Cationic micelle-catalyzed ring-opening reactions of aziridines with thiols in water

Article abstract of DOI:10.1002/cjoc.201190112

An efficient and practical method is described for the ring-opening reactions of N-tosylaziridines with various thiols in water under mild conditions. Various surfactants have been evaluated to optimize the reactions. Under optimal conditions, these react

Full text of DOI:10.1002/cjoc.201190112

FULL PAPER
Cationic Micelle-catalyzed Ring-Opening Reactions of
Aziridines with Thiols in Water
Yang, Mina(杨民)
Yang, Qina,b(杨琴)
Chen, Puqinga(陈朴青)
Peng, Yiyuan*,a,b(彭以元)
a Key Laboratory of Functional Small Organic Molecule, Ministry of Education and College of Chemistry and
Chemical Engineering, Nanchang, Jiangxi 330022, China
b Jiangxi Key Laboratory of Green Chemistry and College of Life Science, Jiangxi Normal University,
Nanchang, Jiangxi 330022, China
An efficient and practical method is described for the ring-opening reactions of N-tosylaziridines with various
thiols in water under mild conditions. Various surfactants have been evaluated to optimize the reactions. Under op-
timal conditions, these reactions gave rise to the corresponding β-amino sulfides in good to excellent yields.
Keywords pyridine-N-oxide, ring-opening reaction, N-tosylaziridine, thiol, β-amino sulfide
Introduction
with various thiols in water with a catalytic amount of
cationic surfactant under mild conditions, leading to the
corresponding β-amino sulfides in good to excellent
yields.
Aziridines have recently attracted much attention as
versatile intermediates and important precursors for the
synthesis of many nitrogen-containing biologically in-
teresting molecules.1 Considerable progress has been
achieved in the nucleophilic ring-opening reactions of
aziridines.2 They are known to react with various nu-
cleophiles and their properties to undergo regioselective
ring opening reactions contribute largely to their syn-
thetic value.3 Among these reactions, the ring-opening
reactions of aziridines with thiols are attractive4 because
the resulting β-amino sulfides are crucial for the synthe-
sis of many biologically interesting molecules such as
amino acids,1b,1h heterocycles,5 and alkaloids.6 However,
most of these reactions require a strong base or Lewis
acid.7 For example, cinchonine,2b DABCO,2c or
DMSO2d has been used as catalyst or promoter to facili-
tate the ring-opening reactions of aziridines with thiols.
On the other hand, organic reactions in aqueous me-
dium have attracted lots of attention, since water is an
environmentally friendly and safe medium, which
avoids pollutions that are inherent with organic sol-
vents.8 Hou9 and co-workers described ring-opening
reaction promoted by tributylphosphine. Recently, Rao
et al.10 reported the reactions occurred in the presence of
β-cyclodextrin. Qu and co-workers11 reported the ring-
opening reactions of aziridines with thiophenols in hot
water, of which the reaction time is very long. Hence, an
efficient and environmentally friendly new methodology
is needed for the ring opening of aziridines under con-
venient and mild conditions.12 In our continuous efforts
in green chemistry13 and ring-opening reactions of
aziridines,14 we describe herein an efficient and practical
procedures for the ring-opening reactions of aziridines
Results and discussion
Initially, aziridine 1a and p-methylbenzenethiol 2a
were used as model substrates to optimize the reaction
conditions (Table 1). No reaction was observed at room
temperature in pure water, or with 20 mol% of nonionic
surfactant such as PEG-200 (Table 1, Entries 1— 2).
However, when 20 mol% of anionic surfactant such as
sodium dodecylbenzenesulfonic (SDBS) was added, the
reaction gave rise to the desired product in 54% yield
(Entry 3). Other cationic surfactants were evaluated as
well, and the reaction proceeded smoothly to afford the
corresponding product in moderate to excellent yields
(Entries 4— 11). The dependence of the efficiency on
substitutent on ammonium cation shows an inverted
U-curve. The reaction gave 60% yield with dodecyl-
trimethylammoium chloride (Entry 4), while 73% yield
of product was observed when dodecyldimethylben-
zylammoium chloride was used (Entry 5). When am-
monium salts with longer substituents were utilized, the
yields decreased (Entries 6— 10). The counterion of the
ammonium salts also contributed to the catalytic effi-
ciency. When dodecyldimethylbezylammoium bromide
(DDBAB) was used, the product was obtained in 93%
yield within 0.5 h (Entry 11).
Effects of thios on the ring-opening reactions
The scope of this reaction was investigated under
these optimized conditions. The ring-opening reactions
between aziridine 1a and various aryl and alkyl thios
*
E-mail: yiyuanpeng@yahoo.com
Received August 24, 2009; revised October 27, 2009; accepted November 25, 2009.
Project supported by the National Natural Science Foundation of China (Nos. 20862009, 20962010), Jiangxi Educational Committee (No. GJJ10386)
and the National Natural Science Foundation of Jiangxi Province (No. 2008GQH0026).
Chin. J. Chem. 2011, 29, 499— 503
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
499

Yang et al.
FULL PAPER
Table 1 Ring-opening reactions of aziridine with 4-methyl-
Table 2 Ring-Opening reactions of aziridine 1a with various
benzenethiol in H2O with 20 mol% surfactant
thios in water with 20 mol% DDBAB
Entry
1
Product
3aa
Time/h
0.5
Yielda/%
93
Entry
Surfactant
None
Time/h Yielda/%
1
2
24
24
12
12
6
0
PEG-200
0
3
C12H25C6H4SO3Na
C12H25N(CH3)3Cl
54
60
73
40
65
50
50
45
93
4
5
C12H25(PhCH2)N(CH3)2Cl
C16H33N(CH3)3Cl
6
12
12
12
12
12
0.5
2
3
4
5
6
7
8
0.5
97
98
86
93
80
61
0
7
C16H33N(CH3)3Br
C16H33(PhCH2)N(CH3)3Cl
C18H37N(CH3)3Cl
3ab
3ac
8
9
10
11
C5H5N(C16H33)Cl
1
C12H25(PhCH2)N(CH3)2Br
a Isolated yield based on the aziridine.
were first examined in the presence of 20 mol%
DDBAB in water at room temperature. The results are
present in Table 2. Thiophenols reacted faster and af-
forded higher yields than alkyl thiols (Entries 1— 6 vs.
7— 8). Sterically hindered thiophenols reacted slower
(Entries 5, 6). No product was detected when propyl
thiol was used as the nucleophile under standard condi-
tions (Entry 8). Interestingly, 2-aminobenzenethiol,
which is inert in ring-opening reactions in previous re-
ports,2 reacted with aziridine 1a smoothly to afford the
corresponding product in 80% yield. In this transforma-
tion, it is noteworthy that no N-attacked product was
detected (Table 2, Entry 6).
1
3ad
3ae
2.5
3.5
24
24
Effects of aziridines on the ring-opening reaction
3af
The ring-opening reactions between a variety of
aziridines and benzenethiol were examined subsequently
under optimized conditions, and the results are summa-
rized in Table 3. Moderate to excellent yields (70%—
97%) were obtained for all aziridines in Table 3. In the
case of the unsymmetric aziridines (1c and 1d), regiose-
lective attack of the thiol on the less substituted
aziridine carbon was observed (Table 3, Entries 3 and 4).
When electronic effect participates, such as substrates
1e, 1f, 1g and 1h, the regioselectivity decreased (Table 3,
Entries 5, 6, 7, and 8) as previously reported.2d,14
3ag
3ah
a Isolated yield based on the arziridine.
Conclusions
Experimental
In summary, we have developed an efficient and
clean method for the ring-opening of aziridines with
various thiols catalyzed by cationic surfactant. The
method provides several synthetic features: (1) neither a
base nor an acid catalyst is needed in the reaction; (2)
water is the solvent; (3) the reaction conditions are mild.
General procedure for the reactions of aziridines
with various thiols
The thiophenols (1.1 equiv.) was added to a solution
of substrate 1 (0.20 mmol) in H2O with surfactant (0.04
mmol surfactant in 2.0 mL water). The reaction mixture
500
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Chin. J. Chem. 2011, 29, 499— 503

Cationic Micelle-catalyzed Ring-Opening Reactions of Aziridines with Thiols in Water
Table 3 Ring-opening reactions of aziridine with benzenethiol
in H2O with 20 mol% DDBAB
3H), 2.87—2.97 (m, 2H), 5.04 (brs, 1H, NH), 7.18—
7.30 (m, 6H), 7.73 (d, J＝7.6 Hz, 2H); 13C NMR
(CDCl3, 100 MHz) δ: 21.6, 23.2, 24.4, 31.4, 32.0, 51.4,
54.9, 127.3, 129.1, 129.7, 131.3, 133.8, 134.4, 137.2,
143.5.
N-[2-(4-Fluorophenylthio)cyclohexyl]-4-methyl-
benzenesulfonamide (3ad)14 White solid; yield 86%;
1
m.p. 102—103 ℃; H NMR (CDCl3, 400 MHz) δ:
1.24—1.39 (m, 5H), 1.60 (t, J＝6.0 Hz, 1H), 1.96—1.97
(m, 1H), 2.27—2.28 (m, 1H), 2.45 (s, 3H), 2.78—2.79 (m,
1H), 2.91—2.92 (m, 1H), 5.29 (brs, 1H, NH), 6.92—6.97
(m, 2H), 7.25—7.32 (m, 4H), 7.74 (d, J＝8.0 Hz);
13C NMR (CDCl3, 100 MHz) δ: 21.6, 23.3, 24.6, 31.4,
32.1, 51.9, 55.0, 115.9 (d), 127.2 (d), 129.6, 136.0 (d),
137.3, 143.4, 161.4, 163.9; IR (KBr) ν: 3294.4, 3028.8,
2934.7, 2852.6, 1597.2, 1494.9, 1443.9, 1327.0, 1158.4,
1083.8, 817.0, 710.0, 668.0 cm－ 1; HRMS calcd for
C19H22FNO2S2 379.1076, found 379.1072.
N-[2-(2-Chlorophenyl)thiocyclohexyl]-4-methyl-
benzenesulfonamide (3ae)14 White solid; yield 93%;
m.p. 100—101 ℃; 1H NMR (CDCl3, 400 MHz) δ: 1.25
—1.31 (m, 4H), 1.33—1.36 (m, 1H), 1.61—1.64 (m,
1H), 2.01—2.05 (m, 1H), 2.28—2.31 (m, 1H), 2.43 (s,
3H), 3.05—3.06 (m, 2H), 5.10 (d, J＝2.8 Hz, 1H, NH),
7.18—7.20 (m, 2H), 7.25—7.30 (m 2H), 7.36—7.40 (m,
2H), 7.75 (d, J＝8.4 Hz, 2H); 13C NMR (CDCl3, 100
MHz) δ: 21.6, 23.2, 24.3, 31.4, 32.5, 50.2, 55.3, 127.2,
127.4, 128.5, 129.7, 130.0, 133.0, 133.2, 136.4, 136.9,
143.5.
Entry Azirisine Time/h
Product
3aa
Yielda/%
1
2
3
4
5
6
7
8
1a
1b
1c
1d
1e
1f
0.5
5.0
1.0
0.5
1.0
1.5
1.5
2.5
97
79
74
70
79
70
70
3ba
3ca
3da
3ea/4ea (1.7/1.0)b
3fa/4fa (1.0/3.3)b
3ga/4ga (1.0/3.9)b
1g
1h
3ha/4ha (1.0/1.8)b
71
a
b
1
Isolated yield based on aziridine. Ratio was determined by H
NMR.
was stirred at room temperature for time indicated in
Tables 3 and 4. After the reaction was completed (as
indicated by TLC), the mixture was extracted with
CH2Cl2. The organic extracts were dried (MgSO4), and
concentrated under reduced pressure. Purification by
silica gel column chromatography afforded the corre-
sponding products. All the products are known com-
pounds, and confirmed by 1H NMR and 13C NMR.
N-[2-(4-Methylphenyl)thiocyclohexyl]-4-methyl-
benzenesulfonamide (3aa)2c White solid; yield 93%;
m.p. 94—96 ℃; 1H NMR (CDCl3, 400 MHz) δ: 1.31—
1.36 (m, 4H), 1.59—1.65 (m, 2H), 1.97—2.01 (m, 1H),
2.27—2.28 (m, 1H), 2.32 (s, 3H), 2.43 (s, 3H), 2.76—
2.82 (m, 1H), 2.91—2.95 (m, 1H), 5.31 (brs, 1H, NH),
7.06 (d, J＝8.0 Hz, 2H), 7.16 (d, J＝8.0 Hz, 2H), 7.30
(d, J＝8.0 Hz, 2H), 7.75 (d, J＝8.0 Hz, 2H); 13C NMR
(CDCl3, 100 MHz) δ: 21.1, 21.5, 22.7, 23.4, 29.7, 39.8,
51.9, 55.3, 126.9, 127.3, 129.7, 129.9, 133.9, 137.1,
138.0, 143.3.
N-[2-(2-Aminophenyl)thiocyclohexyl]-4-methyl-
benzenesulfonamide (3af)14 Solid; yield 80%; m.p.
1
133—135 ℃; H NMR (CDCl3, 400 MHz) δ: 1.18—
1.25 (m, 4H), 1.37—1.38 (m, 1H), 1.56—1.62 (m, 1H),
1.91—2.02 (m, 1H), 2.18—2.19 (m, 1H), 2.43 (s, 3H),
2.71—2.72 (m, 1H), 2.98—3.10 (m, 1H), 4.45 (br, 2H),
5.15 (d, J＝5.2 Hz, 1H), 6.61—6.65 (m, 1H), 6.71 (d, J＝
7.6 Hz, 1H), 7.11—7.16 (m, 2H), 7.28 (d, J＝8.4 Hz,
2H), 7.74 (d, J＝8.0 Hz, 2H); 13C NMR (CDCl3, 100
MHz) δ: 21.6, 23.7, 24.9, 32.3, 52.0, 56.1, 60.5, 115.2,
115.7, 118.6, 127.2, 129.7, 130.4, 137.4, 137.6, 143.3,
149.1; IR (KBr) ν: 3468.2, 3371.7, 3279.8, 2931.1,
2861.4, 1615.3, 1481.9, 1447.5, 1408.4, 1334.2, 1311.1,
1154.8, 1094.8, 814.0, 749.7, 671.0; HRMS calcd for
C19H24N2O2S2 376.1279, found 376.1278.
N-(2-Benzylthio-cyclohexyl)-4-methyl-benzenesul-
N-(2-Phenyl)thiocyclohexyl-4-methylbenzenesul-
1
fonamide (3ag)2d Yellow liquid; yield 61%; H NMR
fonamide (3ab)2e White solid; yield 97%; m.p. 131—
1
(CDCl3, 400 MHz) δ: 1.18—1.26 (m, 4H), 1.38—1.39
(m, 1H), 1.59—1.69 (m, 1H), 1.99—2.04 (m, 1H), 2.20
—2.24 (m, 1H), 2.39—2.42 (m, 1m), 2.43 (s, 3H), 2.89
—2.93 (m, 1H), 4.11 (dd, J＝3.2, 14.4 Hz, 2H), 5.11 (d,
J＝4.0 Hz, 1H), 7.21—7.34 (m, 7H), 7.75 (d, J＝8.4 Hz,
2H); 13C NMR (CDCl3, 100 MHz) δ: 21.1, 21.6, 23.7,
25.1, 34.3, 48.2, 55.4, 60.4, 127.2, 127.3, 128.6, 128.8,
129.6, 137.2, 137.9, 143.4.
132 ℃; H NMR (DMSO-d6, 400 MHz) δ: 1.21—1.35
(m, 4H), 1.47—1.51 (m, 2H), 1.61—1.68 (m, 1H), 1.96—
1.97 (m, 1H), 2.37 (s, 3H), 3.04—3.12 (m, 2H), 7.25—
7.29 (m, 5H), 7.34 (d, J＝7.2 Hz, 2H), 7.63 (d, J＝8 Hz,
2H), 7.79 (d, J＝7.2 Hz, 1H); 13C NMR (CDCl3, 100
MHz) δ: 21.4, 22.7, 23.5, 30.5, 31.0, 49.7, 54.5, 126.8,
127.0, 129.4, 129.9, 131.4, 134.9, 139.4, 142.8.
N-[2-(4-Chlorophenyl)thiocyclohexyl]-4-methyl-
benzenesulfonamide (3ac)2d White solid; yield 98%;
N-[(2-Phenyl)thiocyclopentyl]-4-methylbenzene-
sulfonamide (3ba)2a White solid; yield 79%; m.p. 78—
1
m.p. 109—111 ℃; H NMR (CDCl3, 400 MHz) δ:
1
80 ℃; H NMR (CDCl3, 400 MHz) δ: 1.51—1.61 (m,
1.25—1.38 (m, 4H), 1.39—1.42 (m, 1H), 1.59—1.62 (m,
2H), 1.65—1.73 (m, 2H), 2.08—2.18 (m, 2H), 2.44 (s,
1H), 1.97—2.01 (m, 1H), 2.26—2.27 (m, 1H), 2.45 (s,
Chin. J. Chem. 2011, 29, 499— 503
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Yang et al.
FULL PAPER
3H), 3.22—3.26 (m, 1H), 3.27—3.35 (m, 1H), 4.62 (d,
J＝4.4 Hz, 1H, NH), 7.24—7.34 (m, 7H), 7.64 (d, J＝
8.8 Hz, 2H); 13C NMR (CDCl3, 100 MHz) δ: 21.5, 21.6,
30.2, 31.6, 52.6, 59.4, 127.3, 128.9, 129.7, 132.3, 133.6,
143.5.
7.62 (d, J＝8.0 Hz, 1.6H); 13C NMR (CDCl3, 100 MHz)
δ: 21.6, 46.9, 52.2, 121.9, 127.0, 127.2, 128.0, 128.8,
129.8, 132.3, 132.8, 136.6, 137.4, 138.1, 143.7.
N-[1-(2-Chlorophenyl)-2-(phenylthio)ethyl]-4-
methylbenzenesulfonamide14 (3ha) and N-[2-(2-
chlorophenyl)-2-(phenylthio)ethyl]-4-methylbenzene-
sulfonamide14 (4ha) Mixture (3ha/4ha＝10/90): Liq-
4-Methyl-N-(1-(phenylthio)hexan-2-yl)benzene-
sulfonamide (3ca)2e Liquid; yield 74%; 1H NMR
(CDCl3, 400 MHz) δ: 0.74 (t, J＝7.2 Hz, 3H), 1.11—
1.14 (m, 4H), 1.25—1.26 (m, 1H), 1.55—1.56 (m, 1H),
2.40 (s, 3H), 2.75—2.80 (m, 1H), 3.10—3.14 (m 1H),
3.30—3.35 (m, 1H), 4.76 (d, J＝8.0 Hz, 1H), 7.20—
7.26 (m, 7H), 7.63 (d, J＝8.0 Hz, 2H); 13C NMR
(CDCl3, 100 MHz) δ: 13.8, 21.5, 22.2, 27.3, 33.5, 39.3,
52.9, 126.5, 127.1, 129.0, 129.6, 129.8, 137.5, 143.4.
4-Methyl-N-(1-phenylthiomethyl-heptadecyl)-
benzenesulfonamide (3da)2d White solid; yield 70%;
1H NMR (CDCl3, 400 MHz) δ: 0.88 (t, J＝6.8 Hz, 3H),
1.14—1.42 (m, 30H), 2.39 (s, 3H), 2.78—2.81 (m, 1H),
3.18—3.19 (m, 1H), 3.31—3.38 (m, 1H), 4.70 (d, J＝
7.6 Hz, 1H), 7.20—7.28 (m, 7H), 7.63 (d, J＝8.0 Hz,
2H); 13C NMR (CDCl3, 100 MHz) δ: 14.2, 22.7, 25.2,
29.0, 29.4, 29.5, 29.7, 31.9, 39.4, 52.9, 126.5, 127.1,
129.0, 129.6, 129.8.
1
uid; yield 71%; H NMR (CDCl3, 400 MHz) δ: 2.34 (s,
0.3H), 2.35 (s, 2.7H), 2.89—3.90 (m, 0.1H), 3.31—3.37
(m, 0.9H), 3.42—3.49 (m, 0.9H), 3.57—3.60 (m, 0.1H),
4.65 (t, J＝7.2 Hz, 0.9H), 4.67—4.68 (m, 0.1H), 4.99 (t,
J＝6.4 Hz, 0.9H), 5.01 (t, J＝5.6 Hz, 0.1H), 7.08—7.53
(m, 11H), 7.68 (d, J＝8.0 Hz, 1.8H), 7.73 (d, J＝8.0 Hz,
0.2H); 13C NMR (CDCl3) δ: 21.6, 45.9, 48.5, 127.1, 127.6,
128.0, 128.5, 129.1, 129.06, 129.9, 132.4, 133.9, 135.6,
136.6, 143.6; IR (KBr) ν: 3287.5, 2926.4, 1598.1, 1439.3,
1331.7, 1265.7, 1160.6, 1092.0, 739.9 cm－ 1; HRMS
calcd for C21H20ClNO2S2 417.0624, found 417.0624.
References
1
For some reviews of syntheses and reactions of activated
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4-Methyl-N-[1-phenyl-2-(phenylthio)ethyl]benzene-
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1
60/40): Colourless liquid; yield 79%; H NMR (CDCl3,
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400 MHz) δ: 2.40 (s, 1.8H), 2.41 (s, 1.2H), 3.25—3.40
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0.4H), 4.25—4.30 (m, 0.6H), 4.62—4.71 (m, 0.4H),
5.25 (d, J＝8.4 Hz, 0.6H), 6.99—7.26 (m, 12H), 7.49 (d,
J＝8.4 Hz, 1.2H), 7.70 (d, J＝8.0 Hz, 0.8H); 13C NMR
(CDCl3, 100 MHz) δ: 21.6, 47.1, 52.4, 126.8, 127.1,
127.8, 127.9, 128.1, 128.9, 129.0, 129.8, 132.6, 136.8,
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2
N-(1-(4-Chlorophenyl)-2-(phenylthio)ethyl)-4-
methylbenzenesulfonamide (3fa)2e and N-[2-(4-
chlorophenyl)-2-(phenylthio)ethyl]-4-methylbenzene-
sulfonamide (4fa)2e Mixture (3fa/4fa＝25/75): White
solid; yield 70%; 1H NMR (CDCl3, 400 MHz) δ: 2.39 (s,
0.75H), 2.42 (s, 2.25H), 3.12—3.15 (m, 0.5H), 3.31—
3.35 (m, 1.5H), 4.13 (t, J＝6.4 Hz, 0.75H), 4.18—4.19
(m, 0.25H), 4.71 (t, J＝6.4 Hz, 0.75H), 5.30 (d, J＝8.4
Hz, 0.25H), 7.02—7.06 (m, 2H), 7.12—7.28 (m, 9H),
7.48 (d, J＝8.4 Hz, 0.5H), 7.62 (d, J＝8.0 Hz, 1.5H);
13C NMR (CDCl3, 100 MHz) δ: 21.6, 47.0, 52.1, 127.0,
128.0, 128.1, 128.9, 129.0, 129.1, 129.2, 129.8, 132.8,
136.7, 136.9, 143.7.
3
4
N-[1-(4-Bromophenyl)-2-(phenylthio)ethyl]-4-
methylbenzenesulfonamide (3ga)15 and N-[2-(4-bromo-
phenyl)-2-(phenylthio)ethyl]-4-methylbenzenesulfon-
amide (4ga)15 Mixture (3g/4g＝20/80): White solid;
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1
yield 70%; H NMR (CDCl3, 400 MHz) δ: 2.39 (s,
0.6H), 2.42 (s, 2.4H), 3.11—3.14 (m, 0.4H), 3.30—3.37
(m, 1.6H), 4.11 (t, J＝7.6 Hz, 0.8H), 4.28—4.29 (m,
0.2H) 4.70 (t, J＝6.4 Hz, 0.8H), 5.20 (d, J＝4.0 Hz,
0.2H) 6.93 (d, J＝8.4 Hz, 0.4H), 6.99 (d, J＝8.4 Hz,
1.6H), 7.12—7.37 (m, 9H), 7.47 (d, J＝8.0 Hz, 0.4H),
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Uneyama, K. J. Org. Chem. 1999, 64, 7323.
(e) Wu, J.; Hou, X. L.; Dai, L. X. J. Chem. Soc., Perkin
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