A rapid and simple method for quantitative aziridination from aminobrominated derivatives of olefins under solvent-free and mild conditions

Article abstract of DOI:10.1002/cjoc.201100176

The urea-catalyzed aziridination of 1,2-vicinal haloamines derived from aminohalogenation of olefins has been developed. This rapid and simple method was carried out by simply grinding the solid mixture of the substrate, K ₂CO₃ and c

Full text of DOI:10.1002/cjoc.201100176

FULL PAPER
DOI: 10.1002/cjoc.201100176
A Rapid and Simple Method for Quantitative Aziridination from
Aminobrominated Derivatives of Olefins under Solvent-free
and Mild Conditions
,
a,b
a
a
Wei, Junfa* (魏俊发)
Chen, Zhanguo (陈战国)
Gao, Yanni (高艳妮)
a
a
a
Zhang, Peng (张鹏)
Wang, Chuanning (王传宁)
Zhao, Pengfei (赵朋飞)
a
a
Wang, Yun (王芸)
Shi, Xianying (石先莹)
a
b
School of Chemistry and Chemical Engineering, Key Laboratory for Macromolecular Science of Shaanxi
Province, Shaanxi Normal University, Xi'an, Shaanxi 710062, China
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, Gansu730000, China
The urea-catalyzed aziridination of 1,2-vicinal haloamines derived from aminohalogenation of olefins has been
developed. This rapid and simple method was carried out by simply grinding the solid mixture of the substrate,
K CO and catalytic amount of urea at room temperature in air. The reaction provides a protocol for quantitative
2
3
preparation of aziridines in a large scope of aminohalogenated derivatives of olefins including α,β-unsaturated ke-
tones, α,β-unsaturated esters and simple olefins. The possible mechanism involving an H-bond promoting deproto-
nation has been suggested for this reaction.
Keywords rapid, quantitative, aziridination, aminobromination derivative, solvent-free, olefins
[
54-57]
Introduction
lysts.
Urea (or its derivatives) was found to activate
nitro, imine and carbonyl functionality via hydrogen
bonding in organocatalytic reactions.
Aziridines are an important class of fundamental
structural unites in natural products and in pharmaceu-
ticals and flexible intermediate compounds as precur-
sors for the synthesis of many nitrogen-containing bio-
logically active molecules, such as amino acids,
β-lactam antibiotics and alkaloids.
Although the preparation of aziridines is generally
achieved by the direct aziridination of alkenes with
[58-65]
It has the
advantages of readily commercial availability, low price,
non-toxicity, smiple removal from the reaction mixture
and thus eliminates the toxicity issues associated with
metal-based catalysts besides help to achieve high
yields.
[
1-19]
As a continuation of our works on aminobromination
of olefins,
[47-52]
we now report a very rapid and simple
[
20-30]
nitrene precursors,
or by addition of Schiff bases
a promising alternative to access
method for quantitative preparation of aziridines from
,2-vicinal haloamines by grinding the substrate, anhy-
drous K CO and a catalytic amount of urea at room
temperature and under solvent-free conditions. Various
vicinal haloamines derived from electron-deficient con-
jugated and simple olefins can be converted into the
corresponding aziridines by this method in quantitative
yields under very mild conditions and in short reaction
times.
[
31-37]
with carbenes,
1
aziridines is the cyclization of 1,2-vicinal haloamines or
[38-42]
2
3
aminoalcohols with assistance of proper bases.
Li
have described the synthesis of
aziridines from aminohalogenated products of olefins
with 2.0 equiv. of K CO in good to excellent yields.
[
38]
and co-workers
2
3
Since vicinal haloamino compounds are now readily
available from a variety of olefins in good to excellent
yield and high region-and stereoselectivities via the im-
[
43-53]
proved aminohalogenations,
it is worthwhile to
Results and Discussion
develop a mild and practical aziridination for quantita-
tive preparation of aziridines from vicinal haloamines.
In recent years, organocatalyst has attracted consid-
erable interest as it presents the option of carrying out
chemical transformations without the requirement for
expensive, toxic, and scarce transition-metal cata-
Table 1 summarizes the results of aziridinations us-
ing the aminobrominated derivative of chalcone
(trans-3-bromo-2-(p-tolylsulfonamido)-2,3-diphenyl
propionone, 1a) as the standard substrate. All of the re-
actions were carried out by grinding the reaction mix-
*
E-mail: weijf@snnu.edu.cn; Tel.: ＋86-029-85303734; Fax: ＋86-029-85307774
Received July 28, 2011; accepted August 23, 2011; published online January 19, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201100176 or from the author.
Chin. J. Chem. 2012, 30, 391—399
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
391

Wei et al.
FULL PAPER
a
Table 1 Urea and various amides to aziridination of 1a
With 50 mol% K
2
CO
3
, the reaction gives 50% con-
version and the desired product obtained in 50% yield,
meaning that the basicity of KHCO , produced in the
Br
O
O
3
Grind, r.t.
reaction, is not strong enough to drive the reaction (En-
try 7). Quantitative yields of the desired aziridinated
product were achieved with stronger basic K3PO within
4
NHTs
N
Ts
1
a
1
b
a very short time (Entry 10). KOH and NaOH are more
reactive, probably due to their strong basicity (Entries
b
Entry Base, mol %
Adductive
Time
Yield /%
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
1
2
K
2
2
CO
3
3
, 100
, 100
Urea, 100
Urea, 50
Urea, 10
Urea, 5
10 min 100
15 min 100
1
2 3 2
2—14). In contrast, Na CO , NaOAc and Ca(OH) are
K
CO
unreactive for the reaction; no trace of the wanted
aziridine was detected after vigorous grinding the reac-
tion mixture for 1 h.
Most notably, the reaction did not work in the ab-
sence of base (Entry 6). Urea itself is unable to give the
aziridine without assistance of other base (Entry 6) ow-
K CO , 100
2
15 min 100
3
c
K CO , 100
2
1.0 h
1.0 h
1.0 h
1.0 h
1.0 h
1.0 h
91
57
3
c
K
2
CO
3
, 100
No
No
K CO , 50
Urea, 100
Urea, 100
Urea, 20
Urea, 100
Urea, 100
Urea, 20
Urea, 100
Urea, 100
No
NR
c
2
3
50
ing to its weak basicity (pK 0.18). This result reflects
a
Na CO , 100
NR
NR
that urea is the actual catalyst of the reaction.
2
3
a
Further investigations show that thiourea (pK 2.03),
Na CO , 100
2
3
the sulphuric analogue of urea, also catalyzes the reac-
tion well with the yield comparable to urea (Entry 21).
In order to gain insight to the role of urea, some amides
including DMI, which has no hydrogen atoms on the
amido nitrogen, have been examined under identical
conditions. The primary (acetamide and benzoylamine)
and tertiary amides (DMF, NMP and DMI) are also ef-
ficient organocatalysts for the reaction (Entries 16—19).
We speculated that the substrate could be activated by
urea, which is known as a strong H-bond acceptor and
donor, via its robust hydrogen bonding to the tolylsul-
fonamide. These observations also reveal the wide ap-
plicability of the procedure as well as tolerance to vari-
ous changes in experimental conditions.
0
1
2
3
4
4
5
6
7
8
9
0
1
K PO , 100
3
≤2 min 100
10 min 100
≤1 min 100
≤1 min 100
4
K
3
PO
4
, 100
NaOH 100
KOH 100
KOH 100
1.0 h
1.0 h
1.0 h
100
NR
NR
NaOAc, 100
Urea, 100
Ca(OH) , 100 Urea, 100
2
K
2
CO
3
, 100
DMI, 50
23 min 100
25 min 100
K CO , 100
2
DMF, 50
3
K CO , 100
2
NMP, 50
23 min 100
3
c
K CO , 100
2
CH CONH , 20
1.0 h
1.0 h
78
93
3
3
2
c
K CO , 100
2
PhCONH , 20
3
2
Most delightfully, a simple workup by wishing the
grinded mixture by common solvent such as ethyl ace-
tate and subsequent removal of the solvent gave the de-
2
K CO , 100
2
Thiourea, 50
12 min 100
3
a
Aminobrominated chlcone (0.25 mmol), anhydrous K
2
CO and
3
b
urea at room temperature; Isolated yields after extracted by
ethyl acetate and the solvent was distilled. Isolated yields after
the grinded mixture was purified by column chromatography.
1
sired aziridine with high purities revealed by its H
c
NMR spectrum. To our knowledge, this is the first time
that urea is employed as organocatalyst in a solid state
organic reaction albeit it has been used widely in the
liquid phase organocatalysis.
ture at room temperature without any organic solvent
and protection with inert gases.
The data reveal that urea is a very efficient organo-
catalyst for aziridination of the aminohalogenated chal-
cone (1a) by using K CO as base. Performing the
aziridination at room temperature led to complete con-
sumption of starting material within 10—15 min to give
the desired aziridine in quantitative yield with the urea
loading of 100 mol%, 50 mol% and 10 mol% (Entries 1
In view of the advantages of K
bases, such as low cost and mild basicity, we used
CO as the base and urea as the organocatalyst to
2 3
CO over the other
K
2
3
2
3
explore the scope and generality of the aziridination
with a series of haloamines derived from α,β-unsatu-
rated and simple olefins. All of the reactions were car-
ried out very easily under the optimized conditions (Ta-
ble 2).
—
3). None of the byproduct could be detected. Even a 5
To our surprise, all of the aminohalogenated deriva-
tives of olefins completely and cleanly converted into
the corresponding aziridines without the formation of
any unwanted waste products. The reaction time of
screened substrates is in less than 35 min, much shorter
mol% loading of urea was able to promote a smooth
aziridination reaction, affording the aziridine in an ex-
cellent yield (Entry 4). Besides, the addition of urea
gave a dramatic increase in the reaction rate and led to a
complete reaction within 15 min. The control experi-
ments showed that the non-catalyzed aziridination af-
forded only a quite low yield (57%) in the absence of
urea (Entry 5). In this case the starting material did not
disappear until 1 h monitored by TLC.
[
4]
than those previously reported in CH CN.
3
For the 1,2-vicinal haloamines chalcones, whether
electron-withdrawing or electron-donating substituents
on either side of the aryl ring of the aminobrominated
chalcones, their activity has no obvious difference by
392
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 391—399

Quantitative Aziridination from Aminobrominated Derivatives of Olefins
using the catalyst to promote this reaction. It is also
noteworthy that the aminohalogenated chalcones with
regioselective reversal gave the same aziridines
smoothly (Table 2, 1a, 2a, 4a, 6a—8a, compared with
It is worthy to point out that quite pure products
were obtained by simple workup as aforementioned.
These results indicate that our aziridination method has
advantages of subjecting to large scope of substrates,
excellent yield, time saving, mild conditions and simple
workup.
3
a, 5a, 9a—18a).
The aminohalogenated derivatives of cinnamates
gave the corresponding aziridinecarboxylates in quanti-
tative yields, too (14a—18a). The haloamines derived
from simple olefins (19a—23a) also generated the cor-
responding aziridines in quantitative yield, but needed a
relatively longer reaction time, probably due to the
higher electron density on the carbon where the subse-
The spectral and analytical data of each aziridination
product are perfectly self-consistent. In addition, the
known aziridines (1b—4b, 8b—9b, 14b—19b) have
the identical spectral data, m.p. as those previously re-
[23-25,28,30]
ported,
indicating these aziridines have a
N
quent intramolecular S 2 reaction occurs.
trans-stereochemistry.
a
Table 2 The urea-catalyzed quantitative aziridination of aminohalogenated derivatives of various olefins
b
Entry
1
Substrate
Product
Time/min
Yield
Br
O
O
N
15
Quantity
Quantity
Quantity
Quantity
Quantity
Quantity
Quantity
Quantity
NHTs
Ts
1
a
1b
Br
O
O
2
3
4
5
6
7
8
N
20
20
15
10
5
NHTs
OMe
Ts
OMe
2
a
2b
NHTsO
Br
O
N
MeO
MeO
Ts
3b
3
a
O
Br
O
N
NHTs
Ts
Cl
Cl
4
a
4
b
NHTsO
Br
O
N
MeO
Cl
MeO
Ts
Cl
5
a
5b
Br
Br
O
O
O
O
N
NHTs
F
F
Cl
F
F
Ts
6b
Cl
6
a
O
N
5
NHTs
OMe
Ts
OMe
7
a
7b
Br
O
N
5
NHTs
F
F
Ts
8
a
8b
Chin. J. Chem. 2012, 30, 391—399
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
393

Wei et al.
FULL PAPER
Continued
b
Entry
Substrate
Product
Time/min
5
Yield
O
O
NHTsO
9
N
Quantity
Quantity
Br
MeO
MeO
Ts
NO2
MeO
MeO
NO2
9
a
9
b
Br
Br NHTsO
N
1
0
Br
25
Ts
OMe
OMe
10a
1
0b
O
NHTsO
N
1
1
1
2
35
35
Quantity
Quantity
Br
1a
MeO
Ts
OMe
MeO
OMe
1
1
1b
O
NHTsO
Br
MeO
MeO
MeO
MeO
N
Ts
OMe
Br
OMe
1
2a
1
2b
Br NHTsO
O
N
1
3
Br
25
Quantity
MeO
MeO
Ts
OMe
OMe
1
3a
13b
NHTsO
O
O
O
OMe
OMe
OEt
14
15
16
N
15
15
15
Quantity
Quantity
Quantity
Br
MeO
MeO
MeO
Ts
MeO
MeO
MeO
1
4a
14b
NHTsO
OEt
N
Br
Ts
5b
1
5a
1
NHTsO
OBu-n
OBu-n
N
Br
Ts
1
6a
1
6b
NHTsO
Br
O
MeO
MeO
MeO
MeO
OMe
OMe
N
1
7
15
15
Quantity
Quantity
Ts
OMe
7a
OMe
1
17b
Br NHTsO
Br
O
OMe
OMe
N
1
3
8
Br
MeO
MeO
Ts
OMe
OMe
1
8a
18b
94
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 391—399

Quantitative Aziridination from Aminobrominated Derivatives of Olefins
Continued
b
Entry
Substrate
Product
Time/min
35
Yield
NHTs
N
1
2
9
0
Quantity
Quantity
Ts
Br
1
9b
1
9a
NHTs
Br
Ts
N
15
20b
2
0a
NHTs
Br
N
Ts
21
22
23
15
25
25
Quantity
Quantity
Quantity
2
1b
2
1a
NHTs
N
Ts
Br
2
2a
2
22b
NHTs
Ts
N
Br
2
3b
3a
a
b
Reaction conditions: the mixture of substrate (0.25 mmol), urea (0.025 mmol) and K
The isolated yield after solvent of the extraction was distilled.
2 3
CO (0.25 mmol) was grinded at room temperature.
Since the aminohalogenated derivatives we used
here have a trans-stereochemistry, the present aziridi-
nation is unambiguously a neighboring-group assistant
N
in S 2 reaction.
According to the above results and nature of urea,
such as the strong power for H-bond formation and the
weak basicity, we suggest an H-bonding intermediate
involved mechanism for the urea-catalyzed aziridination
In the first step of this mechanism, urea with the
haloamine forms a possible eight-membered ring 1 via
two H-bonds of C＝O…H—N and N—H…O＝S. Then
the proton on the arylsulfonamide transfers to oxygen
atom of urea with the formation of the nitrogen anion
and urea onium 2. The nitrogen anion, as a nucleophile,
in turn attacks the carbon atom linking a bromide in an
intramolecular S 2 reaction in the manner of neighbor-
N
ing-group assistance to generate the product and urea
hydrobromide 3. The compound 3 was deprotonated by
[
6]
(
Scheme 1).
Scheme 1 Possible mechanism of the urea-catalyzed aziridina-
tion
K
2
3
CO to recover the free urea.
Br
In conclusion, we have demonstrated that urea can
R2
R1
Br
H
catalyze aziridination of haloamino compounds with
unexpectedly high efficiency and developed a very easy
and eco-friendly procedure for aziridination of amino-
halogenated derivatives of olefins by simply grinding
O
R2
N
R1
H
S
Ar
O
S
N
O
O
Ar
Br
H
O
H
H N
N
R2
2
2 3
the solid mixture of the substrate, K CO and catalytic
R1
H
O
amount of urea at room temperature in air. The reaction
proceeded completely and cleanly to give aziridines in
quantitative yields, and thus provides a “real” green
protocol for preparation of aziridines from a large scope
of aminohalogenated derivatives of simple and elec-
tron-deficient conjugated olefins. Compared with the
standard procedures, our method has many advantages
such as quantitative yields, mild conditions, short reac-
tion times, easy work-up and elimination of the toxicity
issues related to metal catalysts.
1
N
S
O
Ar
O
H
O
H N
N
H
2
+
H
H N
N
H
2
2
KHCO3
OH
+
KBr
H
H N
N
H
3
Br-
2
R1
R2
K2CO3
N
Ts
Chin. J. Chem. 2012, 30, 391—399
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
395

Wei et al.
FULL PAPER
Experimental
N-(p-Tolylsulfonyl)-2-benzoyl-3-(4-methoxyphe-
nyl) aziridine (3b) The reaction was completed in 20
General information
1
min, 100% yield. m.p.: 115—117 ℃ (EtOH); H NMR
The 1,2-vicinal haloamine starting materials were
prepared in our laboratory. Unless otherwise stated,
other reagents were purchased from commercial sources
and used without further purification. Reaction progress
was monitored by TLC using Merck silica gel 60 F-254
with detection by UV. Flash chromatography was per-
formed using Merck silica gel 60 with freshly distilled
solvents. Columns were typically packed as slurry and
equilibrated with the appropriate solvent system prior to
(CDCl , 300 MHz) δ: 7.69 (d, J＝7.20 Hz, 2H), 7.49—
7.35 (m, 5H), 7.85 (d, J＝8.10 Hz, 2H), 6.99 (d, J＝
3
7.50 Hz, 2H), 6.75 (d, J＝8.10 Hz, 2H), 5.04 (d, J＝
6.60 Hz, 1H), 4.39 (d, J＝6.30 Hz, 1H), 3.78 (s, 3H),
1
3
2.26 (s, 3H); C NMR (CDCl , 75.45 MHz) δ: 198.6,
3
159.6, 143.2, 133.3, 129.3(3), 128.6(3), 128.2(3),
127.2(3), 113.7(3), 64.68, 61.08, 55.21, 21.40. Anal.
calcd for C23H21NO S: C 67.79, H 5.19, N 3.44; found
4
C 67.61, H 5.30, N 3.35.
1
13
use. H (300 MHz) and C (75.45 MHz) NMR spectra
were recorded using CDCl as a solvent. Chemical
N-(p-Tolylsulfonyl)-2-(4-clorobenzoyl)-3-phenyl-
aziridine (4b) The reaction was completed in 15 min,
3
1
shifts (δ) are reported relative to TMS as an internal
100% yield. m.p.: 142—144 ℃ (EtOH); H NMR
standard. Data are presented as follows: chemical shift
3
(CDCl , 300 MHz) δ: 7.99 (s, 2H), 7.71 (d, J＝7.80 Hz,
(δ), multiplicity (s＝singlet, d＝doublet, t＝triplet, q＝
2H), 7.46 (d, J＝8.40 Hz, 2H), 7.33—7.26 (m, 7H),
4.53 (d, J＝4.20 Hz, 1H), 4.19 (d, J＝4.20 Hz, 1H),
quartet, sept＝septet, m＝multiplet), coupling constant
J (Hz) and integration. Elemental analysis was carried
out on an analyzer. Melting points were uncorrected.
1
3
2.41 (s, 3H); C NMR (CDCl
3
, 75.45 MHz) δ: 189.3,
44.6, 140.8, 134.3, 132.9, 130.4(2), 129.6(2), 129.2(2),
29.0(2), 128.7(2), 127.7(2), 127.4(2), 50.30, 47.19,
1.67. Anal. calcd for C22 S: C 64.15, H 4.40,
1
1
2
General procedure
H18ClNO
3
1
,2-Vicinal haloamine (0.25 mmol), urea (1.5 mg,
N 3.40; found C 64.35, H 4.56, N 3.25.
0
.025 mmol) and anhydrous K CO (34.5 mg, 0.25
2
3
N-(p-Tolylsulfonyl)-2-(4-clorobenzoyl)-3-(4-meth-
mmol) were admixed in a agate mortar. Then, the solid
mixture was grinded at room temperature in air. The
reaction progress was monitored by TLC for each 5 min
interval. After completion of the reaction, the reaction
mixture was extracted by ethyl acetate (6 mL×3). The
organic layer was washed with brine (10 mL×3) and
oxyphenyl)aziridine (5b)
The reaction was
completed in 10 min, 100% yield. m.p. 123—125 ℃
1
3
(EtOH); H NMR (CDCl , 300 MHz) δ: 7.99 (d, J＝
8.40 Hz, 2H), 7.70 (d, J＝8.10 Hz, 2H), 7.46 (s, 3H),
7.25 (s, 3H), 4.43 (d, J＝4.20 Hz, 1H), 4.26 (d, J＝4.20
Hz, 1H), 3.81 (s, 3H), 2.41 (s, 3H); C NMR (CDCl ,
3
1
3
water, dried by anhydrous Na
2
SO
4
and concentrated
75.45 MHz) δ: 190.3, 144.8, 140.5, 135.4, 132.9, 131.3,
129.9, 129.3, 129.2, 129.0, 128.7, 128.3, 128.1, 127.8,
127.1, 126.7, 126.0, 124.6, 113.7, 55.07, 48.12, 43.36,
under reduced pressure to dryness to give almost pure
product which gave a satisfactory NMR spectrum and
analytical data.
4
20.98. Anal. calcd for C23H20ClNO S: C 62.51, H 4.56,
N 3.17; found C 62.48, H 4.53, N 3.25.
N-(p-Tolylsulfonyl)-2-(4-clorobenzoyl)-3-(4-fluro-
phenyl)aziridine (6b) The reaction was completed in
Characterization data of compounds
N-(p-Tolylsulfonyl)-2-benzoyl-3-phenylaziridine
1
(
1b) The reaction was completed in 15 min, 100%
5 min, 100% yield. m.p.: 130—132 ℃ (EtOH); H
1
yield. m.p.: 132—134 ℃ (EtOH); H NMR (CDCl
3
, 300
NMR (CDCl , 300 MHz) δ: 7.99 (d, J＝8.40 Hz, 2H),
3
MHz) δ: 8.06 (d, J＝8.40 Hz, 2H), 7.71 (d, J＝2.40 Hz,
7.70 (d, J＝7.80 Hz, 2H), 7.46 (d, J＝8.40 Hz, 2H),
2
2
1
1
2
3
H), 7.73—7.24 (m, 12H), 4.53 (s, 1H), 4.29 (s, 1H),
.39 (s, 3H); C NMR (CDCl , 75.45 MHz) δ: 190.4,
3
44.4, 140.0, 134.1, 132.9, 129.6(2), 129.0(2), 128.9(2),
28.8(2), 128.7(2), 127.7(2), 127.5(2), 50.24, 47.51,
7.33—7.24 (m, 4H), 7.05—7.00 (t, J＝8.40 Hz, 2H),
4.50 (d, J＝3.90 Hz, 1H), 4.17 (d, J＝4.20 Hz, 1H),
1
3
1
3
2.42 (s, 3H); C NMR (CDCl , 75.45 MHz) δ: 188.6,
3
164.2, 160.9, 144.2, 140.3, 135.9, 133.8, 129.8(3),
1.66. Anal. calcd for C22
H19NO
3
S: C 70.00, H 5.07, N
129.1(3), 128.7(2), 127.2(2), 115.4, 115.1, 49.55, 46.01,
21.09. Anal. calcd for C H ClFNO S: C 61.47, H 3.99,
.71; found C 70.12, H 5.13, N 3.65.
2
2
17
3
N-(p-Tolylsulfonyl)-2-(4-methoxybenzoyl-3-phe-
N 3.26; found C 61.52, H 4.06, N 3.25.
nylaziridine (2b) The reaction was completed in 20
min, 100% yield; m.p.: 109—111 ℃ (EtOH); H NMR
N-(p-Tolylsulfonyl)-2-(4-methoxybenzoyl)-3-(4-
1
flurophenyl)aziridine (7b)
The reaction was
(
CDCl
3
, 300 MHz) δ: 8.06 (d, J＝9.00 Hz, 2H), 7.82 (d,
completed in 5 min, 100% yield. m.p.: 123—125 ℃
1
J＝8.40 Hz, 2H), 7.72 (d, J＝8.40 Hz, 2H), 7.33 (s, 5H),
(EtOH); H NMR (CDCl , 300 MHz) δ: 8.03 (d, J＝
3
6
3
.96 (d, J＝9.30 Hz, 2H), 5.30 (s, 1H), 4.72 (s, 1H),
.89 (s, 3H), 2.42 (s, 3H); C NMR (CDCl , 75.45
3
8.10 Hz, 2H), 7.71 (d, J＝7.80 Hz, 2H), 7.32—7.22 (m,
4H), 7.02—6.94 (m, 4H), 4.47 (d, J＝3.90 Hz, 1H),
4.24 (d, J＝4.20 Hz, 1H), 3.89 (s, 3H), 2.41 (s, 3H); C
13
1
3
MHz) δ: 188.5, 164.4, 144.3, 136.6, 133.1, 131.4(2),
1
1
29.5(2), 129.1(2), 128.8(2), 128.6(2), 127.7, 127.6,
14.0(2), 55.62, 50.13, 47.39, 21.65. Anal. calcd for
NMR (CDCl , 75.45 MHz) δ: 190.3, 144.8, 140.5, 135.4,
132.9, 131.3, 129.9, 129.3, 129.2, 129.0, 128.7, 128.3,
3
C
23
H
21NO
4
S: C 67.79, H 5.19, N 3.44; found C 67.92,
128.1, 127.8, 127.1, 126.7, 126.0, 124.6, 113.7, 55.07,
48.12, 43.36, 20.98. Anal. calcd for C H ClNO S: C
H 5.13, N 3.65.
2
3
20
4
396
www.cjc.wiley-vch.de
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 391—399

Quantitative Aziridination from Aminobrominated Derivatives of Olefins
6
2.51, H 4.56, N 3.17; found C 62.48, H 4.53, N 3.25.
N-(p-Tolylsulfonyl)-2-benzoyl-3-(4-flurophenyl)-
7.50 Hz, 2H), 7.75 (d, J＝8.10 Hz, 2H), 7.49 (d, J＝
7.50 Hz, 2H), 7.24 (s, 2H), 6.49 (s, 2H), 4.48 (d, J＝
Aziridine (8b) The reaction was completed in 5 min,
3.90 Hz, 1H), 4.18 (d, J＝3.60 Hz, 1H), 3.79 (s, 9H),
1
13
1
00% yield. m.p.: 133—135 ℃ (EtOH); H NMR
CDCl , 300 MHz) δ: 8.045 (d, J＝8.40 Hz, 2H), 7.70
d, J＝7.80 Hz, 2H), 7.62 (d, J＝6.90 Hz, 1H), 7.51 (s,
2.41 (s, 3H); C NMR (CDCl
3
, 75.45 MHz) δ: 189.6,
(
(
3
152.9, 143.9, 135.5, 133.6, 129.0 (3), 128.5 (3), 128.3
(3), 127.3 (3), 103.9 (2), 60.31, 55.61 (2), 50.42, 46.81,
1
7
4
H), 7.48 (d, J＝7.20 Hz, 1H), 7.35—7.06 (m, 4H),
.02 (d, J＝8.10 Hz, 2H), 4.49 (d, J＝3.60 Hz, 1H),
6
21.04. Anal. calcd for C25H25NO S: C 64.22, H 5.39, N
3.00; found C 64.38, H 5.43, N 2.97.
N-(p-Tolylsulfonyl)-2-acetyl-3-(2-bromo-4,5-di-
methoxyphenyl)aziridine (13b) The reaction was
1
3
.28 (d, J＝3.60 Hz, 1H), 2.41 (s, 3H); C NMR
, 75.45 MHz) δ: 190.2, 164.7, 161.4, 144.6,
(CDCl
3
1
1
34.2, 129.6(3), 129.0(3), 128.9(3), 127.8(3), 115.9,
15.6, 50.02, 46.83, 21.66. Anal. calcd for
completed in 25 min, 100% yield. m.p.: 104—106 ℃
1
(EtOH); H NMR (CDCl
3
, 300 MHz) δ: 7.82 (d, J＝
C
22
H
18FNO
3
S: C 66.82, H 4.59, N 3.54; found C 66.93,
7.50 Hz, 2H), 7.32 (d, J＝7.50 Hz, 2H), 6.98 (s, 1H),
6.46 (s, 1H), 4,36 (d, J＝2.70 Hz, 1H), 3.86 (s, 3H),
H 4.46, N 3.65.
N-(p-Tolylsulfonyl)-2-(4-nitrobenzoyl)-3-(4-meth-
oxyphenyl)aziridine (9b) The reaction was com-
13
3.60 (s, 3H), 3.53 (s, 1H), 2.44 (s, 3H); C NMR
(CDCl , 75.45 MHz) δ: 199.0, 149.5, 147.8, 144.1,
3
pleted in 5 min, 100% yield. m.p.: 139—141 ℃ (EtOH);
H NMR (CDCl , 300 MHz) δ: 8.21 (d, J＝8.40 Hz,
3
136.4, 129.1(2), 127.3(2), 123.7, 114.8, 114.0, 110.7,
55.76, 55.25, 51.60, 48.30, 28.30, 21.06. Anal. calcd for
1
2
7
H), 7.87 (d, J＝8.10 Hz, 2H), 7.40 (d, J＝8.10 Hz, 2H),
.11—7.00 (m, 4H), 6.74 (d, J＝8.40 Hz, 2H ), 4.89 (t,
19 5
C H20BrNO S: C 50.23, H 4.44, N 3.08; found C 50.45,
H 4.46, N 3.00.
J＝8.40 Hz, 1H), 4.34 (d, J＝7.5 Hz, 1H), 3.79 (s, 3H),
N-(p-Tolylsulfonyl)-2-methoxycarbonyl-3-(4-
methoxyphenyl)aziridine (14b) The reaction was
1
3
2
1
1
1
3
.30 (s, 3H); C NMR (CDCl , 75.45 MHz) δ: 190.3,
44.8, 140.5, 135.7, 135.2, 132.9, 131.5, 129.9, 129.2,
28.9, 128.5, 127.8, 127.1, 126.7, 126.0, 124.6, 113.8,
13.6, 55.06, 48.12, 43.36, 20.98. Anal. calcd for
completed in 15 min, 100% yield. m.p.: 107—109 ℃
1
(EtOH); H NMR (CDCl
3
, 300 MHz) δ: 7.62 (d, J＝
7.80 Hz, 2H), 7.22 (d, J＝7.80 Hz, 2H), 7.09 (d, J＝
8.10 Hz, 2H), 6.82 (d, J＝8.10 Hz, 2H), 4.48 (d, J＝
5.40 Hz, 1H), 4.16—4.11 (m, 1H), 3.80 (s, 3H), 3.43
23 20 2 6
C H N O S: C 61.05, H 4.46, N 6.19; found C 61.48,
H 4.53, N 6.55.
N-(p-Tolylsulfonyl)-2-benzoyl-3-(2-bromo-4,5-di-
methoxyphenyl)aziridine (10b) The reaction was
13
3
(s,3H), 2.40 (s, 3H); C NMR (CDCl , 75.45 MHz) δ:
170.1, 159.7, 143.4, 136.7, 129.4(2), 128.6, 128.1(2),
127.3(2), 113.8(2), 64.89, 60.68, 55.23, 52.14, 21.53.
Anal. calcd for C18H19NO S: C 59.82, H 5.30, N 3.88;
5
completed in 25 min, 100% yield. m.p.: 130—131 ℃
1
(
EtOH); H NMR (CDCl
3
, 300 MHz) δ: 8.091 (d, J＝
7
7
6
4
2
1
1
5
.20 Hz, 2H), 7.83 (d, J＝8.10 Hz, 2H), 7.63 (d, J＝
found C 59.95, H 5.16, N 3.75.
N-(p-Tolylsulfonyl)-2-ethoxycarbonyl-3-(4-meth-
oxyphenyl)aziridine (15b)
.20 Hz, 1H), 7.52 (d, J＝7.50 Hz, 2H), 7.30 (s, 2H),
.98 (s, 1H), 6.52 (s, 1H), 4.64 (d, J＝3.90 Hz, 1H),
.13 (d, J＝3.90 Hz, 1H), 3.85 (s, 3H), 3.62 (s, 3H),
The reaction was
completed in 15 min, 100% yield. m.p.: 106—108 ℃
1
3
1
.42 (s, 3H); C NMR (CDCl
3
, 75.45 MHz) δ: 189.1,
3
(EtOH); H NMR (CDCl , 300 MHz) δ: 7.64 (d, J＝
49.4, 147.9, 144.0, 136.5, 135.5, 133.5, 129.1(2),
28.5(2), 128.2(2), 127.4(2), 124.8(2), 114.9, 110.4,
5.75, 55.26, 50.17, 47.45, 21.06. Anal. calcd for
6.60 Hz, 2H), 7.22 (d, J＝6.90 Hz, 2H), 7.11 (d, J＝
6.60 Hz, 2H), 6.82 (d, J＝6.90 Hz, 2H), 4.49 (d, J＝
3.60 Hz, 1H), 4.13—4.09 (d, J＝5.70 Hz, 1H), 3.83 (s,
3H), 3.42—3.28 (m, 2H), 2.39 (s, 3H), 1.11 (t, J＝6.90
24 5
C H22BrNO S: C 55.82, H 4.29, N 2.71; found C 55.93,
H 4.82, N 2.67.
5
Hz, 3H). Anal. calcd for C19H21NO S: C 60.78, H 5.64,
N-(p-Tolylsulfonyl)-2-(4-methoxybenzoyl)-3-(4-
methoxyphenyl)aziridine (11b) The reaction was
N 3.73; found C 60.52, H 5.86, N 3.75.
N-(p-Tolylsulfonyl)-2-n-butyloxycarbonyl-3-(4-
methoxyphenyl)aziridine (16b) The reaction was
completed in 35 min, 100% yield. m.p.: 130—132 ℃
1
(
EtOH); H NMR (CDCl
3
, 300 MHz) δ: 8.05 (d, J＝
completed in 15 min, 100% yield. m.p.: 84—86 ℃
1
8
4
2
3
.70 Hz, 2H), 7.70 (d, J＝7.80 Hz, 2H), 7.29—7.20 (m,
(EtOH); H NMR (CDCl
3
, 300 MHz) δ: 7.64 (d, J＝
H), 6.95 (d, J＝8.40 Hz, 2H ), 6.86 (d, J＝8.40 Hz,
H), 4.39 (s, 1H), 4.34 (d, J＝4.20 Hz, 1H), 3.88 (s, 3H),
7.50 Hz, 2H), 7.23 (d, J＝8,10 Hz, 2H), 7.10 (d, J＝
7.80 Hz, 2H), 6.83 (d, J＝7.50 Hz, 2H), 4.49 (d, J＝
5.10 Hz, 1H), 4.14—4.09 (m, 1H), 3.80 (s, 3H), 3.40—
3.30 (m, 2H), 2.39 (s, 3H), 1.26—1.09 (m, 4H), 0.85 (t,
13
3
.80 (s, 3H), 2.39 (s, 3H); C NMR (CDCl , 75.45
MHz) δ: 188.3, 163.8, 159.6, 143.7, 132.7, 130.8(2),
1
3
1
1
29.1, 128.9, 128.7(2), 127.1, 126.6(2), 123.9, 113.5(3),
13.1, 55.06, 54.79, 48.77, 47.39, 21.06. Anal. calcd for
3
J＝7.20 Hz, 3H); C NMR (CDCl , 75.45 MHz) δ:
168.9, 159.2, 142.8, 136.5, 128.9(2), 128.5, 127.6(2),
126.8(2), 113.3(2), 64.56, 60.25, 54.72, 29.75, 20.96,
24 5
C H23NO S: C 65.89, H 5.30, N 3.20; found C 65.48,
H 5.63, N 3.25.
5
18.38, 14.47, 13.06. Anal. calcd for C21H25NO S: C
N-(p-Tolylsulfonyl)-2-benzoyl-3-(3,4,5-trimeth-
62.51, H 6.25, N 3.47; found C 62.85, H 6.16, N 3.75.
N-(p-Tolylsulfonyl)-2-methoxycarbonyl-3-(3,4,5-
trimethoxyphenyl)aziridine (17b) The reaction was
completed in 15 min, 100% yield. m.p.: 144—146 ℃
oxyphenyl) aziridine (12b)
The reaction was
completed in 35 min, 100% yield. m.p.: 143—144 ℃
1
(
3
EtOH); H NMR (CDCl , 300 MHz) δ: 8.08 (d, J＝
Chin. J. Chem. 2012, 30, 391—399
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
397

Wei et al.
FULL PAPER
1
(EtOH); H NMR (CDCl
3
, 300 MHz) δ: 7.81 (d, J＝
NMR (CDCl
3
, 300 MHz) δ: 7.82 (d, J＝7.50 Hz, 2H),
7
4
1
1
1
4
.80 Hz, 2H), 7.31 (d, J＝7.50 Hz, 2H), 6.42 (s, 2H),
.39 (s, 1H), 3.82—3.77 (m, 12H), 3.47 (d, J＝2.40 Hz,
7.33 (d, J＝7.50 Hz, 2H), 2.70 (s, 1H), 2.62 (d, J＝6.90
Hz, 1H), 2.43 (s, 3H), 1.53 (s, 1H), 1.32—1.23 (m, 6H),
0.87—0.80 (m, 3H). Anal. calcd for C13H19NO S: C
2
1
3
H), 2.43 (s, 3H); C NMR (CDCl
3
, 75.45 MHz) δ:
65.4, 149.4, 147.9, 144.0, 136.7, 129.1(2), 127.2(2),
24.1, 114.8, 113.6, 110.4, 60.31, 55.74, 55.20, 52.68,
7.57, 46.51, 29.17, 21.07. Anal. calcd for C20H23NO S:
7
61.63, H 7.56, N 5.53; found C 61.52, H 7.58, N 5.52.
Acknowledgement
C 57.00, H 5.50, N 3.32; found C 57.15, H 5.46, N 3.55.
The authors are grateful to the National Natural Sci-
ence Foundation of China (No. 20572066), the Natural
Science Foundation of Shaanxi Province (No.
N-(p-Tolylsulfonyl)-2-methoxycarbonyl-3-(2-
bromo-4,5-dimethoxyphenyl)aziridine (18b)
reaction was completed in 15 min, 100% yield. m.p.:
1
7
6
The
1
2
009JM2011), and the Innovation Foundation of Post-
graduate Cultivation of Shaanxi Normal University (No.
008CXB009).
3
08—110 ℃ (EtOH); H NMR (CDCl , 300 MHz) δ:
.87 (d, J＝7.80 Hz, 2H), 7.33 (d, J＝7.80 Hz, 2H),
.98 (s, 1H), 6.42 (s, 1H), 4,54 (d, J＝6.00 Hz,1H), 3.90
2
(
s, 3H), 3.85 (s, 3H), 3.39 (d, J＝3.30 Hz, 1H), 2.44 (s,
13
3
1
1
3
H); C NMR (CDCl , 75.45 MHz) δ: 165.4, 149.4,
References
47.9, 144.0, 136.7, 129.1(2), 127.3(2), 124.1, 114.8,
13.6, 110.4, 55.74, 52.68, 47.54, 46.51, 29.17, 21.07.
[
1] Pearson, W. H.; Lian, B. W.; Bergmeier, S. C. Comprehensive
Heterocyclic Chemistry II, Vol. 1, Eds.: Katritzky, A. R.; Rees, C.
W.; Scriven, E. F. V. Pergamon, New York, 1996, pp. 1—97.
6
Anal. calcd for C19H20 BrNO S: C 48.52, H 4.29, N 2.98;
found C 48.75, H 4.46, N 2.85.
[2] Tanner, D. Angew. Chem., Int. Ed. 1994, 33, 599.
[3] Ibuka, T. Chem. Soc. Rev. 1998, 27, 145.
N-(p-Tolylsulfonyl)-2-phenylaziridine (19b) The
[
4] Hu, X. E. Tetrahedron 2004, 60, 2701.
reaction was completed in 35 min, 100% yield. m.p.: 84
1
[5] Li, A. H.; Dai, W. M.; Aggarwal, V. K. Chem. Rev. 1997, 97, 2341.
—
86 ℃ (EtOH); H NMR (CDCl
3
, 300 MHz) δ: 7.88—
[
[
[
6] Müller, P.; Fruit, C. Chem. Rev. 2003, 103, 2905.
7] Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247.
8] Dahanukar, V. H.; Zavialov, L. A. Curr. Opin. Drug Discovery Dev.
7
2
.86 (m, 2H), 7.35—7.20 (m, 7H), 3.80—3.76 (m, 1H),
1
3
.98 (d, J＝7.20 Hz, 1H), 2.42 (s, 3H), 2.38 (s, 1H); C
, 75.45 MHz) δ: 144.6, 136.0, 129.7(2),
28.5(2), 128.3(2), 127.9(2), 126.5(2), 41.02, 36.93,
1.05. Anal. calcd for C15 S: C 65.91, H 5.53, N
NMR (CDCl
3
2
002, 5, 918.
1
2
5
[9] Ghorai, M. K.; Shukla, D.; Das, K. J. Org. Chem. 2009, 74, 7013.
[10] Forbeck, E. M.; Evans, C. D.; Gilleran, J. A.; Li, P.; Joullié, M. M. J.
Am. Chem. Soc. 2007, 129, 14463.
11] Tomasini, C.; Vecchione, A. Org. Lett. 1999, 1, 2153.
12] Ghorai, M. K.; Das, K.; Shukla, D. J. Org. Chem. 2007, 72 5859.
13] Minakata, S.; Hotta, T.; Oderaotoshi, Y.; Komatsu, M. J. Org. Chem.
H15NO
2
.12; found C 65.72, H 5.43, N 5.34.
[
[
[
N-(p-Tolylsulfonyl)-indeneaziridine (20) The re-
action was completed in 15 min, 100% yield. m.p.: 160
1
℃
(EtOH); H NMR (CDCl
3
, 300 MHz) δ: 7.83 (d, J＝
2
006, 71, 7471.
7
1
.50 Hz, 2H), 7.41—7.17 (m, 6H), 4.30 (d, J＝4.80 Hz,
[
14] Li, Z.; Fernández, M.; Jacobsen, E. N. Org. Lett. 1999, 1, 1611.
13
H), 3.40 (s, 1H), 3.13 (s, 2H), 2.43 (s, 3H); C NMR
, 75.45 MHz) δ: 144.5, 143.6, 138.2, 135.4,
29.7(2), 128.7, 127.8(2), 126.7, 125.6, 125.1, 50.16,
4.96, 34.65, 21.68. Anal. calcd for C16 S: C
7.34, H 5.30, N 4.91; found C 67.52, H 5.56, N 4.72.
-[4-Methyl-7-(phenylsulfonyl)]-7-azabicyclo-
4.1.0]heptane (21b) The reaction was completed in
[15] Han, H.; Bae, I.; Yoo, E. J.; Lee, J.; Do, Y.; Chang, S. Org. Lett.
2004, 6, 4109.
(CDCl
3
[
[
[
16] Liu, Y.-K.; Li, R.; Yue, L.; Li, B.-J.; Chen, Y.-C.; Wu, Y.; Ding,
L.-S. Org. Lett. 2006, 8, 1521.
17] Sureshkumar, D.; Ganesh, V.; Vidyarini, R. S.; Chandrasekaran, S. J.
Org. Chem. 2009, 74, 7958.
18] Musio, B.; Clarkson, G. J.; Shipman, M.; Florio, S.; Luisi, R. Org.
Lett. 2009, 11, 325.
1
4
6
H15NO
2
7
[
1
3
1
5 min, 100% yield. m.p.: 55—56 ℃; H NMR (CDCl
3
,
[19] Li, P.; Evans, C. D.; Joullié, M. M. Org. Lett. 2005, 7, 5325.
[20] Evans, D. A.; Faul, M. M.; Bilodeau, M. T.; Anderson, A. B.; Bar-
nes, M. D. J. Am. Chem. Soc. 1993, 115, 5328.
00 MHz) δ: 7.83 (d, J＝8.70 Hz, 2H), 7.33 (d, J＝8.70
Hz, 2H), 2.976 (t, J＝1.50 Hz, 2H), 2.44 (s, 3H), 1.81—
[
21] Lowenthal, R. E.; Masamune, S. Tetrahedron Lett. 1991, 32, 7373.
[22] Hodgson, D. M.; Humphreys, P. G.; Ward, J. G. Org. Lett. 2006, 8,
95.
23] Chanda, B. M.; Vyas, R.; Bedekar, A. V. J. Org. Chem. 2001, 66,
0.
1
.77 (m, 4H), 1.27—1.23 (m, 2H), 1.21—1.18 (m, 2H);
1
3
C NMR (CDCl
27.6(2), 39.78(2), 22.76(2), 21.60, 19.39(2). Anal.
S: C 62.12, H 6.82, N 5.57; found
C 62.19, H 6.92, N 5.50.
-[4-Methyl-9-(phenylsulfonyl)]-9-azabicyclo-
6.1.0]nonane (22b) The reaction was completed in
3
, 75.45 MHz) δ: 144.0, 136.9, 129.6(2),
9
1
[
calcd for C13H17 NO
2
3
[24] Han, J.; Li, Y.-F.; Zhi, S.-J.; Pan, Y.; Timmonsc, C.; Li, G. Tetra-
hedron Lett. 2006, 47, 7225.
9
[
25] Thakur, V. V.; Sudalai, A. Tetrahedron Lett. 2003, 44, 989.
[26] Denolf, B.; Leemans, E.; Kimpe, N. D. J. Org. Chem. 2007, 72,
211.
[
1
2
5 min, 100% yield. m.p. 123—124 ℃ (EtOH); H
NMR (CDCl , 300 MHz) δ: 7.82 (d, J＝7.80 Hz, 2H),
.33 (d, J＝7.80 Hz, 2H), 2.78 (d, J＝9.30 Hz, 2H),
.44 (s, 3H), 2.01 (d, J＝13.5 Hz, 2H), 1.56—1.26 (m,
0H). Anal. calcd for C15 S: C 64.48, H 7.58, N
3
3
[
27] Ando, T.; Kano, D.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahe-
dron 1998, 54, 13485.
28] Ma, L.; Du, D.-M.; Xu, J.-X. J. Org. Chem. 2005, 70, 10155.
7
2
1
5
[
H21NO
2
[29] Jain, S. L.; Sain, B. Tetrahedron Lett. 2003, 44, 575.
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2
N-(p-Tolylsulfonyl)-2-n-butylaziridine (23b) The
1
reaction was completed in 25 min, 100% yield. H
2
398
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