A convenient and efficient ring-opening reaction of aziridines with acetylenes and synthesis of dihydropyrroles

Article abstract of DOI:10.1016/j.tet.2005.07.076

In the presence of BuOK, reaction of acetylenes with N-Ts substituted aziridines derived from both cyclic and acyclic alkenes at room temperature gave rise to homopropargylamines in good to high yields and in high regioselectivity. Not only Ph- and Me₃Si-substituted acetylenes but also acetylene itself was suitable reagents. Treatment of ring-opening products with I₂ and AgOAc in the presence of K₂CO₃ provided dihydropyrroles in high yields. One-pot synthesis of dihydropyrroles was also realized by the reaction of aziridines and phenylacetylene in the presence of NaH followed by the treatment with I₂ and AgOAc.

Full text of DOI:10.1016/j.tet.2005.07.076

Tetrahedron 61 (2005) 9586–9593
A convenient and efficient ring-opening reaction of aziridines with
acetylenes and synthesis of dihydropyrroles
Chang-Hua Ding,b Li-Xin Daia and Xue-Long Houa,b,
*
aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, China
bShanghai–Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, China
Received 4 July 2005; revised 22 July 2005; accepted 22 July 2005
Available online 10 August 2005
Abstract—In the presence of tBuOK, reaction of acetylenes with N-Ts substituted aziridines derived from both cyclic and acyclic alkenes at
room temperature gave rise to homopropargylamines in good to high yields and in high regioselectivity. Not only Ph- and Me3Si-substituted
acetylenes but also acetylene itself was suitable reagents. Treatment of ring-opening products with I2 and AgOAc in the presence of K2CO3
provided dihydropyrroles in high yields. One-pot synthesis of dihydropyrroles was also realized by the reaction of aziridines and
phenylacetylene in the presence of NaH followed by the treatment with I2 and AgOAc.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
and efficient alkynylation of aziridines using acetylene and
phenyl acetylene in the presence of base as well as the
synthesis of dihydropyrroles using these ring-opening
products.
Aziridines are widely used as intermediates in organic
synthesis.1 Many transformations of aziridines have well
been documented. Among them, ring-opening reactions of
aziridines with nucleophiles provide a useful protocol, and
many reagents have recently been developed to realize the
opening of aziridine ring. However, the most often used
reagents are those O-,2 S-,3 and N-4 nucleophiles; only a few
examples were reported using carbon nucleophiles, such as
Grignard reagents, organolithiums, Wittig reagents, cup-
rates and malonates, in the ring-opening reaction of
aziridines, although these transformations are more import-
ant because a new carbon–carbon bond is formed.5 Besides,
some limitations were also reported when carbon nucleo-
philes were the reagent. For example, only aziridines
derived from acyclic alkenes gave good results when
alkynyllithiums were used.6 During the course of studies
on the ring-opening reactions of aziridines,7 we developed
an effective alkynylation of aziridines using CuOTf as
catalyst.8 But the reaction needed 2 equiv of BuLi as base
and it also suffered from the long reaction time. Besides,
acetylene was not suitable reagent. All of these limit its use
in organic synthesis. To overcome such limitations, further
studies were made. Herein we reported a simple, convenient
2. Results and discussions
Considering the acidity of acetylene group, the effect of a
variety of bases on the reaction of aziridine 1 and
phenylacetylene 2a in DMSO was investigated initially
(Eq. 1). The results are compiled in Table 1.
(1)
As shown in Table 1, the property of base has a crucial
influence on the yield of products and reaction time. The
yield increased when basicity of base was enhanced from
Cs2CO3, NaOH, KOH to NaH (entries 1–4). When Cs2CO3
was used as base aziridine 1a was recovered fully (entry 1).
Corresponding homopropargyl amine was obtained in low
yield employing NaOH or KOH as base and aziridine 1a
could not be consumed completely (entries 2 and 3). When
NaH was used as base the reaction gave the corresponding
product in 71% yield (entry 4), which increased further to
Keywords: Alkynylation; Aziridine; Ring-opening; Cyclization;
Dihydropyrrole.
Corresponding author. Tel.: C86 21 5492 5144; fax: C86 21 5492 5100;
e-mail: xlhou@mail.sioc.ac.cn
*
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.07.076

C.-H. Ding et al. / Tetrahedron 61 (2005) 9586–9593
9587
Table 1. Effect of bases on the ring-opening reaction of aziridine 1a with phenylacetylene 2aa
Entry
Substrate, R1, R2
Base (mol%)
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
1a, –(CH2)4–
1a, –(CH2)4–
1a, –(CH2)4–
1a, –(CH2)4–
1a, –(CH2)4–
1a, –(CH2)4–
1a, –(CH2)4–
1c,–(CH2)5–
1e, n-C6H13, H
1e, n-C6H13, H
1e, n-C6H13, H
1e, n-C6H13, H
1e, n-C6H13, H
1e, n-C6H13, H
Cs2CO3 (200)
NaOH (150)
KOH (150)
NaH (150)
NaH (200)
CsOH$H2O (200)
nBu4NOH (50)
NaH (200)
5
5
5
5
NRc
9
46
71
87
73
NRc
74
45
12
63
68
95
87
1.5d
3d
12
1d
9
NaH (200)
0.5d
0.5
0.5
0.5
0.5
0.5d
10
11
12
13
14
NaOCH3 (150)
iPrONa (150)
tBuONa (150)
tBuOK (150)
tBuOK (150)
a Reactions proceeded with molecular ratio of 1:2aZ1:1.5 at room temperature.
b Isolated yields based on aziridine 1.
c No reaction.
d
˚
4 A molecular sieves was added.
87% if molecular sieves was added (entry 5). Quaternary
ammonium hydroxide and CsOH were also tested. No
reaction occurred using Bu4NOH (entry 7) while product 3a
was provided in 73% yield using CsOH as base and 4 A MS
as additives (entry 6).
To demonstrate the usefulness of this base-mediated ring-
opening reaction of aziridines with alkynes, many kinds of
aziridines 1 as well as Ph- and Me3Si-substituted acetylenes
2 were tested (Eq. 2) and the results are shown in Table 2.
˚
The effect of solvent was also studied. When Et2O, THF or
toluene was used as solvent, no reaction took place and
starting material was recovered. In DMF or CH3CN
aziridines 1a disappeared but only unknown byproducts
were provided.
(2)
Sodium hydride showed its superior in yield when aziridines
1a and 1c derived from cyclic alkenes were used (entries 5
and 8), low yield of product was given when the aziridine 1e
derived from acyclic alkene (entry 9). Thus, further screen
of bases using 1e was carried out. It was found that
corresponding homopropargylamine 3e was provided in
12% yield using NaOCH3 as base (entry 10). However, the
yield dramatically increased to 63 and 68% when more
It can be seen from Table 2 that in the presence of
stoichiometric amount of BuOK, the reaction of aziridines
t
1 with alkynes completed within 0.5–2.5 h to provide the
corresponding ring-opening product 3 in high yields. As
previously observed in CuOTf promoted reaction,8 the
reaction was completely anti stereoselective. Besides, the
attack of acetylenes to aziridines is highly regioselective.
All reactions for aziridines derived from terminal alkenes
gave only one regioisomer arising from terminal attack,
even for phenyl aziridine 1h (entry 8), while in CuOTf
i
t
basic PrONa and BuONa was used, respectively, (entries
11 and 12). Further, great improvement of yield from 68 to
t
t
95% was observed when BuOK instead of BuONa was
used (entry 13). It differs from the reaction using NaH as
base, molecular sieves had no effect when tBuOK was used
as base (entry 13 vs entry 14 and entry 4 vs entry 5).
Table 2. Ring-opening reaction of aziridines 1 with acetylenes 2 in the presence of tBuOKa
Entry
Substrate, R1, R2, R3 and R4
Alkyne, R
Product
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
1a, –(CH2)4–, H, Ts
1b, –(CH2)3–, H, Ts
1c, –(CH2)5–, H, Ts
1d, –(CH2)4–, H, SO2Ph
1e, n-C6H13, H, H, Ts
1f, i-C3H7, H, H, Ts
1g, t-C4H9, H, H, Ts
1h, Ph, H, H, Ts
1i, n-C5H11, H, Me, Ts
1j, –(CH2)4–, H, COPh
1k, –(CH2)4–, H, Bn
1a, –(CH2)4–, H, Ts
1e, n-C6H13, H, H, Ts
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2b, Me3Si
2b, Me3Si
3a
3b
3c
3d
3e
3f
3g
3h
3i
1.5
2.5
1.5
1
0.5
1
85
77c
74c
73
95
84
67
85
92
29
—
83
98
1
1.5
1.5
1
—
1
9
10
11
12
13
3j
—
4a
4e
0.5
a Reactions run with molecular ratio of 1:2:baseZ1:1.5:1.5.
b Isolated yield based on aziridine.
c NaH (200 mol%) was used.

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C.-H. Ding et al. / Tetrahedron 61 (2005) 9586–9593
promoted reaction, phenyl aziridine gave two regioisomers
arising from the benzylic and terminal attack.8 Many kind of
aziridines, derived both from cyclic and acyclic alkenes
including terminal disubstituted alkenes 1i (entry 9) are
suitable substrate. However, the choice of substituent on the
nitrogen atom of aziridines is important. For example,
N-COPh aziridine 1j gave low yield of product (entry 10)
while no reaction took place for N-Bn aziridine 1k (entry
11), but N-SO2Ph aziridine 1d delivered good yield of
product (entry 4). It seems from these results that the
presence of electron-withdrawing substituents on nitrogen is
necessary. It is worthwhile to point out that for aziridine 1c
corresponding product 3c was provided in 74% yield
(entry 3) while in the CuOTf catalyzed reaction only trace
product was obtained when 1c was substrate. Trimethylsilyl
substituted acetylene is also a suitable reagent, but the
product was desilylated product 4 (entries 9 and 10,
Table 2).
(3)
Dihydropyrroles are useful intermediates in natural products
synthesis. Recently, Knigh and co-workers reported a
simple procedure for the synthesis of dihydropyrroles
from iodo-cyclization of homopropargylamines.10
Obviously, such kind of homopropargylamines in turn can
be produced from the ring-opening reaction of aziridines
and alkynes. Under the reaction condition reported by
Knigh and co-workers,10 homopropargylic sulfonamide 3a
underwent smooth 5-endo-dig cyclization upon exposure to
excess iodine in acetonitrile containing potassium carbonate
affording 4-iodo-2,3-dihydropyrrole 6a in 30% yield
(Eq. 4). To improve the yield of product, the modification
of reaction condition was made. It was found that the yield
of dihydropyrrole increase to 83% from 30% when
300 mol% of AgOAc was added (Eq. 4). Under this reaction
condition, iodocyclization of several homopropargylamines
3 derived from our base-mediated and CuOTf-catalyzed8
ring-opening of aziridines to dihydropyrroles proceeded
(Eq. 5, Table 4).
Acetylene is a commercially available chemical. It is also
one of the cheapest carbon sources. The addition of
acetylene to carbonyl compound is one general method to
form carbon–carbon bond.9 However, no ring-opening
reaction of aziridine with acetylene was reported. Based
on the success of alkynylation of activated aziridines in the
presence of base, we tried to use acetylene as nucleophile.
Under above reaction condition, reaction of aziridines 1
with acetylene 2c was carried out (Eq. 2, RZH) and the
results are given in Table 3.
(4)
Table 3. Ring-opening reaction of aziridines 1 with acetylene 2c using
tBuOK as basea
Entry
Substrate, R1, R2, R3 and R4 Product
Time
(h)
Yield
(%)b
1
2
3
4
5
6
7
8
9
10
1a, –(CH2)4–, H, Ts
1b, –(CH2)3–, H, Ts
1c, –(CH2)5–, H, Ts
1d, –(CH2)4–, H, SO2Ph
1e, n-C6H13, H, H, Ts
1f, i-C3H7, H, H, Ts
1g, t-C4H9, H, H, Ts
1h, Ph, H, H, Ts
4a
4b
4c
4d
4e
4f
4g
4h
4i
0.5
0.5
2
1
0.5
2
0.5
0.5
0.5
0.5
87
82
55
76
78
71
61
77
67
63
(5)
1i, n-C5H11, H, Me, Ts
1m, n-C16H33, H, H, Ts
It is showed in Table 4 that all reactions gave desired
products in good yields. When the amount of I2, and AgOAc
decreased to 150 mol%, the reaction still provided the
product in good yield (entry 4). Many kinds of homo-
propargylamines, including those from ring-opening
reaction of hexynes and aziridines (entry 6) and
4m
a Reactions run in DMSO with molecular ratio of 1:tBuOKZ1:1.5.
b Isolated yield based on aziridine.
From Table 3, it can be seen that the ring-opening of
aziridine 1 with acetylene proceeded smoothly in DMSO
and various homopropargylamines 4 were afforded in good
yields by the reaction of aziridine 1 with acetylide generated
in situ. It is the same as that in the reactions with
phenylacetylene and trimethylsilylacetylene, all tested
aziridines derived both from cyclic and acyclic alkenes
including terminal disubstituted alkenes gave expected
products. One of advantages using acetylene is that the
products still contain terminal acetylene group, thus provide
an opportunity to convert it to other products.9
Table 4. Synthesis of dihydropyrroles 7 from cyclization of homopro-
pargylamines 3a
Entry
Substrate, R1, R2, R3
Time
(h)
Product
Yield
(%)b
1
2
3
4
5
6
7
8
3a, –(CH2)4–, Ph
3a, –(CH2)4–, Ph
3n, n-C4H9, H, Ph
3d, n-C4H9, H, Ph
3e, n-C6H13, H, Ph
3o, n-C6H13, H, n-C4H9,
3h, Ph, H, Ph
20
3
6a
6a
6n
6n
6e
6o
6h
6p
30c
83
78
56d
76
73
69
87
12
24
15
16
18
15
3p, Bn, H, Ph
However, reaction of aziridine 1e and 1-hexnye 2d failed to
yield the expected product; instead, only product 5 resulting
from attack of tert-butoxide on less substituted carbon of
aziridines was separated (Eq. 3).
a The reaction condition is showed in Eq. 6.
b Isolated product based on homopropargyl amine.
c No AgOAc was added.
d The amount of I2, and AgOAc were 150 mol%.

C.-H. Ding et al. / Tetrahedron 61 (2005) 9586–9593
9589
phenylacetylene and benzylaziridine (entry 8) are suitable
substrates. However, homopropargylamine derived from the
reaction of acetylene and aziridines gave an unstable
product with uncertain reason.
Then reaction mixture was quenched with 5 mL of 1 N HCl
aqueous solution. The resulting mixture was poured into
diethyl ether (60 mL), and washed with H2O (10 mL) and
saturated aqueous NaHCO3 (10 mL) solution. The organic
layer was dried over anhydrous MgSO4. The solvent was
removed in vacuum and the crude product was purified by
flash column chromatography on silica gel to provide
corresponding homopropargyl amine.
It is interesting that dihydropyrroles can be provided in one-
pot reaction manner. When 300 mol% of I2 and 150 mol%
of AgOAc were added to the reaction mixture of aziridines
1a and phenylacetylene 2a, dihydropyrrole 6a was
separated in 74% yield (Eq. 6).
3.3. General procedure for ring-opening reaction of
aziridines 1 with acetylene 2c using BuOK as base
t
t
A stirred solution of BuOK (0.375 mmol) in DMSO
(3.0 mL) was saturated with acetylene 2c by bubbling for
30 min, then aziridine 1 (0.25 mmol) was added under
argon. The reaction mixture was stirred at room temperature
till complete consumption of substrate (monitored by TLC).
Then reaction mixture was quenched carefully with 5 mL of
1 N HCl aqueous solution. The resulting mixture was
poured into diethyl ether (60 mL), and washed with H2O
(10 mL) and saturated aqueous NaHCO3 (10 mL) solution.
The organic layer was dried over anhydrous MgSO4. The
solvent was removed in vacuum and the crude product was
purified by flash column chromatography on silica gel to
provide corresponding homopropargyl amine.
(6)
In conclusion, a base-mediated ring-opening reaction of
aziridines and a variety of acetylenes was developed in a
simple and convenient way. Homopropargyl amines were
provided in high yields and in high regioselectivity. The use
of acetylene extends the utility of reaction. Besides, the
reaction has the advantages of wider range of substrates and
better regioselectivity over that catalyzed by CuOTf.8 Based
upon it, a facile preparation of dihydropyrroles was realized,
even in a one-pot manner. The investigations on the extension
of the reaction to other substrates and on the asymmetric
version of the reaction are in progress in our laboratory.
3.3.1. N-(2-Phenyl-1-ynyl-cyclohexyl)-4-methyl-benzene-
1
sulfonamide (3a).8 White solid; mp 118–120 8C; H NMR
(CDCl3/TMS) dZ1.24–1.27 (m, 4H), 1.46–1.69 (m, 2H),
1.99–2.05 (m, 1H), 2.24–2.28 (m, 1H), 2.31 (s, 3H), 2.41–2.49
(m, 1H), 3.02–3.12 (m, 1H), 4.81 (d, JZ5.4 Hz, 1H), 7.11 (d,
JZ8.1 Hz, 2H), 7.12–7.29 (m, 5H), 7.75 (d, JZ8.4 Hz, 2H);
13C NMR (75 MHz, CDCl3) dZ13.77, 21.39, 22.16, 25.87,
27.55, 33.90, 52.22, 83.29, 84.93, 123.09, 126.95, 127.89,
128.14, 129.55, 131.55, 137.99, 143.21; IR (film) n~Z3286,
2248, 1599, 1320, 1165 cmK1; EI-MS m/z (%): 353 (MC,
1.48), 198 (35), 155 (23), 115 (35), 91 (100). Anal. Calcd for
C21H23NO2S: C, 71.35; H, 6.56; N, 3.96. Found: C, 71.42; H,
6.57; N: 3.80.
3. Experimental
3.3.2. N-(2-Phenyl-1-ynyl-cyclopentyl)-4-methyl-benzene-
1
sulfonamide (3b).8 White solid; mp 111–113 8C; H NMR
3.1. General experimental conditions
(CDCl3/TMS) dZ1.45–1.53 (m, 1H), 1.68–1.75 (m, 3H),
2.04–2.15 (m, 2H), 2.32 (s, 3H), 2.69–2.74 (m, 1H), 3.52–3.56
(m, 1H), 4.80 (d, JZ6.0 Hz, 1H), 7.20 (d, JZ8.1 Hz, 2H),
7.23–7.29 (m, 5H), 7.78–7.82 (m, 2H); 13C NMR (75 MHz,
CDCl3) dZ21.38, 21.93, 30.77, 32.64, 37.79, 60.94, 81.93,
90.39, 123.32, 127.15, 127.67, 128.02, 129.53, 131.49,
All reactions were performed under an atmosphere of dry
argon using oven-dried glassware. Solvents were distilled
under an atmosphere of dry argon before use. The
commercially available reagents were used as received
without further purification. Melting points are uncorrected.
1H NMR spectra were recorded on a Brucker AM-300
(300 MHz) spectrometer, and the chemical shifts were
referenced to CHCl3 (d 7.27) in CDCl3. Chemical shifts are
given in parts per million relative to tetramethylsilane as an
137.24, 143.19; IR (film) n~Z3269, 1489, 1320, 1149 cmK1
;
EI-MS m/z (%): 339 ((MC1)C, 1.31), 184 (46), 168 (100),
115 (48), 91 (67). Anal. Calcd for C20H21NO2S: C, 70.77; H,
6.24; N, 4.13. Found: C: 71.08; H, 6.51; N: 3.80.
internal standard. IR spectra were measured in cmK1
.
3.3.3. N-(2-Phenyl-1-ynyl-cycloheptyl)-4-methyl-benzene-
sulfonamide (3c). White solid; mp 71–73 8C; 1H NMR
(CDCl3/TMS)dZ1.47–2.02(m, 10H), 2.29(s, 3H), 2.76–2.90
(m, 1H), 3.40–3.46 (m, 1H), 5.43 (d, JZ6.9 Hz, 1H), 7.12 (d,
JZ7.8 Hz, 2H), 7.25 (s, 5H), 7.79 (d, JZ8.1 Hz, 2H); 13C
NMR (75 MHz, CDCl3) dZ21.34, 22.26, 24.49, 27.58, 29.40,
32.74, 38.19, 58.32, 82.77, 91.18, 123.28, 127.02, 127.62,
127.95, 129.43, 131.41, 137.16, 142.97; IR (film) n~Z3273,
1598, 1322, 1162 cmK1. Anal. Calcd for C22H25NO2S: C,
71.90; H, 6.86; N, 3.81. Found: C, 71.99; H, 6.86; N, 3.52.
3.2. General procedure for ring-opening reaction of
aziridines 1 with acetylenes 2a and 2b in the presence of
tBuOK
t
To a stirred solution of BuOK (0.375 mmol) in DMSO
(2.0 mL) was added acetylenes 2a or 2b (0.375 mmol) and
aziridine 1 (0.25 mmol) successively under argon. The
reaction mixture was stirred at room temperature until the
substrate was completely consumed (monitored by TLC).

9590
C.-H. Ding et al. / Tetrahedron 61 (2005) 9586–9593
3.3.4. N-(2-Phenyl-1-ynyl-cyclohexyl)-benzenesulfona-
mide (3d).8 White solid; mp 146–148 8C; 1H NMR
(CDCl3/TMS) dZ1.21–1.69 (m, 6H), 1.99–2.05 (m, 1H),
2.23–2.27 (m, 1H), 2.42–2.50 (m, 1H), 3.07–3.13 (m, 1H),
4.88 (d, JZ5.4 Hz, 1H), 7.24–7.47 (m, 8H), 7.87–7.89 (m,
2H); IR (film) n~Z3253, 1491, 1322, 1161 cmK1; EI-MS m/z
(%): 339 (MC, 0.59), 141 (27), 115 (29), 77 (100). Anal.
Calcd for C20H21NO2S: C, 70.77; H, 6.24; N, 4.13. Found:
C: 70.56; H, 6.35; N: 3.94.
58.79, 83.37, 85.58, 123.20, 126.84, 127.74, 128.05, 129.29,
131.44, 140.16, 142.72; IR (film) n~Z3277, 1598, 1323,
1158 cmK1; EI-MS m/z (%): 268 ((MK115)C, 100), 155
(41), 115 (20), 91 (58). Anal. Calcd for C23H29NO2S: C,
72.02; H, 7.62; N, 3.65. Found: C, 71.90; H, 7.68; N, 3.38.
3.3.10. N-(2-Phenyl-1-ynyl-cyclohexyl)-benzoylamide
(3j). White solid; mp 201–203 8C; H NMR (CDCl3/TMS)
1
dZ1.23–1.41 (m, 3H), 1.45–1.85 (m, 3H), 2.05–2.16 (m,
1H), 2.25–2.30 (m, 1H), 2.56–2.64 (m, 1H), 4.07–4.10 (m,
1H), 6.23 (d, JZ7.5 Hz, 1H), 7.20–7.33 (m, 5H), 7.38–7.50
(m, 3H), 7.79 (d, JZ7.2 Hz, 2H); IR (film) n~Z3307, 2937,
1613, 1551 cmK1; EI-MS m/z (%): 303 (MC, 2.17), 183
(11), 182 (74), 105 (100), 77 (61). Anal. Calcd for
C21H21NO: C, 83.13; H, 6.98; N, 4.62. Found: C, 82.88;
H, 6.91; N, 4.54.
3.3.5. 1-Phenyl-4-N-(p-toluenesulfonyl)aminodecyne-1
1
(3e).8 White solid; mp 63–65 8C; H NMR (CDCl3/TMS)
dZ0.85 (t, JZ6.9 Hz, 3H), 1.17–1.29 (m, 8H), 1.52–1.62
(m, 2H), 2.41 (s, 3H), 2.50 (d, JZ4.8 Hz, 2H), 3.37–3.45
(m, 1H), 4.67 (d, JZ9.0 Hz, 1H), 7.26–7.38 (m, 7H), 7.78 (d,
JZ8.1 Hz, 2H); IR (film) n~Z3279, 1599, 1327, 1162 cmK1
;
EI-MS m/z (%): 268 ((MK115)C, 100), 269 (21), 155 (43),
115 (21), 91 (49). Anal. Calcd for C23H29NO2S: C, 72.02; H,
7.62; N, 3.65. Found: C, 72.19; H, 7.64; N: 3.45.
3.3.11. N-(2-Acetenyl-cyclohexyl)-4-methyl-benzene-
sulfonamide (4a). White solid; mp 107–109 8C; H NMR
1
(CDCl3/TMS) dZ1.12–1.46 (m, 4H), 1.59–1.63 (m, 2H),
1.91–1.95 (m, 2H), 2.05–2.08 (m, 1H), 2.25–2.31 (m, 1H),
2.42 (s, 3H), 3.03–3.11 (m, 1H), 5.16 (d, JZ6.0 Hz, 1H),
7.29 (d, JZ7.8 Hz, 2H), 7.80 (d, JZ8.1 Hz, 2H); 13C NMR
(75 MHz, CDCl3) dZ21.46, 23.45, 23.71, 30.63, 32.17,
34.92, 55.92, 70.58, 84.57, 127.22, 129.40, 137.46, 143.14;
IR (film) n~Z3269, 1597, 1323, 1157 cmK1; EI-MS m/z (%):
277 (MC, 2.47), 155 (47), 122 (97), 91 (100). Anal. Calcd
for C15H19NO2S: C, 64.95; H, 6.90; N, 5.05. Found: C,
64.86; H, 6.84; N, 4.80.
3.3.6. 1-Phenyl-5-methyl-4-N-(p-toluenesulfonyl)amino-
hexyne-1 (3f). White solid; mp 101–102 8C; 1H NMR
(CDCl3/TMS) dZ0.88 (d, JZ3.0 Hz, 3H), 0.90 (d, JZ
3.0 Hz, 3H), 1.97–2.04 (m, 1H), 2.39 (s, 3H), 2.43–2.58 (m,
2H), 3.14–3.23 (m, 1H), 4.85–4.88 (m, 1H), 7.24–7.36 (m,
7H), 7.77–7.81 (m, 2H); 13C NMR (75 MHz, CDCl3) dZ
18.09, 19.09, 21.49, 23.36, 31.03, 57.63, 83.21, 84.95,
123.05, 127.02, 127.98, 128.19, 129.60, 131.57, 137.86,
143.27; IR (film) n~Z3298, 1599, 1315, 1163 cmK1; EI-MS
m/z (%): 341 (MC, 0.31), 226 (100), 155 (52), 115 (22), 91
(57); HRMS: Anal. Calcd for C20H24NO2S (MCH):
342.1509. Found: 342.1522.
3.3.12. 4-N-(p-Toluenesulfonyl)aminodecyne-1 (4e).
1
White solid; mp 48–50 8C; H NMR (CDCl3/TMS) dZ
0.84 (t, JZ7.2 Hz, 3H), 1.05–1.22 (m, 8H), 1.45–1.54 (m,
2H), 1.96–1.98 (m, 1H), 2.27–2.29 (m, 2H), 2.43 (s, 3H),
3.29–3.36 (m, 1H), 4.83 (d, JZ8.7 Hz, 1H), 7.29 (d, JZ
8.1 Hz, 2H), 7.78 (d, JZ8.4 Hz, 2H); 13C NMR (75 MHz,
CDCl3) dZ13.99, 21.44, 22.41, 24.98, 25.35, 28.67, 31.52,
33.82, 51.70, 71.30, 79.51, 126.96, 129.56, 137.88, 143.28;
IR (film) n~Z3265, 2118, 1919, 1598, 1164 cmK1; EI-MS
m/z (%): 268 ((MK39)C, 95), 222 (13), 155 (100), 91 (95).
Anal. Calcd for C17H25NO2S: C, 66.41; H, 8.20; N, 4.56.
Found: C, 66.17; H, 8.25; N, 4.26.
3.3.7. 1-Phenyl-5,5-dimethyl-4-N-(p-toluenesulfonyl)
aminohexyne-1 (3g).8 White solid; mp 122–124 8C; 1H
NMR (CDCl3/TMS) dZ0.98 (s, 9H), 2.28–2.36 (m, 1H),
2.39 (s, 3H), 2.49–2.56 (m, 1H), 3.16–3.23 (m, 1H), 4.89 (d,
JZ10.5 Hz, 1H), 7.24–7.35 (m, 7H), 7.79 (d, JZ8.1 Hz,
2H); IR (film) n~Z3298, 1598, 1316, 1151 cmK1; EI-MS m/z
(%): 355 (MC, 0.03), 240 (100), 155 (35), 115 (21), 91 (39).
Anal. Calcd for C21H25NO2S: C, 70.95; H, 7.09; N, 3.94.
Found: C, 70.77; H, 7.09; N: 3.87.
3.3.8.
1,4-Diphenyl-4-N-(p-toluenesulfonyl)amino-
3.3.13. N-(2-Acetenyl-cyclopentyl)-4-methyl-benzene-
sulfonamide (4b). H NMR (CDCl3/TMS) dZ1.37–1.46
butyne-1 (3h). White solid; mp 117–119 8C; 1H NMR
(CDCl3/TMS) dZ2.36 (s, 3H), 2.83 (dd, JZ1.5, 6.0 Hz,
2H), 4.55 (dd, JZ6.6, 12.9 Hz, 1H), 5.19 (d, JZ6.0 Hz,
1H), 7.14 (d, JZ8.1 Hz, 2H), 7.19–7.32 (m, 10H), 7.63 (d,
JZ8.4 Hz, 2H); 13C NMR (75 MHz, CDCl3) dZ21.38,
28.39, 56.27, 83.82, 84.59, 122.80, 126.51, 127.03, 127.65,
128.02, 128.11, 128.30, 129.36, 131.53, 137.09, 139.54,
143.13; IR (film) n~Z3271, 1598, 1320, 1160 cmK1; EI-MS
m/z (%): 375 (MC, 1.04), 260 (76), 155 (48), 115 (22), 91
(100). Anal. Calcd for C23H21NO2S: C, 73.57; H, 5.64; N,
3.73. Found: C, 73.31; H, 5.65; N, 3.61.
1
(m, 1H), 1.61–1.71 (m, 3H), 1.92–2.01 (m, 3H), 2.43 (s,
3H), 2.52–2.59 (m, 1H), 3.47–3.56 (m, 1H), 5.32 (d, JZ
6.9 Hz, 1H), 7.30 (d, JZ7.8 Hz, 2H), 7.80 (d, JZ8.4 Hz,
2H); 13C NMR (75 MHz, CDCl3) dZ 21.49, 21.87, 30.53,
32.25, 37.02, 60.73, 69.83, 85.04, 127.21, 129.56, 137.21,
143.33; IR (film) n~Z3278, 1599, 1158 cmK1; EI-MS m/z
(%): 263 (MC, 2.15), 234 (12), 155 (47), 108 (31), 91 (100).
Anal. Calcd for C14H17NO2S: C, 63.85; H, 6.51; N, 5.32.
Found: C, 63.60; H, 6.52; N, 5.13.
3.3.14. N-(2-Acetenyl-cycloheptyl)-4-methyl-benzene-
1
3.3.9. 1-Phenyl-4-methyl-4-N-(p-toluenesulfonyl)amino-
nonyne-1 (3i). White solid; mp 71–73 8C; 1H NMR (CDCl3/
TMS) dZ0.86 (t, JZ6.3 Hz, 3H), 1.16–1.32 (m, 9H), 1.52–
1.74 (m, 2H), 2.39 (s, 3H), 2.59 (dd, JZ16.8, 19.2 Hz, 2H),
4.94 (s, 1H), 7.22–7.26 (m, 2H), 7.28–7.30 (m, 3H), 7.33–
7.38 (m, 2H), 7.80 (d, JZ8.4 Hz, 2H); 13C NMR (75 MHz,
CDCl3) dZ13.89, 21.32, 22.39, 23.09, 23.98, 31.78, 39.90,
sulfonamide (4c). H NMR (CDCl3/TMS) dZ1.46–1.74
(m, 9H), 1.91–1.99 (m, 2H), 2.43 (s, 3H), 2.55–2.61 (m,
1H), 3.32–3.39 (m, 1H), 5.02 (d, JZ6.0 Hz, 1H), 7.29 (d,
JZ7.8 Hz, 2H), 7.78 (d, JZ8.4 Hz, 2H); 13C NMR
(75 MHz, CDCl3) dZ21.51, 22.24, 24.29, 27.46, 29.25,
32.42, 37.48, 58.17, 70.83, 85.59, 127.30, 129.48, 137.26,
143.26; IR (film) n~Z3281, 1918, 1599, 1158 cmK1; EI-MS

C.-H. Ding et al. / Tetrahedron 61 (2005) 9586–9593
9591
m/z (%): 291 (MC, 0.77), 210 (13), 155 (48), 136 (40), 91
(100). Anal. Calcd for C16H21NO2S: C, 65.95; H, 7.26; N,
4.81. Found: C, 65.73; H, 7.10; N, 4.57.
(65), 91 (100). Anal. Calcd for C17H25NO2S: C, 66.41; H,
8.20; N, 4.56. Found: C, 66.02; H, 7.99; N, 4.27.
1
3.3.20. 4-N-(p-Toluenesulfonyl)aminoicosyne-1 (4m). H
NMR (CDCl3/TMS) dZ0.88 (t, JZ6.3 Hz, 3H), 1.13–1.30
(m, 28H), 1.45–1.54 (m, 2H), 1.96 (t, JZ2.7 Hz, 1H), 2.27–
2.29 (m, 2H), 2.42 (s, 3H), 3.29–3.36 (m, 1H), 4.85 (d, JZ
9.0 Hz, 1H), 7.29 (d, JZ8.4 Hz, 2H), 7.78 (d, JZ8.4 Hz,
2H); IR (film) n~Z3275, 1599, 1171 cmK1; EI-MS m/z (%):
408 ((MK39)C, 39), 155 (55), 91 (100). Anal. Calcd for
C27H45NO2S: C, 72.43; H, 10.13; N, 3.13. Found: C, 72.34;
H, 10.06; N, 2.95.
3.3.15. N-(2-Acetenyl-cyclohexyl)-benzenesulfonamide
(4d). 1H NMR (CDCl3/TMS) dZ1.15–1.42 (m, 4H),
1.59–1.65 (m, 2H), 1.85 (d, JZ2.4 Hz, 1H), 1.90–1.96 (m,
1H), 2.07–2.11 (m, 1H), 2.23–2.29 (m, 1H), 3.05–3.11 (m,
1H), 5.11 (d, JZ5.1 Hz, 1H), 7.48–7.59 (m, 3H), 7.91–7.94
(m, 2H); 13C NMR (75 MHz, CDCl3) dZ23.62, 23.84,
30.91, 32.56, 35.09, 56.21, 70.54, 84.47, 127.21, 128.81,
132.44, 140.48; IR (film) n~Z3264, 1585, 1156 cmK1; EI-
MS m/z (%): 263 (MC, 1.13), 141 (46), 122 (77), 77 (100).
Anal. Calcd for C14H17NO2S: C, 63.85; H, 6.51; N, 5.32.
Found: C, 63.70; H, 6.49; N, 5.28.
3.3.21. Reaction of aziridine 1e with hexyne 2d in the
t
t
presence of BuOK. To a stirred solution of BuOK
(0.375 mmol) in DMSO (2.0 mL) was added 1-hexyne 2d
(0.375 mmol) and aziridine 1e (0.25 mmol) successively
under argon. The reaction mixture was stirred at room
temperature till complete consumption of substrate
(monitored by TLC). After work-up as described above,
the product 511 was obtained as white solid. Yield: 54%; mp
3.3.16. 5-Methyl-4-N-(p-toluenesulfonyl)aminohexyne-1
1
(4f). H NMR (CDCl3/TMS) dZ0.83 (d, JZ5.1 Hz, 3H),
0.85 (d, JZ5.4 Hz, 3H), 1.83–1.97 (m, 2H), 2.15–2.24 (m,
1H), 2.28–2.37 (m, 1H), 2.42 (s, 3H), 3.05–3.14 (m, 1H),
5.01 (d, JZ9.3 Hz, 1H), 7.29 (d, JZ8.1 Hz, 2H), 7.78 (d,
JZ8.4 Hz, 2H); 13C NMR (75 MHz, CDCl3) dZ17.87,
19.14, 21.45, 22.52, 30.57, 57.23, 71.14, 79.58, 126.97,
129.54, 137.80, 143.25; IR (film) n~Z3275, 2121, 1924,
1600, 1164 cmK1; EI-MS m/z (%): 226 ((MK39)C, 50),
222 (29), 155 (72), 91 (100). Anal. Calcd for C14H19NO2S:
C, 63.36; H, 7.22; N, 5.28. Found: C, 63.45; H, 6.96; N,
5.12.
1
44–46 8C; H NMR (CDCl3/TMS) dZ0.85 (t, JZ6.6 Hz,
3H), 1.05 (s, 9H), 1.09–1.26 (m, 8H), 1.42–1.47 (m, 2H),
2.42 (s, 3H), 3.08–3.26 (m, 3H), 4.88 (d, JZ8.4 Hz, 1H),
7.28 (d, JZ8.1 Hz, 2H), 7.76 (d, JZ8.4 Hz, 2H); 13C NMR
(75 MHz, CDCl3) dZ14.02, 21.41, 22.47, 25.52, 27.25,
28.95, 31.63, 32.49, 53.84, 62.52, 72.81, 127.05, 129.42,
138.22, 142.98; IR (film) n~Z3272, 1599, 1331, 1164 cmK1
;
EI-MS m/z (%): 268 ((MK87)C, 100), 155 (38), 91 (38), 57
(12).
3.3.17. 5,5-Dimethyl-4-N-(p-toluenesulfonyl)amino-
1
hexyne-1 (4g). H NMR (CDCl3/TMS) dZ0.92 (s, 9H),
3.4. General procedure for the synthesis of dihydro-
pyrroles 6 from homopropargylamines 3
1.93 (t, JZ2.7 Hz, 1H), 2.07–2.16 (m, 1H), 2.24–2.32 (m,
1H), 2.43 (s, 3H), 3.08–3.14 (m, 1H), 5.11 (d, JZ10.2 Hz,
1H), 7.29 (d, JZ8.1 Hz, 2H), 7.79 (d, JZ8.1 Hz, 2H); 13C
NMR (75 MHz, CDCl3) dZ20.24, 21.47, 26.79, 35.52,
59.22, 72.17, 80.38, 127.04, 129.48, 138.14, 143.18; IR
(film) n~Z3274, 2123, 1599, 1157 cmK1; EI-MS m/z (%):
280 ((MC1)C, 0.64), 240 (29), 222 (57), 155 (86), 91 (100),
57 (12). Anal. Calcd for C15H21NO2S: C, 64.48; H, 7.58; N,
5.01. Found: C, 64.32; H, 7.31; N, 4.82.
The homopropargylic sulfonamide 3 (0.15 mmol) was
stirred in dry acetonitrile (2 mL) with anhydrous potassium
carbonate (0.45 mmol) and silver acetate (0.45 mmol) at
0 8C. Iodine (0.45 mmol) was added and the resulting
mixture allowed to warm to room temperature. The reaction
mixture was stirred at room temperature till complete
consumption of substrate (monitored by TLC). The reaction
was quenched with saturated aqueous sodium thiosulfate
until the mixture was decolorized and the organic layer was
separated. The aqueous layer was then extracted with
dichloromethane (3!10 mL) and the organic solutions
were combined, dried over anhydrous MgSO4 and con-
centrated under reduced pressure. The crude product was
then purified by column chromatography on silica gel.
3.3.18. 4-Phenyl-4-N-(p-toluenesulfonyl)aminobutyne-1
1
(4h). H NMR (CDCl3/TMS) dZ1.93 (t, JZ2.7 Hz, 1H),
2.35 (s, 3H), 2.60 (dd, JZ2.7, 6.0 Hz, 2H), 4.49 (dd, JZ6.3,
13.8 Hz, 1H), 5.72 (d, JZ7.5 Hz, 1H), 7.11–7.19 (m, 7H),
7.62 (d, JZ8.4 Hz, 2H); 13C NMR (75 MHz, CDCl3) dZ
21.36, 27.18, 55.81, 71.88, 79.13, 126.46, 126.98, 127.62,
128.24, 129.29, 137.08, 139.07, 143.14; IR (film) n~Z3299,
1598, 1162 cmK1; EI-MS m/z (%): 299 ((M)C, 0.99), 260
(50), 155 (35), 91 (100), 77 (10). Anal. Calcd for
C17H17NO2S: C, 68.20; H, 5.72; N, 4.68. Found: C, 68.10;
H, 5.74; N, 4.58.
3.4.1. trans-N-Tosyl-3-phenyl-4-iodo-2-azabicyclo[4.3.0]
non-3-ene (6a). White solid; mp 152–154 8C; H NMR
1
(CDCl3/TMS) dZ1.06–1.29 (m, 3H), 1.77–1.93 (m, 4H),
2.31–2.41 (m, 1H), 2.42 (s, 3H), 2.73–2.79 (m, 1H), 3.04–
3.13 (m, 1H), 7.21–7.37 (m, 9H); 13C NMR (75 MHz,
CDCl3) dZ21.59, 25.42, 25.76, 31.32, 31.77, 54.18, 71.04,
87.14, 127.34, 128.13, 128.72, 129.29, 130.11, 132.93,
3.3.19. 4-Methyl -4-N-(p-toluenesulfonyl)aminononyne-1
1
(4i). H NMR (CDCl3/TMS) dZ0.83 (t, JZ6.9 Hz, 3H),
133.86, 143.93, 146.18; IR (film) n~Z1596, 1358, 1174 cmK1
;
1.11–1.28 (m, 6H), 1.20 (s, 3H), 1.47–1.64 (m, 2H), 2.01–
2.04 (m, 1H), 2.40–2.42 (m, 2H), 2.41 (s, 3H), 5.09 (s, 1H),
7.27 (d, JZ7.8 Hz, 2H), 7.79 (d, JZ8.7 Hz, 2H); 13C NMR
(75 MHz, CDCl3) dZ13.91, 21.40, 22.41, 23.07, 23.65,
31.03, 31.76, 39.60, 58.31, 71.50, 80.05, 126.95, 129.36,
EI-MS m/z (%): 479 (MC, 28), 197 (95), 169 (63), 91 (100).
Anal. Calcd for C21H22INO2S: C, 52.62; H, 4.63; N, 2.92.
Found: C, 52.70; H, 4.64; N, 2.78.
140.06, 142.91; IR (film) n~Z3280, 2121, 1600, 1159 cmK1
;
3.4.2. 2-Phenyl-3-iodo-5-hexyl-1-(4-tolylsulfonyl)-2,3-
dihydropyrrole (6e). White solid; mp 91–92 8C; H NMR
1
EI-MS m/z (%): 307 (MC, 0.09), 268 (84), 236 (25), 155

9592
C.-H. Ding et al. / Tetrahedron 61 (2005) 9586–9593
(CDCl3/TMS) dZ0.91 (t, JZ6.6 Hz, 3H), 1.25–1.48 (m,
6H), 1.52–1.62 (m, 3H), 1.74–1.81 (m, 1H), 2.15 (dd, JZ
1.5, 16.2 Hz, 1H), 2.42 (s, 3H), 2.47 (dd, JZ8.7, 16.5 Hz,
1H), 4.18–4.26 (m, 1H), 7.26–7.29 (m, 2H), 7.38–7.43 (m,
3H), 7.53–7.59 (m, 4H); 13C NMR (75 MHz, CDCl3) dZ
14.11, 21.66, 22.61, 24.75, 29.16, 31.74, 36.26, 46.18,
62.66, 79.83, 127.63, 127.66, 128.99, 129.49, 129.52,
132.77, 134.29, 143.00, 143.95; IR (film) n~Z1596, 1353,
1166 cmK1; EI-MS m/z (%): 509 (MC, 59), 354 (65), 298
(32), 156 (71), 91 (100). Anal. Calcd for C23H28INO2S: C,
54.22; H, 5.54; N, 2.75. Found: C, 54.34; H, 5.70; N, 2.81.
(MC, 11), 424 (47), 297 (54), 91 (100). Anal. Calcd for
C24H22INO2S: C, 55.93; H, 4.30; N, 2.72. Found: C, 55.75;
H, 4.36; N, 2.80.
3.5. One-pot preparation of dihydropyrrole 6a from
reaction of aziridine 1a with phenylacetylene 2a and
iodo-cyclization
˚
To a stirred solution of NaH (0.50 mmol) and 4 A molecular
sieves in DMSO (2.0 mL) was added phenylacetylene 2a
(0.375 mmol) and aziridine 1a (0.25 mmol) successively
under argon. The reaction mixture was stirred at room
temperature for 2 h. Then silver acetate (0.30 mmol) and
Iodine (0.75 mmol) was added. The reaction mixture was
warmed to 40 8C and stirred at room temperature for 5 h.
The reaction was quenched with saturated aqueous sodium
thiosulfate until the mixture was decolorized and the
organic layer was separated. The aqueous layer was then
extracted with dichloromethane (3!10 mL) and the organic
solutions were combined, dried over anhydrous MgSO4 and
concentrated under reduced pressure. The crude product
was then purified by column chromatography on silica gel to
provide product 6a.
3.4.3.
2,5-Diphenyl-3-iodo-1-(4-tolylsulfonyl)-2,3-
dihydropyrrole (6h). White solid; mp 124–125 8C; 1H
NMR (CDCl3/TMS) dZ2.46 (s, 3H), 2.66 (dd, JZ2.4,
16.8 Hz, 1H), 3.01 (dd, JZ9.6, 16.8 Hz, 1H), 5.34 (dd, JZ
2.4, 9.3 Hz, 1H), 7.26–7.44 (m, 8H), 7.51–7.58 (m, 6H); 13C
NMR (75 MHz, CDCl3) dZ21.63, 48.32, 64.34, 77.99,
125.82, 127.64, 127.68, 127.88, 128.84, 129.13, 129.53,
129.67, 132.19, 134.42, 142.26, 143.62, 144.09; IR (film)
n~Z1597, 1356, 1168 cmK1; EI-MS m/z (%): 502 ((MC
1)C, 88), 346 (78), 219 (100), 218 (96), 116 (93), 91 (62).
Anal. Calcd for C23H20INO2SNa (MCNa): 524.0152.
Found: 524.0157.
3.4.4. 2-Phenyl-3-iodo-5-butyl-1-(4-tolylsulfonyl)-2,3-
dihydropyrrole (6n). White solid; mp 116–117 8C; 1H
NMR (CDCl3/TMS) dZ0.95 (t, JZ6.6 Hz, 3H), 1.36–1.62
(m, 5H), 1.73–1.82 (m, 1H), 2.13 (dd, JZ1.2, 16.2 Hz, 1H),
2.43 (s, 3H), 2.48 (t, JZ8.4 Hz, 1H), 4.19–4.26 (m, 1H),
7.26 (d, JZ8.4 Hz, 2H), 7.38–7.41 (m, 3H), 7.53–7.59 (m,
4H); 13C NMR (75 MHz, CDCl3) dZ14.05, 21.60, 22.54,
26.90, 35.89, 46.17, 62.58, 79.82, 121.58, 127.62, 128.95,
129.45, 129.49, 132.74, 134.25, 142.95, 143.92; IR (film)
n~Z1597, 1355, 1168 cmK1; EI-MS m/z (%): 482 ((MC
1)C, 31.7), 326 (68), 156 (58), 115 (67), 91 (100). Anal.
Calcd for C21H24INO2S: C, 52.39; H, 5.03; N, 2.91. Found:
C, 52.45; H, 5.16; N, 2.69.
Acknowledgements
This work was supported by National Natural Science
Foundation of China, the Major Basic Research Develop-
ment Program (Grant No. G2000077506), National Out-
standing Youth Fund and Chinese Academy of Sciences.
C. H. D. gratefully acknowledged Hong Kong Croucher
Foundation for a Studentship.
References and notes
3.4.5. 2-Butyl-3-iodo-5-hexyl-1-(4-tolylsulfonyl)-2,3-
dihydropyrrole (6o). Liquid; H NMR (CDCl3/TMS) dZ
1. (a) McCoull, W.; Davis, F. A. Synthesis 2000, 1347. (b)
Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (c)
Kump, J. E. G. In Trost, B.M, Fleming, I., Eds.; Comprehen-
sive Organic Synthesis; Pergamon: Oxford, 1991; Vol. 7,
p 467. (d) Stamm, H. J. Prakt. Chem. 1999, 319. (e) Hu, X. E.
Tetrahedron 2004, 60, 2701.
1
0.87 (t, JZ6.9 Hz, 3H), 0.94 (t, JZ7.2 Hz, 3H), 1.28–1.75
(m, 14H), 1.89–1.94 (m, 1H), 2.18–2.27 (m, 1H), 2.43 (s,
3H), 2.46–2.56 (m, 1H), 2.77–2.87 (m, 1H), 3.97–4.03 (m,
1H), 7.28 (d, JZ7.8 Hz, 2H), 7.60 (d, JZ8.1 Hz, 2H); 13C
NMR (75 MHz, CDCl3) dZ13.91, 14.06, 21.58, 22.07,
22.54, 24.62, 29.06, 29.38, 29.97, 31.66, 36.13, 44.05,
62.56, 79.16, 127.19, 129.56, 134.46, 143.75, 144.86; IR
(film) n~Z1598, 1353, 1167 cmK1; EI-MS m/z (%): 489
(MC, 33), 362 (69), 334 (41), 256 (44), 91 (100). Anal.
Calcd for C20H20INO2S: C, 51.53; H, 6.59; N, 2.86. Found:
C, 51.34; H, 6.55; N, 2.75.
2. Some examples of the reaction of aziridine with alcohols or
phenols see: (a) Jacques, B.; Josette, C. R.; Roger, V. Synthesis
1992, 288. (b) Bellos, K.; Stamm, H. J. Org. Chem. 1995, 60,
5661. (c) Wipf, P.; Uto, Y. Tetrahedron Lett. 1999, 40, 5165.
(d) Stamm, H.; Schneider, L. Chem. Ber. 1974, 107, 2870.
3. Some examples of the reaction of aziridine with thiols see: (a)
Antolini, L.; Bucciarelli, M.; Caselli, E.; Davoli, P.; Forni, A.;
Moretti, I.; Prati, F.; Torre, G. J. Org. Chem. 1997, 62, 8784.
(b) Maligres, P. E.; See, M. M.; Askin, D.; Reider, P. J.
Tetrahedron Lett. 1997, 38, 5253. (c) Bae, J. H.; Shin, S. H.;
Park, C. S.; Lee, W. K. Tetrahedron 1999, 55, 10041. (d)
Katagiri, T.; Takahashi, M.; Fujiwara, Y.; Ihara, H.; Uneyama,
K. J. Org. Chem. 1999, 64, 7323. (e) Wu, J.; Hou, X. L.; Dai,
L. X. J. Chem. Soc., Perkin Trans. 1 2001, 1314.
3.4.6. 2-Phenyl-3-iodo-5-benzyl-1-(4-tolylsulfonyl)-2,3-
dihydropyrrole (6p). White solid; mp 93–94 8C; 1H
NMR (CDCl3/TMS) dZ2.33 (dd, JZ2.4, 16.8 Hz, 1H),
2.42 (s, 3H), 2.45 (dd, JZ8.7, 16.5 Hz, 1H), 2.92 (dd, JZ
9.3, 13.5 Hz, 1H), 3.23 (dd, JZ5.4, 13.5 Hz, 1H), 4.52–4.55
(m, 1H), 7.21–7.39 (m, 10H), 7.43–7.47 (m, 2H), 7.51–7.54
(m, 2H); 13C NMR (75 MHz, CDCl3) dZ21.56, 42.01,
44.78, 63.28, 78.64, 126.75, 127.52, 127.56, 128.49, 128.99,
129.44, 129.64, 132.31, 134.36, 136.55, 142.96, 143.91; IR
(film) n~Z1595, 1491, 1352 cmK1; EI-MS m/z (%): 515
4. Some examples of the reaction of aziridine with amines see:
(a) Nakajima, K.; Tanaka, T.; Morita, K.; Okawa, K. Bull.
Chem. Soc. Jpn. 1980, 53, 283. (b) Meguro, M.; Yamamoto, Y.
Heterocycles 1996, 43, 2473. (c) Lucet, D.; Gallo, T. L.;

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9593
Mioskowski, C. Angew. Chem., Int. Ed. 1998, 37, 2580. (d)
Sekar, G.; Singh, V. K. J. Org. Chem. 1999, 64, 2537.
3328. (g) Fuji, K.; Kawabata, T.; Kiryu, Y.; Sugiura, Y.
Heterocycle 1996, 42, 701.
5. (a) Oppolzer, W.; Flaskamp, E. Helv. Chim. Acta 1977, 60,
204. (b) Osborn, H. M.; Sweeney, J. B.; Howson, B. Synlett
1993, 675. (c) Tanner, D.; He, H. M.; Somfai, P. Tetrahedron
1992, 48, 6069. (d) Baldwin, J. E.; Adlington, R. M.;
Robinson, N. G. J. Chem. Soc., Chem. Commun. 1987, 153.
(e) Lygo, B. Synlett 1993, 764. (f) Dubois, L.; Mehta, A.;
Tourette, E. J. Org. Chem. 1994, 59, 434. (g) Bouayed, Z.;
Chanet-Ray, J.; Ducher, S.; Vessiere, R. J. Heterocycl. Chem.
1991, 28, 1757. (h) Mu¨ller, P.; Nury, P. Org. Lett. 1999, 1, 439.
6. (a) Gronquist, M. R.; Meinwald, J. J. Org. Chem. 2001, 66,
1075. (b) Rainier, J. D.; Imbriglio, J. E. J. Org. Chem. 2000,
65, 7272. (c) Daub, G. W.; Heering, D. A.; Overman, L. A.
7. (a) Wu, J.; Hou, X. L.; Dai, L. X. J. Org. Chem. 2000, 65,
1344. (b) Hou, X. L.; Fan, R. H.; Dai, L. X. J. Org. Chem.
2002, 67, 5295. (c) Fan, R. H.; Hou, X. L. J. Org. Chem. 2003,
68, 726. (d) Fan, R. H.; Zhou, Y. G.; Zhang, W. X.; Hou, X. L.;
Dai, L. X. J. Org. Chem. 2004, 69, 335. (e) Fan, R. H.; Hou,
X. L.; Dai, L. X. J. Org. Chem. 2004, 69, 689. (f) Ding, C. H.;
Dai, L. X.; Hou, X. L. Synlett 2004, 2218.
8. Ding, C. H.; Dai, L. X.; Hou, X. L. Synlett 2004, 1691.
9. (a) Backes, J. In Hanack, M., Ed. 4th ed.; Houben-Weyl
Methoden der Organischen Chemie; Thieme: Stuttgart, 1993;
Vol. E19d. (b) Patai, S. The Chemistry of the Carbon Carbon
Triple Bond; Wiley: New York, 1978.
´
`
Tetrahedron 1988, 44, 3919. (d) Compain, P.; Gore, J.; Vatele,
J. M. Tetrahedron 1996, 52, 10405. (e) Church, N. J.; Young,
D. W. Tetrahedron Lett. 1995, 36, 151. (f) Ooi, T.; Kagoshima,
N.; Ichikama, H.; Maruoka, K. J. Am. Chem. Soc. 1999, 121,
10. Knigh, D. W.; Redfern, A. L.; Gilmore, J. J. Chem. Soc.,
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