A direct route to C-vinylaziridines: Reaction of N-sufonylimines with allylic ylides under phase-transfer conditions or with preformed ylides at low temperature

Article abstract of DOI:10.1021/jo952245d

Allylic sulfonium salts 3, 5, 7, 11, 12, 13, and arsonium salt 14 react with aromatic, heteroaromatic, and α,β-unsaturated N-sulfonylimines under solid-liquid phase-transfer conditions in the presence of KOH at room temperature to produce, respectively, vinyl-, (α-phenylvinyl)-, and [α-(trimetriylsilyl)-vinyl]aziridines in excellent yields within several minutes. In some cases, pyrroline compound 9 is obtained as a minor product. This aziridination reaction has also been carried out with preformed ylides, generated from sulfonium salts 3, 7, arsonium salt 14, and telluronium salts 15, 16 with a base in THF at -78°C. In most examples, quantitative yields were achieved. However, the trans/ cis selectivity of the reaction was not high in either case. A semistable allylic sulfonium ylide, i.e., dimethylsulfonium 3-(trimethylsilyl)allylide, was found to not undergo an expected [2,3]-σ-rearrangement and so can also be used in this reaction.

Full text of DOI:10.1021/jo952245d

J . Org. Chem. 1996, 61, 4641-4648
4641
A Dir ect Rou te to C-Vin yla zir id in es: Rea ction of N-Su fon ylim in es
w ith Allylic Ylid es u n d er P h a se-Tr a n sfer Con d ition s or w ith
P r efor m ed Ylid es a t Low Tem p er a tu r e
An-Hu Li,† Li-Xin Dai,*,† Xue-Long Hou,† and Min-Bo Chen‡
Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 354 Fenglin Lu, Shanghai 200032, China, and Laboratory of Computer Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China
Received December 20, 1995X
Allylic sulfonium salts 3, 5, 7, 11, 12, 13, and arsonium salt 14 react with aromatic, heteroaromatic,
and R,â-unsaturated N-sulfonylimines under solid-liquid phase-transfer conditions in the presence
of KOH at room temperature to produce, respectively, vinyl-, (â-phenylvinyl)-, and [â-(trimethylsilyl)-
vinyl]aziridines in excellent yields within several minutes. In some cases, pyrroline compound 9
is obtained as a minor product. This aziridination reaction has also been carried out with preformed
ylides, generated from sulfonium salts 3, 7, arsonium salt 14, and telluronium salts 15, 16 with a
base in THF at -78 °C. In most examples, quantitative yields were achieved. However, the trans/
cis selectivity of the reaction was not high in either case. A semistable allylic sulfonium ylide, i.e.,
dimethylsulfonium 3-(trimethylsilyl)allylide, was found to not undergo an expected [2,3]-σ-
rearrangement and so can also be used in this reaction.
Sch em e 1
In tr od u ction
Because of their useful chemical reactivity, aziridines
have seen extensive applications in organic synthesis.1,2
Among the variously functionalized aziridines, vinylaziri-
dine 1 has proven to be the most interesting, and many
useful intermediates have derived from it through vari-
ous transformations3 and rearrangements.4 However,
methods for the preparation of vinylaziridines are few.
A multistep sequence with low overall yields and trouble-
some operations has often been used.3a,4a,d Therefore, the
development of practical and facile methods for preparing
vinylaziridines is warranted. A retrosynthetic analysis
of vinylaziridine reveals that paths a and b are two
discrete disconnections of the nitrogen-containing three-
membered ring (Scheme 1). For path b, desired chemose-
lectivity might be diminished when unsymmetric dienes
are used.5 Path a involves the reaction of an imine with
a vinylcarbene or an allylic ylide. To our knowledge, no
method using vinylcarbenes has been reported. For the
allylic ylide route, two problems must first be solved: the
activation of the imine6 and the prevention of [2,3]-σ-
rearrangement7 of the allylide if sulfonium ylide is used.
In our preliminary paper,8 we reported an efficient
method for preparing N-sulfonylvinylaziridines via an
ylide route by very simple operations under extremely
mild conditions. We disclose herein our detailed inves-
tigation of this reaction.
† Laboratory of Organometallic Chemistry.
‡ Laboratory of Computer Chemistry.
Resu lts a n d Discu ssion
X Abstract published in Advance ACS Abstracts, J une 15, 1996.
(1) (a) Davis, F. A.; Reddy, G. V.; Liu, H. J . Am. Chem. Soc. 1995,
117, 3651. (b) Wong, C.-H.; Provencher, L.; Porco, J . A., J r.; J ung, S.-
H.; Wang, Y.-F.; Chen, L.; Wang, R.; Steensma, D. H. J . Org. Chem.
1995, 60, 1492. (c) Schkeryantz, J . M.; Danishefsky, S. J . J . Am. Chem.
Soc. 1995, 117, 4722. (d) Tian, X.; Hudlicky, T.; Ko¨nigsberger, K. J .
Am. Chem. Soc. 1995, 117, 3643. (e) Hudlicky, T.; Tian, X.; Ko¨nigs-
berger, K.; Rouden, J . J . Org. Chem. 1994, 59, 4037. (f) Shao, H.; Zhu,
Q.; Goodman, M. J . Org. Chem. 1995, 60, 790.
P r ep a r a tion of N-Su lfon ylvin yl-, (â-P h en ylvin yl)-,
an d [â-(Tr im eth ylsilyl)vin yl]azir idin es u n der P h ase-
Tr a n sfer Con d ition s. In contrast to the extensive
research reported on ylide olefination, cyclopropanation,
and epoxidation reactions,9 aziridination via an ylide
route has attracted little attention and only a few
examples (limited to a methylene group transferring to
CdN bond) have appeared in the literature.10 This is due
to the low reactivity of N-alkyl- oraryl-substituted imines
(2) For recent reviews on the chemistry of aziridines: (a) Tanner,
D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (b) Tanner, D. Angew.
Chem. 1994, 106, 625. (c) Tanner, D. Pure Appl. Chem. 1993, 65, 1319.
(d) Hudlicky, T.; Seoane, G.; Price, J . D.; Gadamasetti, K. G. Synlett
1990, 433.
(3) (a) Satake, A.; Shimizu, I.; Yamamoto, A. Synlett 1995, 64. (b)
Ibuka, T.; Nakai, K.; Habashita, H.; Hotta, Y.; Fujii, N.; Mimura, N.;
Miwa, Y.; Taga, T.; Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1994,
33, 652. (c) Fujii, N.; Nakai, K.; Tamamura, H.; Otaka, A.; Mimura,
N.; Miwa, Y.; Taga, T.; Yamamoto, Y.; Ibuka, T. J . Chem. Soc., Perkin
Trans. I 1995, 1359. (d) Spears, G. W.; Nakanishi, K.; Ohfune, Y.
Synlett 1991, 91. (e) Tanner, D.; Somfai, P. Bioorg. Med. Chem. Lett.
1993, 3, 2415.
(4) For vinylaziridine to pyrroline rearrangement: (a) Hudlicky, T.;
Reed, J . W. In Comprehesive Organic Synthesis; Trost, B. M. Fleming,
I., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, pp 899-970. For aza-
[2,3]-Wittig rearrangement: (b) A° hman, J .; Somfai, P. J . Am. Chem.
Soc. 1994, 116, 9781. (c) Somfai, P.; A° hman, J . Tetrahedron Lett. 1995,
36, 1953. (d) A° hman, J .; Somfai, P. Tetrahedron Lett. 1995, 36, 303.
(5) (a) Mishra, A.; Rice, S. N.; Lwowski, W. J . Org. Chem. 1968, 33,
481. (b) Atkinson, R. S.; Rees, C. W. Chem. Commun. 1967, 1230.
(6) Volkmann, R. A. In Comprehesive Organic Synthesis; Trost, B.
M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 1, pp 355-
396.
(7) (a) LaRochelle, R. W.; Trost, B. M.; Krepski, L. J . Org. Chem.
1971, 36, 1126. (b) Trost, B. M.; LaRochelle, R. Tetrahedron Lett. 1968,
3327.
(8) Partial results from Table 2 have been published as a com-
munication: Li, A.-H.; Dai, L.-X.; Hou, X.-L. J . Chem. Soc., Chem.
Commun. 1996, 491.
(9) Huang, W.-F. Ylide Chemistry; Central China Normal University
Press: Wuhan, 1993 (in Chinese).
S0022-3263(95)02245-6 CCC: $12.00 © 1996 American Chemical Society

4642 J . Org. Chem., Vol. 61, No. 14, 1996
Li et al.
Sch em e 2
reaction under solid-liquid phase-transfer conditions,
considering that in our previous attempt to prepare
vinyloxirane with sulfonium salt 5 the reaction of the
dimethylsulfonium cinnamylide, generated in situ by the
deprotonation of sulfonium salt 5 with KOH, with Ph-
CHO to form an epoxide was much faster than the [2,3]-
σ-rearrangement of the same ylide. We were lucky to
find that the reaction of the activated imine, N-tosylimine
2c, with dimethylcinnamylsulfonium bromide (5) is
tremendously different from that of the unactivated
imines, in the presence of KOH at room temperature. The
reaction afforded vinylaziridine 6c much more readily
than we expected (eq 4 in Scheme 2).
In order to optimize the conditions for the reaction
shown in eq 4 in Scheme 2, the effects of solvent and base
on this reaction were investigated (Table 1).
Acetonitrile, dichloromethane, and tetrahydrofuran are
suitable solvents for this reaction, acetonitrile being the
best. Among various bases, solid KOH gave the highest
yield. Under such conditions, the reaction proceeded so
fast that no aldehyde from the hydrolysis of the imine
was detected. Interestingly, even an organic base NEt3
could be used in this reaction (entry 9 in Table 1).
Results from the reaction of N-sulfonylimines with
dimethylallylsulfonium bromide (3a ), diphenylallylsul-
fonium perchlorate (3b), dimethylcinnamylsulfonium
bromide (5), [3-(trimethylsilyl)allyl]dimethylsulfonium
bromide (7a ), and [3-(trimethylsilyl)allyl]diphenylsul-
fonium perchlorate (7b) under the optimized condition
are summarized in Table 2.
A variety of allylic ylides, i.e., from the simplest
dimethylsulfonium allylide to cinnamylide and silylated
dimethylsulfonium allylide, and various N-sulfonylimines
containing aromatic, heteroaromatic, and R,â-unsatur-
ated moieties perform in this aziridination reaction. But,
in the case of the R,â-unsaturated N-sulfonylimine (entry
19 in Table 2), we obtained a mixture of N-(benzene-
sulfonyl)-trans-2,3-bis(â-phenylvinyl)aziridine (trans-6g)
and N-(benzenesulfonyl)-cis-4,5-diphenyl-4,5-dihydroaze-
pine (18), which was derived from a rapid, room temper-
ature Cope rearrangement of the cis isomer (cis-6g)15
(Scheme 3).
The reaction was complete, usually within several
minutes in almost quantitative yields in most examples.
However, the trans/cis ratio of the product was rather
low and needed to be improved. Attempts to improve the
trans/cis selectivity of this reaction by introducing an
ortho-substituent, such as a methoxy (entries 2, 11, 14,
21, and 25 in Table 2) or two chlorine atoms (entry 3 in
Table 2) on the phenyl ring proved to be inefficient. The
steric hindrance only diminished the yield and prolonged
the reaction time (entry 3 in Table 2). A bulky R-naph-
thyl substituent on the imino carbon of N-tosylimine also
failed to improve the trans/cis ratio of the product (entries
9, 12, 23, and 26 in Table 2). A possible mechanism for
this reaction is shown in Scheme 4.
toward the attack of nucleophiles relative to that of
carbonyl compounds and Michael acceptors, an activator
being required in several instances.11 Our success with
asymmetric epoxidations by way of optically active sul-
fonium ylides under phase-transfer conditions12 encour-
aged us to apply our ylides to the aziridination of imines,
considering that aziridines are sometimes even more
useful intermediates in the synthesis of nitrogen-contain-
ing biologically important substances.1a,4b,c In Scheme 2,
the reaction of dimethylsulfonium cinnamylide, gener-
ated from salt 5, with PhCHdNPh gave no sign of
aziridine either under phase-transfer conditions (eq 1)
or using a preformed ylide (eq 2). From both experi-
ments, the recovered imine and the rearranged allylide
were obtained. The same is true even for the more
reactive sulfinimines (eq 3). It is the previously-
mentioned two obstacles that make these ylide aziridi-
nation reactions unsuccessful. The former obstacle, i.e.,
the low reactivity of common imines, may be overcome
by using activated imines. The atomic net charges of
PhCHO, PhCHdNPh, and PhCHdNTs according to
semiempirical AM1 calculations (HyperChem Release 3
from Hypercuban, Inc., and Autodesk, Inc., 1993) indicate
that the qualitative order of electrophilicity is PhCHdNTs
> PhCHO . PhCHdNPh.13 In addition, we observed
that sulfonium salt 5 reacts with PhCHO in the presence
of solid KOH in CH3CN at room temperature to furnish
the corresponding vinyloxirane in 74% yield within 30
min.14 So, the reactive N-tosylimine 2c might be a
suitable candidate for our designed ylide aziridination
reaction from the perspective of reactivity. The second
obstacle, i.e., the [2,3]-σ-rearrangement of allylic sulfo-
nium ylides, might be overcome by carrying out our
(10) For methylene group transfer: (a) Ruano, J . L. G.; Fernandez,
I.; Hamdouchi, C. Tetrahedron Lett. 1995, 36, 295. (b) Mosset, P.; Gre´e,
R. Synth. Commun. 1985, 15, 749. (c) Tewari, R. S.; Awasthi, A. K.;
Awasthi, A. Synthesis 1983, 330. (d) Elmes, B. C. Tetrahedron Lett.
1971, 4139. (e) Corey, E. J .; Chaykovsky, M. J . Am. Chem. Soc. 1965,
87, 1353. (f) Corey, E. J .; Chaykovsky, M. J . Am. Chem. Soc. 1962, 84,
3782. (g) Franzen, V.; Driesen, H.-E. Chem. Ber. 1963, 96, 1881. (h)
Hortmann, A. G.; Robertson, D. A. J . Am. Chem. Soc. 1967, 89, 5974.
(i) Hortmann, A. G.; Robertson, D. A. J . Am. Chem. Soc. 1972, 94, 2758.
For ethylidene group transfer: (j) J ohnson, C. R.; J aniga, E. R. J . Am.
Chem. Soc. 1973, 95, 7692.
One proton R to the sulfur atom of sulfonium salt I is
first extracted by the base to form an ylide II. Imine is
then attacked by the ylidic carbon to produce a zwitte-
rionic intermediate III. Sulfide is subsequently lost,
furnishing vinylaziridine IV.
(11) (a) Keck, G. E.; Enholm, E. J . J . Org. Chem. 1985, 50, 146. (b)
Wang, D.-K.; Dai, L.-X.; Hou, X.-L. Tetrahedron Lett. 1995, 36, 8649.
(12) Li, A.-H.; Dai, L.-X.; Hou, X.-L.; Huang, Y.-Z.; Li, F.-W. J . Org.
Chem. 1996, 61, 489.
Several allylic sulfonium salts were employed to in-
vestigate the effect of ligands connected to the sulfur
(13) The atomic net charge data for the carbon in the CdX bonds of
PhCHdNTs, PhCHO, and PhCHdNPh are, respectively, 0.313, 0.223,
and -0.009.
(15) (a) Stogryn, E. L.; Brois, S. J . J . Org. Chem. 1965, 30, 88. (b)
Pommelet, J . C.; Chuche, J . Can. J . Chem. 1976, 54, 1571. (c)
Pommelet, J . C.; Chuche, J . Tetrahedron Lett. 1974, 3897.
(14) Li, A.-H. Unpublished results.

A Direct Route to C-Vinylaziridines
J . Org. Chem., Vol. 61, No. 14, 1996 4643
Ta ble 1. Effects of Solven t a n d Ba se on th e Ylid e Azir id in a tion of N-Su lfon ylim in es 2 w ith Dim eth yla llylsu lfon iu m
Br om id e (3a ) u n d er P h a se-Tr a n sfer Con d ition sa
reaction
time (min)
recovered
entry
R1
phenyl
phenyl
phenyl
p-chlorophenyl
p-chlorophenyl
p-chlorophenyl
p-chlorophenyl
p-chlorophenyl
p-chlorophenyl
p-chlorophenyl
p-chlorophenyl
p-chlorophenyl
base/solvent
KOH/CH3CN
KOH/CH2Cl2
KOH/THF
KOH/CH3CN
NaOH/CH3CN
50% NaOH(aq)/CH3CN
K2CO3/CH3CN
KF.Al2O3/CH3CN
NEt3/CH3CN
yield,b %
trans/cisc
aldehyde,d %
1
2
3
4
5
6
7
8
9
5
6
5
93 (4h )
83 (4h )
81 (4h )
82 (4g)
63 (4g)
53 (4g)e
71 (4g)
53 (4g)
32 (4g)
26 (4g)
17 (4g)
14 (4g)
58/42
52/48
66/34
47/53
58/42
62/38
60/40
63/37
61/39
59/41
56/44
52/48
0
5
9
5
0
15
20
55
60
40
80
150
300
18
23
13
22
37
56
62
39
10
11
12
Ba(OH)2.8H2O/CH3CN
LiOH.H2O/CH3CN
KF.2H2O/CH3CN
a
All reactions were carried out under solid-liquid phase-transfer conditions at room temperature in a ratio of imine:sulfonium salt:
base ) 1:1.2:1.2 on a 0.5-mmol scale in a solvent. Isolated yields based on imine. c Determined by 300 MHz 1H-NMR analysis. Produced
b
d
by the hydrolysis of imine. e 18% of 2-(p-chlorophenyl)-3-vinyloxirane (trans/cis: 58/42) was isolated.
Ta ble 2. P r ep a r a tion of Vin yl-, (â-P h en ylvin yl)-, a n d [â-(Tr im eth ylsilyl)vin yl]a zir id in es 4, 6, or 8 by th e Rea ction of
Su lfon iu m Sa lts 3, 5, or 7 a n d N-Su lfon ylim in es 2 u n d er P h a se-Tr a n sfer Con d ition sa
reaction
time (min)
entry
R1
R2
R3
R
X
yield,b %
cis/transc
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
p-nitrophenyl
o-methoxyphenyl
2,6-dichlorophenyl
3-pyridinyl
p-methylphenyl
p-methoxyphenyl
p-chlorophenyl
phenyl
Me
Me
Me
Me
H
H
H
H
H
H
H
H
H
H
H
H
H
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Me
Me
Me
Me
Me
Me
Me
Me
Me
Ph
Br
Br
Br
Br
Br
Br
Br
Br
5
15
80
5
5
15
5
5
30
5
10
8
5
10
5
5
5
5
5
4
18
4
20
4
54 (4a )
92 (4b)
36 (4c)d
82 (4d )e
84 (4e)
95 (4f)
82 (4g)
93 (4h )
75 (4i)
69 (4g)
77 (4b)
75 (4i)
75 (6a )
96 (6b)
95 (6c)
89 (6d )
94 (6e)
96 (6f)
92 (6g)
97 (8a )
96 (8b)
86 (8c)
93 (8d )
85 (8a )
97 (8b)
97 (8d )
53/47
61/39
56/44
65/35
34/66
45/55
53/47
58/42
55/45
44/56
27/73
46/54
51/49
70/30
63/37
75/25
57/43
52/48
64/36f
29/71
32/68
42/58
35/65
25/75
45/55
29/71
H
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
H
Me
H
Me
Me
Me
Me
Me
Me
Me
R-naphthyl
Br
p-chlorophenyl
o-methoxyphenyl
R-naphthyl
ClO4
ClO4
ClO4
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
ClO4
ClO4
ClO4
Ph
Ph
p-nitrophenyl
o-methoxyphenyl
phenyl
p-methylphenyl
p-methoxyphenyl
p-chlorophenyl
trans-PhCHdCH
phenyl
o-methoxyphenyl
p-chlorophenyl
R-naphthyl
phenyl
o-methoxyphenyl
R-naphthyl
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Ph
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
Ph
Ph
12
15
a
All reactions were carried out under solid-liquid phase-transfer conditions at room temperature in a ratio of imine:sulfonium salt:
KOH(s) ) 1:1.2:1.2 on a 0.5-mmol scale in acetonitrile. Isolated yields based on imine. c Determined by 300 MHz 1H-NMR analysis.
b
53% of imine was recovered. The yield could not be improved by lengthening the reaction time. e 16% of 2-(3-pyridinyl)-3-vinyloxirane
d
(trans/cis ) 2:1) from the reaction of ylide and aldehyde generated by the hydrolysis of imine was isolated. f This ratio refers to that of
the rearranged product N-(benzenesulfonyl)-cis-4,5-diphenyl-4,5-dihydroazepine (18) and N-(benzenesulfonyl)-trans-2,3-bis(â-phenylvinyl)-
aziridine (trans-6g).
atom of sulfonium salts in our ylide aziridination (Table
3). It was found that an increase in the bulkiness of the
ligands on the sulfur atom did not improve the trans/cis
selectivity of the reaction, but rather led to the formation

4644 J . Org. Chem., Vol. 61, No. 14, 1996
Li et al.
Ta ble 3. Effect of Liga n d s on th e Su lfu r Atom in Allylic Su lfon iu m Sa lts on th e Ylid e Azir id in a tion u n d er
P h a se-Tr a n sfer Con d ition sa
a
All reactions were carried out under solid-liquid phase-transfer conditions at room temperature in a ratio of imine:sulfonium salt:
KOH(s) ) 1:1.2:1.2 on a 0.5-mmol scale in CH3CN. Isolated yields based on imine. c Determined by 300 MHz 1H-NMR analysis.
b
Sch em e 3
Sch em e 5
tively. The obviously high reactivity of allylic sulfonium
ylides, compared with the corresponding arsonium, tel-
luronium, and phosphorus ylides, made them the best
choice for the aziridination reaction.
Sch em e 4
It is noteworthy that N-sulfonylimines have been
reported to react with an oxosulfonium methylide
Me2S(O)+CH2- to give azetidines instead of aziridines.16
In all of our reactions, no azetidine was detected.
Recently, Matano et al.17 found that triphenylbismutho-
nium 2-oxoalkylides reacted with N-sulfonylimines to
form aziridinyl ketones.
P r ep a r a tion of Vin yla zir id in es w ith P r efor m ed
Ylid es a t Low Tem p er a tu r e. Clearly, the trans/cis
selectivity in forming the above-mentioned vinylaziri-
dines under phase-transfer conditions is low. Efforts to
improve the stereoselectivity of this reaction by exposure
of N-sulfonylimines to preformed sulfonium, arsonium,
and telluronium ylides have been made. Results are
shown in Table 4.
Allylic sulfonium, arsonium, or telluronium salts in
THF were treated with a base at -78 °C for 5-30 min
to generate the corresponding ylides. Imines in THF
were subsequently added to the ylide solution and
allowed to warm to room temperature. Vinylaziridines
were obtained after workup. Ylides generated from
of a pyrroline product 9 as a minor product (entries 2-4
in Table 3). Product 9 is thought to be formed by an
intramolecular 1,5-elimination of the zwitterionic inter-
mediate III in Scheme 4.
Several allylides of As, Te, and P have also been
studied in our aziridination reaction. Allylic arsonium
ylide generated in situ from allyltriphenylarsonium
bromide (14) by KOH reacts with N-sulfonylimine 2c to
give vinylaziridine 4h in moderate yield (Scheme 5).
However, allylic telluronium (from 15) and phosphorus
(triphenylphosphonium allylide) ylides did not form an
aziridine with N-sulfonylimine 2c, but rather the hydro-
lyzed product, PhCHO, was recovered almost quantita-
(16) Nadir, U. K.; Koul, V. K. Synthesis 1983, 554.
(17) Matano, Y.; Yoshimune, M.; Suzuki, H. J . Org. Chem. 1995,
60, 4663.

A Direct Route to C-Vinylaziridines
J . Org. Chem., Vol. 61, No. 14, 1996 4645
Ta ble 4. P r ep a r a tion of Vin yla zir id in e 4g a n d [â-(Tr im eth ylsilyl)vin yl]a zir id in es 8 by th e Rea ction of Allylic or
Silyla ted Allylic Su lfon iu m , Ar son iu m , a n d Tellu r on iu m Ylid es a n d N-Su lfon ylim in es a t -78 °Ca
4g or 8
entry
R
R1
salt
base
yield,b %
trans/cisc
9, %
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-ClC6H4
o-MeOC6H4
R-naphthyl
R-naphthyl
H
H
H
H
H
H
H
H
H
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
SiMe3
3a
3a
14
14
15
15
3b
3b
3b
16
7b
7b
7b
7b
7a
7a
7a
7a
7a
7a
7a
n-BuLi
32 (4g)
35 (4g)
25 (4g)
21 (4g)
57 (4g)
79 (4g)
68 (4g)
83 (4g)
61 (4g)
39 (8c)
97 (8c)
98 (8c)
98 (8c)
98 (8c)
95 (8c)
92 (8c)
92 (8c)
98 (8c)
98 (8b)
98 (8d )
98 (8d )
59/41
61/39
70/30
54/46
55/45
45/55
41/59
41/59
35/65
33/67
37/63
42/58
39/61
45/55
61/39
67/33
59/41
29/71
22/78
64/36
73/27
0
0
10
15
0
KN(SiMe3)2
LiN(SiMe3)2
KN(SiMe3)2
LiBr + KN(SiMe3)2
KN(SiMe3)2
n-BuLi
LiN(SiMe3)2
KN(SiMe3)2
KN(SiMe3)2
n-BuLi
LiN(SiMe3)2
NaN(SiMe3)2
KN(SiMe3)2
n-BuLi
LiN(SiMe3)2
NaN(SiMe3)2
KN(SiMe3)2
KN(SiMe3)2
KN(SiMe3)2
NaN(SiMe3)2
0
23
12
17
a
b
All reactions were carried out at -78 °C in a ratio of imine:salt:base ) 1:1.2:1.2 on a 0.5-mmol scale in THF. Isolated yields based
on imine. c Determined by 300 MHz 1H-NMR analysis.
sulfonium salt 3a , because of a known [2,3]-σ-rearrange-
ment,7 and arsonium salt 14, due to the relatively low
reactivity, gave low yields (entries 1-4 in Table 4).
Ylides from telluronium salt 15 and from sulfonium salt
3b reacted with N-tosylimines to form the desired aziri-
dines in reasonable yields (entries 5-9 in Table 4).
However, the trans/cis ratio of the product remained
almost the same as that obtained from phase-transfer
reactions, even in the presence of lithium ion (entries 1,
3, 5, 7, 8, 11, 12, 15, and 16 in Table 4), which is known
to play an important role in the control of the stereo-
chemistry in ylide chemistry.18 In some cases, pyrroline
product 9 was produced as a minor product (entries 3, 4,
and 7-9 in Table 4), the combined total yields still being
very high.
Considering that good stereoselectivity has never been
achieved in ylide epoxidation7a,19 and ylide cyclo-
propanation7a with the simplest sulfonium,7a,19a,b ar-
sonium,19c,d and telluronium19e,g allylides, we tried to
improve the trans/cis selectivity by using a bulky tri-
methylsilyl-substituted allylide. It was not efficient
either through a telluronium ylide (entry 10 in Table 4)
or through sulfonium ylides, although quantitative yields
were achieved in all examples with sulfonium ylides
(entries 11-21 in Table 4). It is noteworthy that the ylide
generated from sulfonium salt 7a did not undergo the
expected [2,3]-σ-rearrangement. This ylide could stand
for several hours at -78 °C without significant change.
Its extreme stability to rearrangement and its transform-
able SiMe3 may make the dimethylsulfonium 3-tri-
methylsilylated allylide a very useful reagent for prepar-
ing vinyloxiranes, vinylcyclopropanes, and vinylaziri-
dines.
Con clu sion s
A method for preparing N-sulfonylvinylaziridines via
an ylide route, which may be regarded as the simplest
direct way to this kind of potentially useful compound
for organic synthesis, is reported. Allylic sulfonium salts
3, 5, and 7 reacted with aromatic, heteroaromatic, and
R,â-unsaturated N-sulfonylimines in CH3CN with KOH
as the base at room temperature to produce, respectively,
vinyl-, (â-phenylvinyl)-, and [â-(trimethylsilyl)vinyl]aziri-
dines in excellent yields. Generally, the reaction was
complete within several minutes. This aziridination
reaction has also been carried out with preformed ylides,
(18) (a) Maryanoff, B. E.; Reitz, A. B.; Mutter, M. S.; Inners, R. R.;
Almond, H. R., J r. J . Am. Chem. Soc. 1985, 107, 1068. (b) Maryanoff,
B. E.; Reitz, A. B.; Mutter, M. S.; Inners, R. R.; Almond, H. R., J r.;
Whittle, R. R.; Olofson, R. A. J . Am. Chem. Soc. 1986, 108, 7664. (c)
Schlosser, M.; Christmann, K. F. Angew. Chem., Int. Ed. Engl. 1966,
5, 126. (d) Vedejs, E.; Meier, G. P.; Snoble, K. A. J . J . Am. Chem. Soc.
1981, 103, 2823. (e) Tang, Y. Ph.D. thesis, Shanghai Institute of
Organic Chemistry, CAS, 354 Fenglin Lu, Shanghai 200032, China,
1995.
(19) Epoxidation with sulfonium allylides: (a) Hatch, M. J . J . Org.
Chem. 1969, 34, 2133. (b) Feldman, K. S.; Fisher, T. E. Tetrahedron
1989, 45, 2969. With arsonium allylides: (c) Ousset, J . B.; Mioskowski,
C.; Solladie, G. Tetrahedron Lett. 1983, 24, 4419. (d) Ousset, J . B.;
Mioskowski, C.; Solladie, G. Synth. Commun. 1983, 13, 1193. With
telluronium allylides: (e) Osuka, A.; Suzuki, H. Tetrahedron Lett. 1983,
24, 5109. (f) Zhou, Z.-L.; Sun, Y.-S.; Shi, L.-L.; Huang, Y.-Z. J . Chem.
Soc., Chem. Commun. 1990, 1439. (g) Zhou, Z.-L.; Shi, L.-L.; Huang,
Y.-Z. Tetrahedron Lett. 1990, 31, 7657.

4646 J . Org. Chem., Vol. 61, No. 14, 1996
Li et al.
trans-4b: 1H NMR (CDCl3) δ 2.38 (s, 3 H), 3.25 (dd, J ) 4.2,
9.5 Hz, 1 H), 3.77 (s, 3 H), 4.34 (d, J ) 4.3 Hz, 1 H), 5.45 (d,
J ) 10.5 Hz, 1 H), 5.55 (d, J ) 16.8 Hz, 1 H), 6.35 (ddd, J )
7.1, 9.9, 16.9 Hz, 1 H), 6.77-6.85 (m, 2 H), 7.13-7.32 (m, 4
H), 7.85 (d, J ) 8.4 Hz, 2 H).
generated from sulfonium salts 3 and 7, arsonium salt
14, and telluronium salts 15 and 16 with a base in THF
at low temperature. In most examples, quantitative
yields were achieved. Since the tosyl group can be
cleaved by well-known procedures,20 and the vinylaziri-
dines can be easily transformed to many very useful
synthetic intermediates, the value of this direct method
is apparent.
N-Tosyl-2-(2,6-d ich lor op h en yl)-3-vin yla zir id in e (4c).
cis-4c: 1H NMR (CDCl3) δ 2.44 (s, 3 H), 3.76 (dd, J ) 6.6, 6.7
Hz, 1 H), 4.07 (d, J ) 7.0 Hz, 1 H), 5.09 (dd, J ) 2.0, 9.9 Hz,
1 H), 5.18-5.29 (m, 1 H), 5.35 (dd, J ) 2.1, 16.9 Hz, 1 H),
7.09-7.14 (m, 1 H), 7.19-7.23 (m, 2 H), 7.27-7.36 (m, 2 H),
7.90 (dd, J ) 1.8, 8.3 Hz, 2 H); MS m/ z 370 (1.89), 369 (0.87),
368 (M+, 2.82), 214 (72), 213 (16), 212 (100), 174 (53), 173 (10),
172 (78), 136 (12), 123 (10), 91 (29), 65 (16); HRMS calcd for
Exp er im en ta l Section
Ma ter ia ls a n d Gen er a l P r oced u r e. All reagents and
solvents, unless otherwise specified, are commercially available
and used without further purification. THF was distilled
immediately prior to use from sodium/benzophenone ketyl
under nitrogen. All N-sulfonylimines 2 were prepared accord-
ing to literature method21 in reasonable yields. Sulfonium
salts 3a , 5, 7a , 11, and 13 were prepared by the reaction of
corresponding allylic bromides with sulfides in a small amount
of acetone at rt in excellent yields. Sulfonium salts 3b, 7b,
and 12 were obtained by a literature procedure7a except that
AgClO4 was used instead of AgBF4. Arsonium salt 14 was
prepared by the reaction of Ph3As and allyl bromide.19c
Telluronium salts 15 and 16 were prepared by the reaction of
i-Bu2Te22 with allyl bromide or 3-(trimethylsilyl)allyl bro-
mide,23 respectively, without solvent at room temperature in
quantitative yields.24 Sulfinimine 1725 was obtained according
to a literature procedure.
1
C17H15Cl2NO2S (M+) 367.0201, found 367.0169. trans-4c: H
NMR (CDCl3) δ 2.44 (s, 3 H), 3.50 (dd, J ) 4.5, 9.6 Hz, 1 H),
4.12 (d, J ) 4.5 Hz, 1 H), 5.52 (d, J ) 10.3 Hz, 1 H), 5.65 (d,
J ) 16.8 Hz, 1 H), 6.30 (ddd, J ) 9.9, 9.9, 16.9 Hz, 1 H), 7.09-
7.14 (m, 1 H), 7.19-7.23 (m, 2 H), 7.27-7.36 (m, 2 H), 7.88
(dd, J ) 1.9, 8.3 Hz, 2 H).
N-Tosyl-2-(3-p yr id in yl)-3-vin yla zir id in e (4d ). cis-4d :
1H NMR (CDCl3) δ 2.43 (s, 3 H), 3.67 (dd, J ) 6.9, 7.0 Hz, 1
H), 4.05 (d, J ) 6.9 Hz, 1 H), 5.19-5.31 (m, 2 H), 5.41-5.47
(m, 1 H), 7.19-7.90 (m, 6 H), 8.46-8.51 (m, 2 H); MS m/ z
301 (M+ + 1, 3.9), 300 (M+, 2.6), 261 (9), 171 (23), 155 (37),
139 (8.7), 107 (25), 91 (100), 77 (8.5), 65 (27); HRMS calcd for
C16H16N2O2S (M+) 300.0932, found 300.0894. trans-4d : 1H
NMR (CDCl3) δ 2.40 (s, 3 H), 3.33 (dd, J ) 4.0, 9.7 Hz, 1 H),
4.06 (d, J ) 3.6 Hz, 1 H), 5.51 (d, J ) 10.3 Hz, 1 H), 5.60 (d,
J ) 16.9 Hz, 1 H), 6.35 (ddd, J ) 7.1, 9.8, 16.9 Hz, 1 H), 7.19-
7.90 (m, 6 H), 8.46-8.51 (m, 2 H).
Gen er a l P r oced u r e for Azir id in a tion u n d er Solid -
Liqu id P h a se-Tr a n sfer Con d ition s. A 25-mL flask con-
taining a magnetic stirring bar was charged with imine (2,
1.0 equiv), sulfonium salt (3, 5, 7, 11, 12, or 13, 1.2 equiv) or
arsonium salt 14 (1.2 equiv) and acetonitrile (4 mL, reagent
grade; it need not be dried before use). Powdered potassium
hydroxide (1.2 equiv) was subsequently added under stirring.
After the reaction was complete according to TLC, the reaction
mixture was filtered on a short neutral Al2O3 column to remove
inorganic salts. The filtrate was concentrated and chromato-
graphed on a neutral Al2O3 column with a mixture of light
petroleum (60-90 °C), ethyl acetate, and NEt3 (8 :1 :1) as the
eluent to give pure product.
N-Tosyl-2-(p-n itr op h en yl)-3-vin yla zir id in e (4a ). cis-4a :
1H NMR (CDCl3) δ 2.41 (s, 3 H), 3.69 (dd, J ) 6.6, 7.1 Hz, 1
H), 4.13 (d, J ) 7.3 Hz, 1 H), 5.17-5.24 (m, 2 H), 5.39-5.47
(m, 1 H), 7.27-7.43 (m, 4 H), 7.89 (dd, J ) 1.7, 8.3 Hz, 2 H),
8.12 (dd, J ) 2.7, 4.4 Hz, 2 H); MS m/ z 345 (M+ + 1, 3.3), 344
(M+, 1.2), 189 (100), 173 (3.7), 149 (39), 115 (9.7), 103 (22), 91
(17), 77 (2.8), 65 (9); HRMS calcd for C17H16N2O4S (M+)
344.0831, found 344.0807. trans-4a : 1H NMR (CDCl3) δ 2.45
(s, 3 H), 3.29 (dd, J ) 3.9, 9.6 Hz, 1 H), 4.11 (d, J ) 3.9 Hz, 1
H), 5.16-5.63 (m, 2 H), 6.34 (ddd, J ) 2.8, 7.0, 10.0 Hz, 1 H),
7.27-7.43 (m, 4 H), 7.83 (dd, J ) 1.8, 6.7 Hz, 2 H), 8.15 (dd,
J ) 2.0, 4.7 Hz, 2 H).
N-(Ben zen esu lfon yl)-2-(p-m eth ylp h en yl)-3-vin yla zir i-
d in e (4e). cis-4e: 1H NMR (CDCl3) δ 2.28 (s, 3 H), 3.62 (dd,
J ) 7.2, 7.2 Hz, 1 H), 4.07 (d, J ) 7.2 Hz, 1 H), 5.19-5.31 (m,
2 H), 5.39-5.46 (m, 1 H), 7.06-7.08 (m, 4 H), 7.42-7.61 (m, 3
H), 8.0 (dd, J ) 1.4, 7.3 Hz, 2 H); MS m/ z 300 (M+ + 1, 4),
196 (2.5), 158 (100), 143 (5), 129 (4), 118 (58), 103 (3.9), 91
(10), 77 (19), 65 (4), 51 (7); HRMS calcd for C17H17NO2S (M+)
299.0980, found 299.1024. trans-4e: 1H NMR (CDCl3) δ 2.28
(s, 3 H), 3.32 (dd, J ) 4.1, 9.6 Hz, 1 H), 4.03 (d, J ) 4.2 Hz, 1
H), 5.46 (d, J ) 10.0 Hz, 1 H), 5.55 (d, J ) 16.9 Hz, 1 H), 6.31
(ddd, J ) 7.1, 9.9, 17.0 Hz, 1 H), 7.06-7.08 (m, 4 H), 7.42-
7.61 (m, 3 H), 7.95 (dd, J ) 1.9, 5.6 Hz, 2 H).
N-(Ben zen esu lfon yl)-2-(p-m eth oxyp h en yl)-3-vin yla zir -
id in e (4f). cis-4f: 1H NMR (CDCl3) δ 3.60 (dd, J ) 7.2, 7.2
Hz, 1 H), 3.73 (s, 3 H), 4.05 (d, J ) 7.2 Hz, 1 H), 5.16-5.58
(m, 3 H), 6.75-6.81 (m, 2 H), 7.07-7.14 (m, 2 H), 7.43-7.61
(m, 3 H), 8.0 (d, J ) 7.9 Hz, 2 H); MS m/ z 316 (M+ + 1, 50),
227 (6.7), 196 (10), 174 (100), 160 (34), 147 (9), 137 (34), 122
(6.5), 109 (7.8), 91 (6.5), 77 (38), 56 (11); HRMS calcd for C17H17
-
NO3S (M+) 315.0929, found 315.0939. trans-4f: 1H NMR
(CDCl3) δ 3.32 (dd, J ) 4.2, 9.6 Hz, 1 H), 3.73 (s, 3 H), 4.02 (d,
J ) 4.2 Hz, 1 H), 5.16-5.58 (m, 2 H), 6.3 (ddd, J ) 2.7, 7.2,
10.0 Hz, 1 H), 6.75-6.81 (m, 2 H), 7.07-7.14 (m, 2 H), 7.43-
7.61 (m, 3 H), 7.93 (dd, J ) 1.4, 7.9 Hz, 2 H).
N-Tosyl-2-(p-ch lor op h en yl)-3-vin yla zir id in e (4g). cis-
4g: 1H NMR (CDCl3) δ 2.44 (s, 3 H), 3.61 (dd, J ) 7.1, 7.1 Hz,
1 H), 4.03 (d, J ) 7.1 Hz, 1 H), 5.18-5.30 (m, 2 H), 5.40-5.16
(m, 1 H), 7.09-7.17 (m, 2 H), 7.21-7.35 (m, 4 H), 7.88 (d, J )
8.3 Hz, 2 H); MS m/ z 336 (0.76), 335 (0.50), 334 (1.87), 333
(0.31), 294 (1.4), 210 (6.2), 178 (100), 155 (10), 138 (58), 125
(2.7), 115 (8.5), 91 (20), 65 (8.4), 51 (2). Anal. Calcd for
C17H16ClNO2S: C, 61.20; H, 4.83; N, 4.20. Found: C, 61.13;
N-Tosyl-2-(o-m eth oxyp h en yl)-3-vin yla zir id in e (4b). cis-
4b: 1H NMR (CDCl3) δ 2.40 (s, 3 H), 3.65 (dd, J ) 4.5, 7.3 Hz,
1 H), 3.77 (s, 3 H), 4.20 (d, J ) 7.3 Hz, 1 H), 5.11 (dd, J ) 2.0,
10.1 Hz, 1 H), 5.25 (m, 1 H), 5.35-5.42 (m, 1 H), 6.77-6.85
(m, 2 H), 7.13-7.32 (m, 4 H), 7.88 (dd, J ) 1.6, 6.7 Hz, 2 H);
MS m/ z 330 (M+ + 1, 5.8), 329 (M+, 0.8), 210 (10.7), 174 (100),
155 (11.4), 137 (33), 107 (27), 91 (34), 77 (9.5), 65 (13), 56 (16);
HRMS calcd for C18H19NO3S (M+) 329.1086, found 329.1048.
1
H, 4.65; N, 4.44. trans-4g: H NMR (CDCl3) δ 2.41 (s, 3 H),
3.26 (dd, J ) 4.1, 9.7 Hz, 1 H), 4.01 (d, J ) 4.3 Hz, 1 H), 5.49
(d, J ) 10.2 Hz, 1 H), 5.57 (d, J ) 16.9 Hz, 1 H), 6.32 (ddd, J
) 9.9, 10.0, 17.0 Hz, 1 H), 7.09-7.17 (m, 2 H), 7.21-7.35 (m,
4 H), 7.83 (d, J ) 8.3 Hz, 2 H).
(20) (a) Fukuyama, T.; J ow, C.-K.; Cheung, M. Tetrahedron Lett.
1995, 36, 6373. (b) Roemmele, R. C.; Rapoport, H. J . Org. Chem. 1988,
53, 2367 and references cited therein. (c) Bellos, K.; Stamm, H.; Speth,
D. J . Org. Chem. 1991, 56, 6846. (d) Vedejs, E.; Lin, S. J . Org. Chem.
1994, 59, 1602.
(21) Love, B. E.; Raje, P. S.; Williams, T. C., II. Synlett 1994, 493.
(22) Balfe, M. P.; Chaplin, C. A.; Phillips, H. J . Chem. Soc. 1938,
341.
(23) (a) Tones, T. K.; Denmark, S. E. Org. Synth. 1986, 64, 182. (b)
Grant, B.; Djerassi, C. J . Org. Chem. 1974, 39, 968.
(24) Zhou, Z.-L.; Huang, Y.-Z.; Tang, Y.; Chen, Z.-H.; Shi, L.-P.; J in,
X.-L.; Yang, Q.-C. Organometallics 1994, 13, 1575.
(25) Yang, T.-K.; Chen, R.-Y.; Lee, D.-S.; Peng, W.-S.; J iang, Y.-Z.;
Mi, A.-Q.; J ong. T.-T. J . Org. Chem. 1994, 59, 914.
N-Tosyl-2-ph en yl-3-vin ylazir idin e (4h ). cis-4h : 1H NMR
(CDCl3) δ 2.40 (s, 3 H), 3.61 (dd, J ) 7.3, 8.4 Hz, 1 H), 4.07 (d,
J ) 8.4 Hz, 1 H), 5.14-5.28 (m, 2 H), 5.39 (m, 1 H), 7.15-7.32
(m, 7 H), 7.88 (d, J ) 8.2 Hz, 2 H); MS m/ z 300 (M+ + 1, 1.2),
299 (M+, 0.36), 260 (0.56), 155 (2.8), 144 (100), 128 (1.5), 115
(9.9), 104 (62.6), 91 (18), 77 (7.4), 65 (8.8), 51 (3). Anal. Calcd
for C17H17NO2S: C, 68.20; H, 5.72; N, 4.68. Found: C, 67.74;
1
H, 5.75; N, 4.94. trans-4h : H NMR (CDCl3) δ 2.36 (s, 3 H),
3.30 (dd, J ) 4.1, 9.6 Hz, 1 H), 4.04 (d, J ) 4.2 Hz, 1 H), 5.45

A Direct Route to C-Vinylaziridines
J . Org. Chem., Vol. 61, No. 14, 1996 4647
(d, J ) 16.9 Hz, 1 H), 5.54 (d, J ) 16.9 Hz, 1 H), 6.33 (ddd, J
) 7.1, 9.9, 17.0 Hz, 1 H), 7.15-7.32 (m, 7 H), 7.83 (d, J ) 8.2
Hz, 2 H).
N-Tosyl-2-(r-n a p h th yl)-3-vin yla zir id in e (4i). cis-4i: 1H
NMR (CDCl3) δ 2.39 (s, 3 H), 3.87 (dd, J ) 7.3, 7.5 Hz, 1 H),
4.51 (d, J ) 7.2 Hz, 1 H), 4.98-5.16 (m, 2 H), 5.41 (dd, J )
1.4, 16.9 Hz, 1 H), 7.24-7.51 (m, 6 H), 7.80-7.83 (m, 2 H),
7.92-7.98 (m, 3 H); MS m/ z 349 (M+, 0.56), 210 (1.37), 194
(100), 179 (2.5), 165 (11), 154 (47), 139 (6.8), 127 (10), 115 (3.6),
H), 6.68 (dd, J ) 9.6, 16.1 Hz, 1 H), 6.78 (d, J ) 16.1 Hz, 1 H),
7.12-7.56 (m, 12 H), 7.95 (d, J ) 8.8 Hz, 2 H).
N-Tosyl-2-(p -ch lor op h en yl)-3-(tr a n s-â-p h en ylvin yl)-
a zir id in e (6f). cis-6f: 1H NMR (CDCl3) δ 2.43 (s, 3 H), 3.79
(dd, J ) 7.7, 7.8 Hz, 1 H), 4.09 (d, J ) 7.4 Hz, 1 H), 5.54 (dd,
J ) 8.4, 16.1 Hz, 1 H), 6.74 (d, J ) 16.0 Hz, 1 H), 7.14-7.45
(m, 11 H), 7.83 (d, J ) 8.3 Hz, 2 H); MS m/ z 409 (M+, 16), 294
(38), 254 (100), 219 (69), 202 (9), 155 (36), 140 (14), 115 (26),
91 (57), 77 (8), 65 (14); HRMS calcd for C23H20ClNO2S (M+)
409.0903, found 409.0926. trans-6f: 1H NMR (CDCl3) δ 2.40
(s, 3 H), 3.40 (dd, J ) 4.4, 9.6 Hz, 1 H), 4.11 (d, J ) 4.2 Hz, 1
H), 5.63 (dd, J ) 9.4, 15.8 Hz, 1 H), 6.80 (d, J ) 15.9 Hz, 1 H),
7.14-7.45 (m, 11 H), 7.90 (d, J ) 8.3 Hz, 2 H).
N-(Ben zen esu lfon yl)-2-(tr a n s-â-p h en ylvin yl)-3-(tr a n s-
â-p h en ylvin yl)a zir id in e (6g). trans-6g: 1H NMR (CDCl3)
δ 3.63 (dd, J ) 3.1, 10.9 Hz, 2 H), 6.24 (dd, J ) 10.8, 15.9 Hz,
2 H), 6.79 (d, J ) 15.8 Hz, 2 H), 6.55 (d, J ) 7.3 Hz, 2 H),
7.01-7.51 (m, 11 H), 7.95 (d, J ) 9.0 Hz, 2 H); MS m/ z 387
(M+, 2.1), 272 (10.5), 246 (100), 231 (4), 202 (2.6), 168 (6.6),
130 (12), 115 (45), 103 (4.4), 91 (19), 77 (19), 51 (4.6); HRMS
calcd for C24H21NO2S (M+) 387.1293, found 387.1276.
102 (0.6), 91 (10), 77 (1.5), 65 (5). Anal. Calcd for C21H19
-
NO2S: C, 72.18; H, 5.48; N, 4.01. Found: C, 71.96; H, 5.16;
N, 3.72. trans-4i: 1H NMR (CDCl3) δ 2.39 (s, 3 H), 3.30 (dd, J
) 4.3, 9.8 Hz, 1 H), 4.58 (d, J ) 4.3 Hz, 1 H), 5.55 (d, J ) 10.5
Hz, 1 H), 6.54 (ddd, J ) 10.0, 10.0, 17.0 Hz, 1 H), 7.1 (d, J )
7.1 Hz, 1 H), 7.24-7.51 (m, 5 H), 7.70-7.74 (m, 2 H), 7.92-
7.98 (m, 3 H).
N-Tosyl-2-(p-n itr op h en yl)-3-(tr a n s-â-p h en ylvin yl)a zir -
id in e (6a ). cis-6a : 1H NMR (CDCl3) δ 2.44 (s, 3 H), 3.86 (dd,
J ) 7.5, 7.8 Hz, 1 H), 4.19 (d, J ) 7.3 Hz, 1 H), 5.50 (dd, J )
8.1, 15.9 Hz, 1 H), 6.75 (d, J ) 15.9 Hz, 1 H), 7.13-7.47 (m, 9
H), 7.91 (d, J ) 8.3 Hz, 2 H), 8.16 (d, J ) 6.6 Hz, 2 H); MS
m/ z 420 (M+, 5.4), 278 (5), 265 (100), 244 (7), 219 (30), 191
(7), 155 (12), 139 (19), 115 (50), 91 (51), 77 (11), 65 (19); HRMS
calcd for C23H20N2O4S (M+) 420.1144, found 420.1125. trans-
6a : 1H NMR (CDCl3) δ 2.40 (s, 3 H), 3.43 (dd, J ) 3.9, 9.4 Hz,
1 H), 4.22 (d, J ) 4.0 Hz, 1 H), 6.71 (dd, J ) 9.5, 15.8 Hz, 1
H), 6.82 (d, J ) 15.8 Hz, 1 H), 7.13-7.47 (m, 9 H), 7.84 (d, J
) 8.3 Hz, 2 H), 8.16 (d, J ) 6.8 Hz, 2 H).
N-Tosyl-2-(o-m eth oxyp h en yl)-3-(tr a n s-â-p h en ylvin yl)-
a zir id in e (6b). cis-6b: 1H NMR (CDCl3) δ 2.42 (s, 3 H), 3.77
(s, 3 H), 3.84 (dd, J ) 7.8, 7.7 Hz, 1 H), 4.28 (d, J ) 7.3 Hz, 1
H), 5.56 (dd, J ) 8.2, 15.9 Hz, 1 H), 6.79 (d, J ) 16.3 Hz, 1 H),
7.14-7.46 (m, 11 H), 7.91 (dd, J ) 1.8, 6.9 Hz, 2 H); MS m/ z
405 (M+, 0.71), 250 (100), 235 (5.7), 191 (1.1), 178 (1.6), 134
(4.5), 115 (38), 91 (22), 77 (4), 65 (6), 51 (2.4). Anal. Calcd for
C24H23NO3S: C, 71.08; H, 5.72; N, 3.45. Found: C, 70.82; H,
5.48; N, 3.11. trans-6b: 1H NMR (CDCl3) δ 2.39 (s, 3 H), 3.39
(dd, J ) 4.3, 8.8 Hz, 1 H), 3.81 (s, 3 H), 4.45 (d, J ) 4.2 Hz, 1
H), 6.74 (dd, J ) 9.3, 15.6 Hz, 1 H), 6.85 (d, J ) 15.5 Hz, 1 H),
7.14-7.46 (m, 11 H), 7.86 (d, J ) 8.3 Hz, 2 H).
N-Tosyl-2-ph en yl-3-(tr a n s-â-ph en ylvin yl)azir idin e (6c).
cis-6c: 1H NMR (CDCl3) δ 2.43 (s, 3 H), 3.80 (dd, J ) 7.9, 7.8
Hz, 1 H), 4.14 (d, J ) 7.1 Hz, 1 H), 5.59 (dd, J ) 8.5, 16.1 Hz,
1 H), 6.74 (d, J ) 15.5 Hz, 1 H), 7.15-7.42 (m, 12 H), 7.91 (dd,
J ) 1.4, 6.7 Hz, 2 H); MS m/ z 375 (M+, 0.82), 220 (100), 204
(2.6), 191 (2.8), 178 (1.8), 165 (1.7), 139 (2.8), 115 (67), 104
(9.3), 91 (31), 77 (4.8), 65 (7.8), 51 (2.3). Anal. Calcd for
C23H21NO2S: C, 73.57; H, 5.64; N, 3.73. Found: C, 73.37; H,
5.44; N, 3.32; HRMS calcd for C16H14N (M+ - Ts) 220.1126,
found 220.1134. trans-6c: 1H NMR (CDCl3) δ 2.39 (s, 3 H),
3.44 (dd, J ) 4.1, 9.4 Hz, 1 H), 4.16 (d, J ) 4.1 Hz, 1 H), 6.66
(dd, J ) 9.3, 15.8 Hz, 1 H), 6.80 (d, J ) 15.4 Hz, 1 H), 7.15-
7.42 (m, 12 H), 7.84 (d, J ) 8.4 Hz, 2 H).
N -(Be n ze n e su lfon yl)-cis-4,5-d ip h e n yl-4,5-d ih yd r o-
a zep in e (18): 1H NMR (CDCl3) δ 3.77 (d, J ) 5.9 Hz, 2 H),
5.23 (dd, J ) 6.0, 9.4 Hz, 2 H), 6.84 (d, J ) 9.6 Hz, 2 H), 7.01-
7.51 (m, 13 H), 7.91 (d, J ) 7.6 Hz, 2 H).
N-Tosyl-2-p h en yl-3-[â-(t r im et h ylsilyl)vin yl]a zir id in e
(8a ). cis-8a : 1H NMR (CDCl3) δ -0.04 (s, 9 H), 2.43 (s, 3 H),
3.63 (dd, J ) 7.6, 7.0 Hz, 1 H), 4.01 (d, J ) 7.3 Hz, 1 H), 5.41
(dd, J ) 7.3, 18.71 Hz, 1 H), 6.12 (d, J ) 18.5 Hz, 1 H), 7.15-
7.34 (m, 7 H), 7.89 (d, J ) 8.3 Hz, 2 H); MS m/ z 372 (M+ + 1,
0.32), 228 (0.8), 218 (6), 217 (22), 216 (100), 200 (18), 149 (9.4),
113 (4.3), 91 (19), 85 (7), 73 (47), 59 (11). Anal. Calcd for
C20H25NO2SSi: C, 64.65; H, 6.78; N, 3.77. Found: C, 64.28;
H, 6.84; N, 3.38. trans-8a : 1H NMR (CDCl3) δ 0.03 (s, 9 H),
2.40 (s, 3 H), 3.27 (dd, J ) 4.0, 9.0 Hz, 1 H), 4.08 (d, J ) 4.1
Hz, 1 H), 6.21 (d, J ) 18.4 Hz, 1 H), 6.42 (dd, J ) 8.9, 18.3 Hz,
1 H), 7.15-7.34 (m, 7 H), 7.82 (d, J ) 8.3 Hz, 2 H).
N -Tosyl-2-(o-m e t h oxyp h e n yl)-3-[â-(t r im e t h ylsilyl)-
vin yl]a zir id in e (8b). cis-8b: 1H NMR (CDCl3) δ 0.01 (s, 9
H), 2.51 (s, 3 H), 3.81 (dd, J ) 7.2, 7.2 Hz, 1 H), 3.85 (s, 3 H),
4.27 (d, J ) 7.3 Hz, 1 H), 5.52 (dd, J ) 7.3, 18.8 Hz, 1 H), 6.20
(d, J ) 19.2 Hz, 1 H), 6.89-6.93 (m, 2 H), 7.22 (d, J ) 7.4 Hz,
1 H), 7.31-7.44 (m, 3 H), 8.01 (d, J ) 8.2 Hz, 2 H); MS m/ z
319 (2), 268 (6), 267 (23), 266 (83), 246 (100), 231 (6.2), 216
(7.2), 139 (10), 113 (4), 91 (31), 73 (68), 59 (10), 45 (6). Anal.
Calcd for C21H27NO3SSi: C, 62.80; H, 6.78; N, 3.49. Found:
C, 62.57; H, 6.58; N, 3.64. trans-8b: 1H NMR (CDCl3) δ 0.25
(s, 9 H), 2.49 (s, 3 H), 3.40 (dd, J ) 4.1, 9.1 Hz, 1 H), 3.88 (s,
3 H), 4.54 (d, J ) 4.0 Hz, 1 H), 6.34 (d, J ) 18.6 Hz, 1 H), 6.61
(dd, J ) 9.0, 18.7 Hz, 1 H), 6.89-6.93 (m, 2 H), 7.12 (d, J )
7.0 Hz, 1 H), 7.31-7.44 (m, 3 H), 7.95 (d, J ) 8.3 Hz, 2 H).
N-Tosyl-2-(p-ch lor op h en yl)-3-[â-(tr im eth ylsilyl)vin yl]-
a zir id in e (8c). cis-8c: 1H NMR (CDCl3) δ 0.00 (s, 9 H), 2.50
(s, 3 H), 3.71 (dd, J ) 7.2, 7.1 Hz, 1 H), 4.05 (d, J ) 7.2 Hz, 1
H), 5.48 (dd, J ) 7.1, 18.6 Hz, 1 H), 6.21 (d, J ) 18.5 Hz, 1 H),
7.18-7.23 (m, 2 H), 7.28-7.42 (m, 4 H), 7.96 (dd, J ) 1.4, 6.7
Hz, 2 H); MS m/ z 254 (3), 253 (11), 252 (48), 251 (25), 250
(100), 236 (3.8), 234 (7.6), 199 (8), 169 (3.6), 149 (12), 139 (5.5),
121 (13), 91 (19), 85 (12), 73 (64), 65 (7.8), 59 (20), 45 (8). Anal.
Calcd for C20H24ClNO2SSi: C, 59.16; H, 5.96; N, 3.45.
Found: C, 59.14; H, 5.90; N, 3.68. trans-8c: 1H NMR (CDCl3)
δ 0.21 (s, 9 H), 2.47 (s, 3 H), 3.32 (dd, J ) 4.2, 9.1 Hz, 1 H),
4.13 (d, J ) 4.1 Hz, 1 H), 6.31 (d, J ) 18.4 Hz, 1 H), 6.50 (dd,
J ) 9.0, 18.5 Hz, 1 H), 7.18-7.23 (m, 2 H), 7.28-7.42 (m, 4
H), 7.90 (dd, J ) 1.6, 6.6 Hz, 2 H).
N-(Ben zen esu lfon yl)-2-(p -m et h ylp h en yl)-3-(tr a n s-â-
p h en ylvin yl)a zir id in e (6d ). cis-6d : 1H NMR (CDCl3) δ 2.29
(s, 3 H), 3.81 (dd, J ) 7.9, 7.9 Hz, 1 H), 4.13 (d, J ) 7.2 Hz, 1
H), 5.62 (dd, J ) 8.4, 16.0 Hz, 1 H), 6.73 (d, J ) 15.7 Hz, 1H),
6.99-7.60 (m, 12 H), 8.03 (d, J ) 8.0 Hz, 2 H); MS m/ z 376
(M+ + 1, 12), 375 (M+, 30), 260 (39), 234 (100), 219 (23), 202
(6), 156 (4), 141 (13), 115 (15), 105 (7.6), 91 (9.6), 77 (34), 65
(3.5); HRMS calcd for C23H21NO2S (M+) 375.1293, found
375.1314. trans-6d : 1H NMR (CDCl3) δ 2.25 (s, 3 H), 3.48 (dd,
J ) 4.2, 9.0 Hz, 1 H), 4.15 (d, J ) 4.3 Hz, 1 H), 6.69 (dd, J )
9.0, 15.8 Hz, 1 H), 6.78 (d, J ) 15.8 Hz, 1 H), 6.99-7.60 (m,
12 H), 7.94 (d, J ) 8.2 Hz, 2 H).
N-Tosyl-2-(r-n a p h th yl)-3-[â-(tr im eth ylsilyl)vin yl]a zir i-
d in e (8d ). cis-8d : 1H NMR (CDCl3) δ 0.00 (s, 9 H), 2.68 (s, 3
H), 4.20 (dd, J ) 7.4, 7.3 Hz, 1 H), 4.77 (d, J ) 7.2 Hz, 1 H),
5.55 (dd, J ) 7.5, 18.7 Hz, 1 H), 6.40 (d, J ) 18.7 Hz, 1 H),
7.47-7.63 (m, 4 H), 7.73-7.81 (m, 2 H), 7.99-8.02 (m, 1 H),
8.06-8.12 (m, 1 H), 8.18-8.30 (m, 3 H); MS m/ z 268 (8.4),
267 (30), 266 (100), 250 (12), 193 (4.6), 168 (7.6), 139 (10.4),
127 (2.7), 113 (3.4), 91 (14), 73 (59), 59 (10), 45 (5.4); HRMS
calcd for C17H20NSi (M+ - Ts) 266.1365, found 266.1339.
trans-8d : 1H NMR (CDCl3) δ 0.48 (s, 9 H), 2.66 (s, 3 H), 3.61
(dd, J ) 4.2, 9.2 Hz, 1 H), 4.95 (d, J ) 4.1 Hz, 1 H), 6.57 (d, J
N-(Ben zen esu lfon yl)-2-(p-m eth oxyp h en yl)-3-(tr a n s-â-
p h en ylvin yl)a zir id in e (6e). cis-6e: 1H NMR (CDCl3) δ 3.76
(s, 3 H), 3.79 (dd, J ) 8.4, 8.4 Hz, 1 H), 4.13 (d, J ) 8.4 Hz, 1
H), 5.62 (dd, J ) 8.4, 16.0 Hz, 1 H), 6.79 (d, J ) 16.1 Hz, 1H),
7.12-7.56 (m, 12 H), 8.03 (d, J ) 7.0 Hz, 2 H); MS m/ z 391
(M+, 11), 317 (6), 276 (21), 250 (100), 223 (25), 191 (9), 178
(23), 165 (11), 145 (13), 135 (46), 115 (34), 105 (19), 91 (23), 77
(62), 65 (8), 51 (18); HRMS calcd for C23H21NO3S (M+)
1
391.1242, found 391.1284. trans-6e: H NMR (CDCl3) δ 3.47
(dd, J ) 4.3, 9.3 Hz, 1 H), 3.76 (s, 3 H), 4.13 (d, J ) 4.0 Hz, 1

4648 J . Org. Chem., Vol. 61, No. 14, 1996
Li et al.
) 18.4 Hz, 1 H), 6.96 (dd, J ) 9.2, 18.4 Hz, 1 H), 7.47-7.63
(m, 4 H), 7.73-7.81 (m, 2 H), 7.99-8.02 (m, 1 H), 8.06-8.12
(m, 1 H), 8.18-8.30 (m, 3 H).
and imine (1.0 equiv) in 4 mL THF was subsequently added.
The reaction mixture was then allowed to warm to room
temperature within 2-3 h. The reaction mixture was filtered
on a short neutral Al2O3 column to hydrolyze the excess active
species and remove inorganic salts. The filtrate was concen-
trated and chromatographed on a neutral Al2O3 column with
a mixture of light petroleum (60-90 °C), ethyl acetate, and
NEt3 (8:1:1) as the eluent to give pure product.
N-Tosyl-2-(p-ch lor op h en yl)-3-p yr r olin e (9): 1H NMR
(CDCl3) δ 2.40 (s, 3 H), 4.29 (m, 1 H), 4.34 (ddd, J ) 2.3, 4.8,
14.6 Hz, 1 H), 5.48 (ddd, J ) 2.2, 4.7, 5.3 Hz, 1 H), 5.61 (ddd,
J ) 2.2, 4.4, 6.2 Hz, 1 H), 5.80 (ddd, J ) 2.0, 4.0, 6.2 Hz, 1 H),
7.17-7.26 (m, 6 H), 7.52 (dd, J ) 1.6, 6.6 Hz, 2 H); MS m/ z
336 (6.8), 335 (5), 334 (19), 333 (4.7), 222 (52), 180 (33), 178
(100), 155 (30), 143 (23), 115 (24), 91 (45), 75 (2.8), 65 (13), 51
(2); HRMS calcd for C17H16ClNO2S (M+) 333.0590, found
333.0559.
Ack n ow led gm en t. Financial support from the Na-
tional Natural Foundation of China and Chinese Acad-
emy of Sciences is gratefully acknowledged.
Gen er a l P r oced u r e for Azir id in a tion a t -78 °C.
A
Su p p or tin g In for m a tion Ava ila ble: Copies of NMR
spectra (21 pages). This material is contained in libraries on
microfiche, immediately follows this article in the microfilm
version of the journal, and can be ordered from the ACS; see
any current masthead page for ordering information.
solution of the base (n-BuLi in hexanes, LiN(SiMe3)2, NaN-
(SiMe3)2, KN(SiMe3)2, or LiBr (1.2 equiv) + NaN(SiMe3)2 in
THF, 1.2 equiv) was added dropwise to a solution of a
sulfonium (3a , 3b, 7a , 7b), telluronium (15, 16), or arsonium
(14) salt in 6 mL of THF at -78 °C under N2. The mixture
was stirred for 5-30 min (5 min for 3a , 30 min for others),
J O952245D