine
in good yields. The reaction is found to be an anti-stereoselective.
Key Words: Aziridination; N-Arylsulfonyl aziridine; p-Toluenesulfona-
mide; Alkenes.
*
Correspondence: Upender K. Nadir, Chemistry Department, Indian Institute of
Technology, Delhi, Hauz Khas, New Delhi 110016, India; Fax: 91-11-2658-2037;
E-mail: ukn@chemistry.iitd.ac.in.
1337
DOI: 10.1081/SCC-120030324
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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1. INTRODUCTION
Aziridines are important precursors for the synthesis of alkaloids, amino-
acids, aminosugars, and b-lactams[1] and have been used as ligands in metal
catalyzed asymmetric transformations.[2] N-Arylsulfonylaziridines have
recently attracted attention due to their susceptibility towards nucleophilic
ring opening and ring expansion reactions.[3]
We have been interested in exploring various synthetic uses of N-arylsulf-
onylaziridines and have employed them to access azetidines[4] and imidazoli-
dinones[5] (for eventual conversion to enantiomerically pure diamines and
diaminoacids). So we were looking for a convenient and cost-effective pro-
cedure for the preparation of functionalized N-arylsulfonylaziridines. An
attractive route to aziridines could involve a single atom transfer to double
bonds.[6] (For epoxidation see Ref. [6c].) But carbene addition to imines[7]
and reaction of thermally or photochemically generated nitrenes with olefins[8]
suffer from poor yields and formation of side products. Transition metal
catalyzed addition of nitrenes generated from [N-(arenesulfonyl)-imino]
phenyliodinanes[9,10](PhI ¼ NSO2Ar) to olefins have been more successful.
However, PhI ¼ NSO2Ar is expensive and unstable and the procedure is
inconvenient[11] because it yields beside aziridines, iodobenzene and oxyge-
nated hydrocarbons as substantial by-products. Several literature reports
have described[12] the use of chloramine-T (N-chloro-N-sodio-p-toluenesulfo-
namide) as nitrene source for the aziridination of alkenes but these reactions
fail in the case of electron deficient a,b-unsaturated olefins.[13] To the best
of our knowledge, there are no references on the synthesis of functionalized
aziridines based on dichloramine-T till date. We now report this synthetic
transformation through a two step sequence involving addition of N,N-
dichloroarylsulfonamide to the a,b-unsaturated olefins in the presence of
Cu(acac)2, followed by cyclization with NaOH.
2. RESULTS
Although the aziridination of electron-deficient olefins using PhI ¼ NTs
and Cu(II) catalyst has been reported, the method suffers from the following
restrictions.
(1) Costly reagents and catalysts; (2) inconvenience in handling reagents
and catalysts; (3) poor yields.
In view of above limitations these reactions were investigated with
dichloramine-T using transition metal catalyzed addition of N-arylsulfonyl
group to functionalized a,b-unsaturated olefins by using N,N-dichloroarylsul-
fonamide as nitrogen source and a Cu(II) catalyst.

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Synthesis of N-Arylsulfonyl Aziridines
1339
We have previously prepared N-arylsulfonylaziridines by addition of
N,N-dichloroarylsulfonamides to the appropriate olefin, followed by cleavage
of the N–Cl bond with NaHSO3 and cyclization with a base.[14] However, the
procedure did not work when the olefin had a functional group like –CN,
–COOR, –COR, or –CONH2 on it, since addition of dichloramine-T to the
olefin was unsuccessful.[15] Recently Li et al.[16] have reported somewhat
similar addition to a,b-unsaturated esters to prepare amino halogenated pro-
duct. We followed similar procedure using Cu(acac)2 as catalyst instead of
Cu(OTf)2 to synthesize amino chlorinated products and then cyclized these
amino chlorinated products using a base to get the corresponding aziridines.
The N,N-dichloro-p-toluenesulfonamide (TsNCl2) employed in this
sequence was prepared by the treatment of p-toluenesulfonamide with com-
mercial bleaching powder, followed by CH3COOH acidification.[14c,17] Both
Cu(OTf)2 and Cu(acac)2 were tried for the reaction and we found that yields
are comparable in both cases. Therefore, we chose Cu(acac)2 as the catalyst
because it is less costly and easy to handle.
For cyclization several bases in different solvents were tried, e.g., NaOH–
aq. EtOH, NaOH–aq. MeOH, NaH–THF but best results were obtained with
NaOH in aq. THF.
In some cases (entries 1g, 1i, 1j; Table 1), more concentrated NaOH sol-
ution was required, whereas the sulfonamide corresponding to entry 1a and
1b decomposed by a higher concentration of the base. The reaction was gener-
alized by reacting a variety of electron-deficient a,b-unsaturated olefins with
Table 1. Metal catalyzed aziridination of olefins using N,N-dichloro-
p-toluenesulfonamide.
Ref. of
Product
Product
(yield %)b
Substrate
R1
R2
R3
EWG
1a
1b
1ca
1da
1e
H
Ph
H
H
H
H
H
H
H
H
H
H
H
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
COMe
COPh
CN
[9c]
[9c]
[18]
—
2a (80)
2b (76)
2c (55)
2d (68)
2e (60)
2f (70)
2g (60)
2h (52)
2i (60)
2j (75)
H
Cl–C6H4
NO2–C6H4
H
H
CH3
Ph
CH3
H
[19]
[19]
[20]
[21]
[21]
[22]
1f
1ga
1h
1i
Cl–C6H4
H
H
H
Ph
H
H
CN
CONH2
1j
H
aThe reaction needed 2 eqiuv. of TsNCl2 and 36–48 hr.
bIsolated yield.

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Nadir and Singh
N,N-dichloro-p-toluenesulfonamide using Cu(acac)2 as catalyst. The reaction
sequence is represented in Sch. 1 with the results summarized in Table 1. In all
cases reported in Table 1, only trans-isomer was observed by 1H NMR analysis
of the crude products,a therefore the reaction seems to be stereoselective.[16]
Olefins, bearing electron-withdrawing groups like chloro or nitro on the phenyl
ring (entries 1c, 1d, and 1g) needed 2 equiv. of dichloramine-T and greater reac-
tion time for best results. All these reactions were associated with the formation
of p-toluenesulfonamide as by-product along with the aziridine.
We also examined some dichloramine-T analogs in the aziridination
reaction. The aziridination of methyl acrylate using dichloramine-B, which
contains no substituents on the benzene ring, as nitrogen source afforded the
corresponding aziridine in 65% yield. Similarly p-chloro substituted analog
also reacted with methyl acrylate to give aziridine in 50% yield.
To compare the efficiency of the present method with Evan’s method for
functionalized aziridines we have listed in Table 2 yields of some aziridines
using same catalyst, i.e., Cu(acac)2.
3. CONCLUSION
In conclusion, we have developed a cost-effective and general method for
the synthesis of functionalized N-arylsulfonylaziridines in good yields. The
reaction is performed easily at room temperature and requires a relatively
cheaper copper complex, Cu(acac)2 as catalyst. The possibility of developing
it into an asymmetric aziridination process is being explored.
Scheme 1. Electron withdrawing groups (EWG) ¼ COOMe, COR, CN, CONH2.

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Synthesis of N-Arylsulfonyl Aziridines
1341
Table 2. Comparison of yields of some functionalized aziridines with present
and Evan’s method.
Yield (%)
Entry
Aziridines
Cu(II) catalyst
Evan’s
Present
1
2
3
4
2a
2b
2e
2f
Cu(acac)2
Cu(acac)2
32
36
38
56
80
76
60
70
Cu(CH3CN)4ClO4
Cu(acac)2
4. EXPERIMENTAL
1H and 13C NMR spectra were recorded on a DPX-300 Brucker spec-
trometer. Data are reported as follows: Integration, chemical shift in parts per
million (ppm) from tetramethylsilane (TMS) on the d scale, multiplicity (s ¼
singlet, d ¼ doublet, t ¼ triplet, dd ¼ double doublet, and m ¼ multiplet), coup-
ling constant in Hertz (Hz), and assignment. Melting points were determined
using a ELECTRON-Bombay micro melting point apparatus and are uncor-
rected. IR absorption spectra were recorded on Nicolet 5DX FTIR instrument
and values are reported in cm21. Monitoring of the reactions was performed
using silica gel TLC plates (silica Merck 60 F254). Spots were visualized by
UV light at 254 nm. Column chromatography was performed using silica gel
(60–120 mesh). Organic solvents were purified by standard procedures.
4.1. General Procedure for Aziridination of Functionalized
a,b-Unsaturated Olefins by N,N-Dichloroarylsulfonamides
Into a dry round-bottom flask was added functionalized a,b-unsaturated
olefin (0.74mmol) and freshly distilled acetonitrile (2.5mL). The contents
˚
were stirred at room temperature and 4 A molecular sieves (220mg), TsNCl2
(0.89 mmol, 1.20equiv.), and Cu(acac)2 (8 mol%) were added. The resulting
solution was stirred at room temperature for 24hr. Saturated aqueous Na2SO3
solution (3 mL) was added dropwise at the end of the reaction. Two phases
were separated and the aqueous phase extracted with ethylacetate
(3 ꢀ 15mL). The combined organic layers were washed with 10% aqueous
ammonia and brine, dried over anhydrous sodium sulfate, and concentrated to
dryness. The resultant solid was purified by crystallization (benzene–pet. ether)
to give the corresponding sulfonamide. To a solution of the above sulfonamide
in THF was added dropwise 10% aqueous sodium hydroxide solution in THF.

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Nadir and Singh
This mixture was stirred (15–20 mins) at room temperature. Completion of
the reaction was checked by TLC. The reaction mixture was extracted with
ethylacetate (3 ꢀ 10 mL) and washed with water (3 ꢀ 10 mL) and dried
over anhydrous Na2SO4. The residue was purified by column chromatography
on silica gel (eluent: hexane/EtOAc) to give the corresponding aziridine.
N-(p-Toluensulfonyl)-2-methoxycarbonyl aziridine (2a). Colorless oil
(lit.,[10c] colorless oil); nmax (cm21) 1748 (CO), 1332 and 1163 (SO2) cm21
;
dH (300MHz, CDCl3, Me4Si) 7.84 (2H, d, J 8.3, Ar-H), 7.36 (2H, d, J 8.2,
Ar-H), 3.74 (3H, s, OCH3), 3.34 (1H, dd, J 7.1, 4.1, CHCO2Me), 2.76 (1H, d,
J 7.2, cis-CH), 2.56 (1H, d, J 4.1, trans-CH), 2.45 (3H, s, Ar-CH3); dC (75 MHz,
CDCl3, Me4Si) 167.1, 145.2, 133.9, 129.8, 128.1, 52.7, 35.6, 31.9, 21.5.
trans- N-( p-Toluenesulfonyl)-2-methoxycarbonyl-3-phenylaziridine
(2b). White crystalline solid, m.p. 44–458C (lit.,[10c] 44.2–44.68C); nmax (cm21
)
1752 (CO), 1335 and 1165 (SO2); dH (300 MHz, CDCl3, Me4Si) 7.77 (2H, d, J
8.3, Ar-H), 7.31–7.24 (7H, m, Ar-H), 4.44 (1H, d, J 3.9, C–H), 3.85 (s, 3H, s,
OCH3), 3.53 (1H, d, J 4.0, C–H), 2.41 (3H, s, Ar-CH3); dC (75 MHz, CDCl3,
Me4Si) 166.2, 144.3, 136.9, 132.5, 129.5, 128.9, 128.5, 127.4, 127.3, 53.1,
47.6, 46.7, 21.6.
N-( p-Toluenesulfonyl)-2-methoxycarbonyl-3-(p-chlorophenyl) aziri-
dine (2c). Solid, m.p. 1108C; nmax (cm21) 1742 (CO), 1328 and 1162
(SO2); dH (300 MHz, CDCl3, Me4Si) 7.71 (2H, d, J 8.2, Ar-H), 7.31–7.24
(6H, m, Ar-H), 4.39 (1H, d, J 3.9, C–H), 3.78 (3H, s, OCH3), 3.49 (1H, d,
J 3.9, C–H), 2.43 (3H, s, Ar-CH3); dC (75 MHz, CDCl3, Me4Si) 165.5,
144.5, 136.5, 134.6, 131.0, 129.6, 128.7, 127.8, 127.4, 53.2, 47.9, 45.5, 21.6.
N-( p-Toluenesulfonyl)-2-methoxycarbonyl-3-(p-nitrophenyl) aziridine
(2d). Solid, m.p. 132–1358C (Found: C, 54.04; H, 4.26; N, 7.26.
C17H16N2O6S requires C, 54.25; H, 4.28; N, 7.44%); nmax (cm21) 1758 (CO),
1376 and 1163 (SO2), 1543 (NO2); dH (300 MHz, CDCl3, Me4Si) 8.16 (2H, d,
J 8.7, Ar-H), 7.80 (2H, d, J 8.2, Ar-H), 7.43 (2H, d, J 8.6, Ar-H), 7.33 (2H, d,
J 6.6, Ar-H), 4.53 (1H, d, J 3.6, C–H), 3.88 (3H, s, OCH3), 3.51 (1H, d, J
3.5, C–H), 2.44 (3H, s, Ar-CH3); dC (75 MHz CDCl3 Me4Si) 165.4, 148.1,
144.9, 140.0, 136.4, 134.6, 129.7, 128.1, 127.4, 123.8, 53.3, 47.5, 45.9, 21.6.
Methyl 3,3-dimethyl-N-( p-toluenesulfonyl) aziridine-2-carboxylate
(2e). Viscous oil; nmax (cm21) 1738 (CO), 1335 and 1165 (SO2); dH
(300 MHz, CDCl3, Me4Si) 7.86 (2H, d, J 8.1, Ar-H), 7.32 (2H, d, J 8.1, Ar-
H), 3.70 (3H, s, OCH3), 3.51 (1H, s, C–H), 2.44 (3H, s, Ar-CH3), 1.83 (3H,
s), 1.39 (3H, s); dC (75 MHz, CDCl3, Me4Si) 166.7, 144.1, 137.2, 129.5,
127.2, 52.3, 52.2, 48.7, 21.5, 21.3, 20.7.
trans-2-Acetyl-3-phenyl-N-( p-toluenesulfonyl) aziridine (2f). nmax (cm21
)
1680 (CO), 1335 and 1165 (SO2); dH (300 MHz, CDCl3, Me4Si) 7.93 (2H,
d, J 8.1, Ar-H), 7.55–7.24 (7H, m, Ar-H), 4.16 (1H, d, J 7.8, C–H), 3.62
(1H, d, J 7.9, C–H), 2.47 (3H, s, Ar-CH3), 1.74 (3H, s,); dC (75 MHz,

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1343
CDCl3, Me4Si) 200.3, 144.3, 136.4, 131.5, 129.5, 128.9, 128.3, 127.9, 127.3,
50.9, 48.5, 28.4, 21.4.
trans-2-Benzoyl-3-( p-chlorophenyl-N-(p-toluenesulfonyl) aziridine (2g).
Solid, m.p. 148–149.58C (lit.,[22] 149–1508C); nmax (cm21) 1696 (CO), 1330
and 1161 (SO2); dH (300 MHz, CDCl3, Me4Si) 7.98 (2H, d, J 8.1, Ar-H), 7.65
(7H, m, Ar-H), 4.16 (1H, d, J 7.8, C–H), 3.62 (1H, d, J 7.9, C–H), 2.47 (3H,
s, Ar-CH3), 1.74 (3H, s); dC (75 MHz, CDCl3, Me4Si) 200.3, 144.3, 136.4,
131.5, 129.5, 128.9, 128.3, 127.9, 127.3, 50.9, 48.5, 28.4, 21.4.
N-( p-toluenesulfonyl) aziridine-2-carboxamide (2h). Waxy solid; nmax
(cm21) 3408 and 3370 (NH2), 1674 (CO), 1338 and 1164 n(SO2); dH (300 MHz,
CDCl3, Me4Si) 7.75 (2H, d, J 8.0, Ar-H), 7.30 (2H, d, J 7.9, Ar-H), 3.17 (1H,
dd, J 7.3 and 4.0), 2.74 (1H, d, J 7.6), 2.37 (1H, d, J 4.1), 2.40 (3H, s, Ar-CH3).
2-Cyano-N-(p-toluenesulfonyl)aziridine (2i). Oil; nmax (cm21) 2218
(CN), 1338 and 1164 (SO2); dH (300 MHz, CDCl3, Me4Si) 7.8 (2H, d, J 7.9),
7.41(2 H, d, J 2), 3.23 (1H, dd), 2.89 (1H, d, J 7.0), 2.66 (1H, d, J 3.6), 2.48
(3H, s, Ar-CH3); dC (75 MHz, CDCl3, Me4Si) 146.1, 133.05, 130.15, 128.22,
115.03, 32.11, 23.43, 21.73.
2-Cyano-3-phenyl-N-(p-toluenesulfonyl)aziridine (2j). nmax (cm21
)
2260 (CN), 1339 and 1165 (SO2); dH (300 MHz, CDCl3, Me4Si) 7.9 (2H, d,
J 7.9), 7.31 (7H, m), 4.32 (1H, d), 3.06 (1H, d), 2.48 (3H, s); dC (75 MHz,
CDCl3, Me4Si) 146.6, 134.3, 133.01, 130.9, 130.01, 129.03, 129.01, 127.01,
114.01, 46.02, 32.01, 22.04.
ACKNOWLEDGMENT
This work was supported by project funds from Council of Scientific and
Industrial research (CSIR), New Delhi (Government of India organization).
The financial support provided by CSIR, New Delhi to AS in the form of
senior research fellowship is acknowledged.
NOTE
a. All products (reported in Table 1) are known in literature (except 2d).
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Received in the UK October 31, 2003

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