KOH-oriented ring openings of N-tosylaziridines with carboxylic acids in DMSO

Article abstract of DOI:10.1002/jhet.1962

A facile and efficient KOH-oriented regioselective ring-opening reaction for the acetolysis of N-tosylaziridines in DMSO was developed under mild conditions. This operationally simple protocol could tolerate a variety of functionalized carboxylic acids as well as several N-tosylaziridines.Moreover, this strategy provided the corresponding ring-opening products with good results.

Full text of DOI:10.1002/jhet.1962

284
KOH-Oriented Ring Openings of N-Tosylaziridines
Vol 52
with Carboxylic Acids in DMSO
a
a
*
F. Zhang, H. Chang and W. Wei
Department of Chemistry and Chemical Engineering, Taiyuan University of Technology, 79 West Yingze Street, Taiyuan
030024, People’s Republic of China
*
E-mail: weiwenlong@tyut.edu.cn
Received October 29, 2012
DOI 10.1002/jhet.1962
Published online 12 May 2014 in Wiley Online Library (wileyonlinelibrary.com).
O
O
R
R
Ts
HN
O
R3
R2
Ts
HN
O
R3
40 mol% KOH
DMSO, 45 o
N Ts
+
R3 COOH
+
C
R2
R
R2
26 examples
up to 99% yield
> 99% regioselectivity
A facile and efficient KOH-oriented regioselective ring-opening reaction for the acetolysis of N-tosylaziridines
in DMSO was developed under mild conditions. This operationally simple protocol could tolerate a variety
of functionalized carboxylic acids as well as several N-tosylaziridines. Moreover, this strategy provided the
corresponding ring-opening products with good results.
J. Heterocyclic Chem., 52, 284 (2015).
INTRODUCTION
reaction afforded little ring-opening product in DMSO.
Rising temperature up to 80ꢀC made limited impact (Table 1,
entry 1). Considering they may improve the nucleophilicity
of carboxylic acids, some bases were tried to catalyze this
process. It was found that weaker bases such as K2CO3 and
NEt3 were less effective than strong bases (Table 1, entries
2 and 3 vs. 4). KOH showed the excellent yield (Table 1,
entry 4). In the presence of a catalytic amount of KOH, the
reaction could be carried out smoothly and afforded the
desired ring-opening product in good yield (Table 1, entry
4). Surprisingly, however, this reaction could not take place
with stoichiometric amount of KOH (Table 1, entry 6) [63].
On the other hand, the examination of solvent effect indi-
cated that anhydrous DMSO could remarkably facilitate this
ring-opening reaction with the best yield (Table 1, entry 4),
and NMP indicated worse result (Table 1, entry 7). However,
other polar solvents failed to manifest such property (Table 1,
entries 8–13 vs. 4), which suggested that the positive solvent
effect of DMSO played another important role and its
presence was necessary in this catalytic process. In addition,
it was observed that this reaction worked most efficiently at
45ꢀC (Table 1, entry 15 vs. 4, 14, and 16). In summary,
extensive screening showed that the optimized reaction
conditions were 40mol% KOH and 1.2 equiv of acetic acid
(2a) under air atmosphere in 1.0 mL DMSO at 45ꢀC for 3 h
(Table 1, entry 15).
Aziridines are widely recognized as significant and
versatile building blocks for the synthesis of various bio-
logically active compounds [1–26]. Their activity has led
to wide research and use in the ring-opening reactions with
a range of nucleophiles [27–50]. As a result, this area has
attracted a great deal of attention over nearly three decades,
and the pace of development has shown no sign of abating
in recent years. Although there has been a great deal of
interest in the ring openings of N-tosylaziridines with
various nucleophiles, comparably, few examples on the
ring openings with carboxylic acids and their derivatives
are observed [51–54]. So, the discovery of new catalysts
that are cheaper and more efficient and the development
of new methods that are more effective remain a consider-
able challenge and are a long-standing problem. Inorganic
bases as efficient catalysts have been widely utilized in many
reactions (See Refs [51] and [52]) [55–57]. Moreover,
DMSO [58–62] has been efficiently utilized as an organic
catalyst or solvent in the ring-opening reactions of aziridines
with some nucleophiles. Herein, we wish to report the
successful application of KOH as a simple, inexpensive,
and remarkable catalyst for the efficient regioselective
ring openings of N-tosylaziridines with carboxylic acids
in DMSO.
With the optimized experimental conditions in hand, a
series of carboxylic acids including aromatic, aliphatic,
and heterocyclic acids were examined for the ring-opening
reactions of N-tosylaziridines, and the results are summa-
rized in Table 2. Neither the electronic property of the substi-
tution at the aromatic ring nor the steric hindrance had
obvious influence on the yields. Most aromatic carboxylic
RESULTS AND DISCUSSION
Our investigations began with the screening of catalysts by
selecting the ring-opening reaction of N-tosylcyclohexylaziridine
(1a) with acetic acid (2a) as the model system. Initial stud-
ies revealed that without any catalyst, the ring-opening
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KOH-Oriented Ring Openings of N-Tosylaziridines with Carboxylic Acids
285
Table 1
Ring opening of N-tosylcyclohexylaziridine (1a) with acetic acid (2a)a.
Entry
Base
Amount of base (mol%)
Solvent
T (ꢀC)
t (h)
Yieldb (%)
1
2
3
4
5
6
7
8
–
–
40
40
40
20
100
40
40
40
40
40
40
40
40
40
40
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
NMP
25–80
25
25
25
25
25
25
25
25
25
25
25
25
35
45
55
24
24
24
24
24
24
24
24
24
24
24
24
24
12
3
N.D.
23
30
95
40
K2CO3
TEA
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
trace
64
THF
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
98
9
Acetone
Dioxane
DMF
CH3CN
Toluene
DMSO
DMSO
DMSO
10
11
12
13
14
15
16
99
90
2
N.D., not detected.
aAll reactions were performed with N-tosylcyclohexylaziridine (1a) (50 mg, 0.2 mmol) and acetic acid (2a) (14 mL, 0.24 mmol, 1.2 equiv) in 1.0 mL
DMSO under the specified conditions.
bIsolated yield.
acids underwent rapidly the ring-opening reactions and
afforded the corresponding products in good to excellent
yields (Table 2, entries 2–9). Aliphatic and unsaturated acids
also offered excellent results (Table 2, entries 1, 11, and 12).
Heterocyclic aromatic carboxylic acid was found to be good
substrate and afforded the desired ring-opening product in
84% yield, too (Table 2, entry 10).
opening products was performed for this catalytic system.
As shown in Scheme 1, in the presence of 40 mol% of
KOH, 10 mmol of N-tosylaziridine (1m) reacted with
1.2 equiv of 2h to provide 3x as the single product in a total
yield of 83% (3.656 g). Similarly, subgram quantities of
products 3o and 4o with the isomer 3o as the major product
(4.318 g, 95% total yield, 3o:4o = 91:9) were obtained.
Subsequently, a variety of N-tosylaziridines such as
aromatic, aliphatic, and condensed-ring ones were investi-
gated under the optimal conditions, and the corresponding
major products 3 (aromatic N-tosylaziridines) or 4 (aliphatic
N-tosylaziridines) were provided in good to excellent yields,
as shown in Table 3. In the case of substituted aromatic N-
tosylaziridines, boththe electronicproperty and the steric hin-
drance of the substitution at the aromatic ring had no obvious
influence on the yields and up to 99% yield was obtained (Ta-
ble 3, entries 1–8, 11, and 12). In addition, condensed-ring N-
tosylaziridines were also found to be suitable substrates (Ta-
ble 3, entries 9 and 10). It was noteworthy that excellent
yields could be attained with substituted aliphatic N-tosyla-
ziridines (Table 3, entries 13 and 14). Inspiringly, most N-
tosylaziridines gave single regioisomers or good regioselec-
tivity except for 1c, 1e, 1g, 1h, 1j, 1k, and 1l, which provided
worse regioselectivity (Table 3, entries 2, 4, 6, 7, 9–11).
For the purpose of examining the synthetic potential of
the present approach, a gram-scaled synthesis of ring-
CONCLUSIONS
In conclusion, we developed facile, efficient, and high
atom economy KOH-oriented regioselective ring-open-
ing reactions for the acetolysis of N-tosylaziridines in
DMSO. The combined use of KOH and DMSO was cru-
cial and important to the desired ring-opening reaction.
More importantly, good to excellent yields have been
provided for a wide variety of N-tosylaziridines and
various carboxylic acids, and good to high regioselectivity
were obtained in terms of most N-tosylaziridines under
mild reaction conditions.
EXPERIMENTAL
General information.
Bruker AVANCE III 600 MHz NMR spectrometers. The
1H-NMR spectra were taken with
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F. Zang, H. Chang and W. Wei
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Table 2
Ring-opening reactions of N-tosylcyclohexylaziridine (1a) with various carboxylic acidsa.
Entry
1
Carboxylic acid (2)
CH3COOH
Product
t (h)
Yieldb (%)
2a
3
99
2
3
2
98
98
1.5
4
5
2
2
97
98
6
7
3
6
95
97
(Continued)
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Table 2
(Continued)
Entry
8
Carboxylic acid (2)
Product
t (h)
Yieldb (%)
95
3
9
4
5
94
84
10
11
12
HCOOH
4
80
94
2k
2l
H2C=HCOOH
1.5
aAll reactions were performed with N-tosylcyclohexylaziridine (1a) (50 mg, 0.2 mmol), carboxylic acids (2) (0.24 mmol, 1.2 equiv) and KOH (4.5 mg,
40 mol%) under air atmosphere in DMSO (1.0 mL) at 45ꢀC.
bIsolated yield.
chemical shifts are reported in parts per million (ppm) downfield to
the CDCl3 resonance (d = 7.27). Spectra are reported as follows:
chemical shift (d ppm), multiplicity (s = singlet, d = doublet,
t = triplet, q = quartet, and m = multiplet), coupling constants (Hz),
integration, and assignment. 13C-NMR data were collected at
150 MHz with complete proton decoupling. The chemical shifts
are reported in parts per million downfield to the central CDCl3
are uncorrected. Unless otherwise noted, reagents obtained from
commercial sources were used without further purification. All
solvents were purchased from commercial sources and used with
further purification. Deuterated solvents were purchased from
Aladdin. Column chromatography was performed on silica gel
(200–300 mesh). All yields were referred to isolated yields
(average of two runs) of compounds.
1
resonance (d = 77.0). Coupling constants in H-NMR spectra are
General procedure.
To a mixture of N-tosylaziridine
given in Hertz (Hz). High-resolution mass spectra were performed
on a micrOTOF-Q II instrument with an ESI source. Melting
points were measured with an RD-II melting point apparatus and
(0.2mmol), carboxylic acid (0.24 mmol, 1.2 equiv) and KOH
(4.5mg, 0.08 mmol, 40 mol%) was added DMSO (1 mL). The
reaction mixture was then stirred at 45ꢀC until the N-tosylaziridine
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Table 3
Ring-opening reactions of various N-tosylaziridines (1) with 4-nitrobenzoic acid (2h)a.
Entry
1
N-Tosylaziridine (1)
Product
t (h)
Yieldb (%)
96c (3m:4m = 70:30)
4
2
3
96c (3n:4n = 54:46)
3
3
97d (3o:4o = 91:9)
(Continued)
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Table 3
(Continued)
Entry
4
N-Tosylaziridine (1)
Product
t (h)
Yieldb (%)
5
98c (3p:4p = 62:38)
5
4
96c (3q:4q = 90:10)
6
3.5
97c (3r:4r = 64:36)
(Continued)
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Table 3
(Continued)
Entry
7
N-Tosylaziridine (1)
Product
t (h)
Yieldb (%)
4
72c (3s:4s = 51:49)
8
3
10
5
86c (3t:4t = 75:25)
86c (3u:4u = 56:44)
99d (3v:4v = 61:39)
9
10
11
2.5
92c (3w:4w = 52:48)
(Continued)
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Table 3
(Continued)
Entry
N-Tosylaziridine (1)
Product
t (h)
Yieldb (%)
12
4
80
13
5
98
14
10
92
aAll reactions were performed with N-tosylaziridines (1) (0.2 mmol), 4-nitrobenzoic acid (2h) (40 mg, 0.24 mmol, 1.2 equiv) and KOH (4.5 mg, 40 mol%)
under air atmosphere in DMSO (1.0 mL) at 45ꢀC.
bIsolated yield.
1
cThe ratios of the two isomer products were determined by H-NMR.
dCombined yield of isolated 3 and 4.
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(d, J = 8.4 Hz, 2H), 7.55–7.57 (d, J = 7.8 Hz, 2H)ppm. 13C-NMR
(150 MHz, CDCl3): d 21.3, 21.6, 23.8, 24.2, 31.3, 34.1, 57.3,
74.4, 126.6, 127.0, 128.8, 129.3, 129.8, 138.1, 142.6, 143.6,
166.9 ppm. MS (ESI): Calcd for C21H25NO4S + Na 410.1402,
Scheme 1. Scaled-up version of the ring-opening reactions.
found 410.1402.
2-(4-Methylphenylsulfonamido)cyclohexyl 2-nitrobenzoate
(3f).
White solid; mp 135–137ꢀC. 1H-NMR (600 MHz,
CDCl3): d 1.22–1.37 (m, 4H), 1.47–1.53 (m, 1H), 1.70–1.72
(m, 1H), 1.77–1.79 (m, 1H), 2.04–2.09 (m, 2H), 2.23 (s, 3H),
3.38–3.41 (m, 1H), 4.82–4.86 (m, 1H), 4.90–4.92 (d, J = 7.8 Hz,
1H), 7.02–7.03 (d, J = 8.4 Hz, 2H), 7.61–7.62 (d, J = 8.4 Hz, 2H),
7.98–8.00 (d, J = 9.0 Hz, 2H), 8.20–8.22 (d, J = 8.4 Hz, 2H) ppm.
13C-NMR (150 MHz, CDCl3): d 21.5, 23.4, 24.1, 30.2, 32.8, 56.3,
76.2, 123.6, 126.7, 127.4, 129.4, 130.2, 131.6, 132.9, 138.4,
142.8, 147.9, 165.2 ppm. MS (ESI): Calcd for C20H22N2O6S + Na
441.1096, found 441.1088.
2-(4-Methylphenylsulfonamido)cyclohexyl 3-nitrobenzoate
(3g).
White solid; mp 138–140ꢀC. 1H-NMR (600 MHz,
was consumed completely that was monitored by TLC.
Subsequently, the mixture was washed with 0.36 M of K2CO3
solution (10mL) to remove the remains of the carboxylic acid.
The water phase was extracted with CH2Cl2 (3 Â 5 mL). The
organic extracts were combined and dried over anhydrous
Na2SO4, filtered, and concentrated under reduced pressure to
obtain the remainder. At last, the resulting crude product was
purified by column chromatography on silica gel with petroleum
ether/ethyl acetate to afford the desired corresponding product in
high yield.
CDCl3): d 1.29–1.39 (m, 3H), 1.51–1.53 (m, 1H), 1.71–1.77
(m, 2H), 2.04–2.07 (m, 2H), 2.17 (s, 3H), 3.37–3.39 (m, 1H),
4.87–4.88 (m, 1H), 5.07–5.08 (d, J= 8.4 Hz, 1H), 6.97–6.98
(d, J=7.8Hz, 2H), 7.59–7.61 (d, J= 8.4 Hz, 3H), 8.19–8.20
(d, J = 7.8 Hz, 1H), 8.38–8.40 (m, 1H), 8.56 (t, J = 1.8 Hz,
1H) ppm. 13C-NMR (150MHz, CDCl3): d 21.3, 23.7, 24.2, 31.1,
33.5, 56.9, 75.8, 124.6, 126.6, 127.2, 129.4, 131.7, 135.5,
138.4, 142.8, 148.1, 164.4 ppm. MS (ESI): Calcd for
C20H22N2O6S + Na 441.1096, found 441.1096.
2-(4-Methylphenylsulfonamido)cyclohexyl acetate (3a). White
2-(4-Methylphenylsulfonamido)cyclohexyl 4-nitrobenzoate
1
White solid; mp 150–152ꢀC. 1H-NMR (600 MHz,
solid; mp 124–126ꢀC. H-NMR (600 MHz, CDCl3): d 1.16–1.27
(3h).
(m, 4H), 1.59–1.62 (m, 2H), 1.76 (s, 3H), 1.90–1.91 (m, 2H), 2.36
(s, 3H), 3.12–3.14 (m, 1H), 4.52–4.53 (m, 1H), 5.36–5.37 (d, 1H),
7.24–7.26 (d, J= 8.4 Hz, 2H), 7.71–7.72 (d, J=8.4Hz, 2H)ppm.
2-(4-Methylphenylsulfonamido)cyclohexyl benzoate (3b). White
CDCl3): d 1.27–1.37 (m, 3H), 1.45–1.52 (m, 1H), 1.6–1.75
(m, 2H), 2.01–2.09 (m, 2H), 2.23 (s, 3H), 3.38–3.40 (m, 1H),
4.82–4.86 (m, 1H), 5.04–5.06 (d, J=8.4Hz, 1H), 7.02–7.03
(d, J= 7.8 Hz, 2H), 7.61–7.63 (d, J= 8.4 Hz, 2H), 7.98–8.00
(d, J= 7.8 Hz, 2H), 8.19–8.21 (d, J=9.0Hz, 2H) ppm. 13C-NMR
(150 MHz, CDCl3): d 21.4, 23.7, 24.3, 31.1, 33.6, 56.9, 75.8,
123.2, 126.6, 129.5, 130.9, 135.2, 138.5, 142.9, 150.5, 164.7 ppm.
MS (ESI): Calcd for C20H22N2O6S + Na 441.1096, found 441.1093.
2-(4-Methylphenylsulfonamido)cyclohexyl 4-chlorobenzoate
(3i). White solid; mp 137–139ꢀC. 1H-NMR (600 MHz, CDCl3):
d 1.25–1.36 (m, 3H), 1.46–1.50 (m, 1H), 1.67–1.74 (m, 2H),
2.06–2.09 (m, 2H), 2.22 (s, 3H), 3.33–3.35 (m, 1H), 4.81–4.85
(m, 1H), 5.09–5.11 (d, J = 7.8 Hz, 1H), 6.99–7.01 (d, J = 8.4 Hz,
2H), 7.24–7.26 (m, 1H), 7.41–7.42 (d, J = 3.6 Hz, 2H), 7.63–7.68
(m, 3H) ppm.
1
solid; mp 156–158ꢀC. H-NMR (600 MHz, CDCl3): d 1.28–1.48
(m, 4H), 1.69–1.76 (m, 2H), 2.00–2.04 (m, 1H), 2.18 (s, 3H),
2.22–2.24 (m, 1H), 3.28–3.32 (m, 1H), 4.79–4.83 (m, 1H),
5.03–5.04 (d, 1H), 6.89–6.91 (d, J= 7.8 Hz, 2H), 7.35–7.38
(t, J= 7.8 Hz, 2H), 7.54–7.58 (m, 3H), 7.75–7.76 (m, 2H) ppm.
2-(4-Methylphenylsulfonamido)cyclohexyl 2-methylbenzoate
(3c).
White solid; mp 130–132ꢀC. 1H-NMR (600 MHz,
CDCl3): d 1.25–1.50 (m, 4H), 1.69–1.79 (m, 2H), 1.99–2.02
(m, 1H), 2.19 (s, 3H), 2.21 (m, 1H), 2.45 (s, 3H), 3.29–3.31
(m, 1H), 4.79–4.83 (m, 1H), 5.08–5.09 (d, J = 7.2 Hz, 1H),
6.90–6.91 (d, J = 8.4 Hz, 2H), 7.16–7.19 (m, 2H), 7.38–7.39
(d, J = 1.2 Hz, 1H), 7.57–7.58 (d, J = 8.4 Hz, 2H), 7.64–7.64
(d, J = 1.2 Hz, 1H) ppm. 13C-NMR (150 MHz, CDCl3): d 21.4,
22.0, 23.8, 24.2, 31.3, 34.0, 57.3, 74.3, 125.5, 126.5, 128.8,
129.3, 131.0, 131.6, 132.2, 138.2, 140.6, 142.7, 167.6 ppm.
MS (ESI): Calcd for C21H25NO4S + Na 410.1402, found
410.1403.
2-(4-Methylphenylsulfonamido)cyclohexyl picolinate (3j). White
1
solid; mp 220–222ꢀC. H-NMR (600 MHz, CDCl3): d 1.24–1.41
(m, 4H), 1.55–1.57 (m, 1H), 1.70–1.75 (m, 2H), 2.03–2.06
(m, 1H), 2.18 (s, 3H), 3.38–3.44 (m, 1H), 4.89–4.92 (m, 1H),
5.05–5.06 (d, J = 7.8 Hz, 1H), 6.91–6.93 (d, J = 8.4 Hz, 2H),
7.45–7.47 (m, 1H), 7.60–7.61 (d, J= 7.8 Hz, 2H), 7.75–7.78
(q, 1H), 7.88–7.89 (d, J= 7.8 Hz, 1H), 8.70–8.71 (q, 1H) ppm.
13C-NMR (150 MHz, CDCl3): d 21.4, 23.8, 24.2, 31.1, 34.0,
57.1, 75.6, 125.3, 126.7, 129.3, 136.7, 138.3, 142.5, 147.6, 149.8,
165.1 ppm. MS (ESI): Calcd for C19H22N2O4S + Na 397.1198,
2-(4-Methylphenylsulfonamido)cyclohexyl 3-methylbenzoate
(3d).
White solid; mp 129–131ꢀC. 1H-NMR (600 MHz,
CDCl3): d 1.25–1.49 (m, 4H), 1.68–1.76 (m, 2H), 1.99–2.01
(m, 1H), 2.16 (s, 3H), 2.17–2.20 (m, 1H), 2.37 (s, 3H), 3.29–3.31
(m, 1H), 4.79–4.83 (m, 1H), 5.20–5.21 (d, J= 7.2 Hz, 1H), 6.89–6.91
(d, J= 8.4 Hz, 2H), 7.23–7.26 (m, 1H), 7.34–7.35 (d, J=7.2Hz, 1H),
found 397.1192.
2-(4-Methylphenylsulfonamido)cyclohexyl formate (3k). White
1
solid; mp 116–118ꢀC. H-NMR (600 MHz, CDCl3): d 1.25–1.36
7.55–7.56 (m, 4H) ppm.
2-(4-Methylphenylsulfonamido)cyclohexyl 4-methylbenzoate
(m, 4H), 1.65–1.69 (m, 2H), 1.92–2.01 (m, 2H), 2.41 (s, 3H),
3.24–3.26 (m, 1H), 4.64–4.68 (m, 1H), 4.90–4.91 (d, J = 7.8 Hz,
1H), 7.28–7.29 (d, J = 8.4 Hz, 2H), 7.53 (s, 1H), 7.73–7.74
(3e).
White solid; mp 144–146ꢀC. 1H-NMR (600 MHz,
CDCl3): d 1.28–1.47 (m, 4H), 1.62–1.66 (m, 2H), 1.92–1.94
(m, 1H), 2.09 (s, 3H), 2.10–2.14 (m, 1H), 2.37 (s, 3H), 3.21–3.22
(m, 1H), 4.70–4.74 (m, 1H), 5.11–5.12 (d, J= 7.2 Hz, 1H), 6.82–6.83
(d, J = 8.4Hz, 2H), 7.07–7.08 (d, J = 7.8 Hz, 2H), 7.49–7.50
(d, J = 8.4 Hz, 2H) ppm.
2-(4-Methylphenylsulfonamido)cyclohexyl acrylate (3l). White
1
solid; mp 106–108ꢀC. H-NMR (600 MHz, CDCl3): d 1.21–1.36
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293
(m, 4H), 1.63–1.70 (m, 2H), 1.94–1.96 (m, 1H), 2.05–2.08 (m, 1H),
2.39 (s, 3H), 3.21–3.23 (m, 1H), 4.62–4.64 (m, 1H), 5.00–5.01 (d,
J = 7.2 Hz, 1H), 5.71–5.78 (m, 2H), 6.21–6.24 (dd, J= 16.8,
1.2 Hz, 1H), 7.23–7.24 (d, J= 7.8 Hz, 2H), 7.69–7.70 (d,
J= 8.4 Hz, 2H) ppm.
2-(4-Methylphenylsulfonamido)-1-o-tolylethyl 4-nitrobenzoate
150.6, 164.4 ppm. MS (ESI): Calcd for C22H19ClN2O6S + Na
497.0550, found 497.0550.
Mixture of 3r and 4r. Inseparable white solid (3r:4r= 64:36);
mp 134–137ꢀC. 1H-NMR (600 MHz, CDCl3): d 2.32 (s, 3H), 2.40
(s, 2H), 3.44–3.48 (m, 1H), 4.41–4.49 (m, 2H), 4.74–4.77 (m, 1H),
5.63 (t, 1H), 5.97–5.99 (m, 1H), 6.13–6.14 (d, J = 7.8 Hz, 1H),
7.06–7.07 (d, J = 8.4 Hz, 2H), 7.14–7.15 (d, J = 8.4 Hz, 2H),
7.16–7.17 (m, 2H), 7.22–7.27 (m, 4H), 7.55–7.57 (d, J = 8.4 Hz,
2H), 7.67–7.68 (d, J = 8.4 Hz, 1H), 8.03–8.05 (d, J = 8.4 Hz, 2H),
8.17–8.18 (m, 4H) ppm. 13C-NMR (150 MHz, CDCl3): d 21.5,
29.6, 47.4, 56.3, 67.4, 75.2, 123.5, 126.9, 127.9, 128.2, 128.9,
129.1, 129.5, 129.8, 130.9, 134.3, 134.6, 134.9, 135.0, 135.4,
136.8, 137.1, 143.7, 143.8, 150.7, 163.7, 164.4 ppm. MS (ESI):
(3m). White solid; mp 164–166ꢀC. 1H-NMR (600 MHz, CDCl3):
d 2.17 (s, 3H), 2.39 (s, 3H), 3.38–3.50 (m, 1H), 4.41–4.44 (m, 1H),
5.27–5.30 (t, J=7.2 Hz, 1H), 6.20–6.22 (q, 1H), 7.02–7.04
(d, J= 8.4 Hz, 1H), 7.16–7.19 (m, 1H), 7.20–7.27 (m, 2H),
7.30–7.31 (d, J= 7.8 Hz, 1H), 7.53–7.54 (d, J =8.4Hz, 1H),
7.70–7.72 (d, J=8.4Hz, 1H), 8.07–8.10 (dt, J= 9.0, 1.8 Hz, 1H),
8.15–8.17 (dt, J = 9.0, 1.8 Hz, 1H), 8.22–8.24 (d, J = 8.4 Hz,
2H) ppm. 13C-NMR (150 MHz, CDCl3): d 19.1, 21.4, 46.9, 73.1,
123.5, 125.5, 126.6, 127.0, 128.2, 128.8, 129.4, 129.9, 130.9,
134.9, 135.0, 135.4, 143.7, 150.6, 164.5ppm. MS (ESI): Calcd
Calcd for C22H19ClN2O6S + Na 497.0550, found 497.0556.
2-(4-Methylphenylsulfonamido)-1-(2-methoxyphenyl)ethyl 4-
nitrobenzoate (3s).
White solid; mp 150–152ꢀC. 1H-NMR
(600 MHz, CDCl3): d 2.38 (s, 3H), 3.44–3.49 (m, 1H), 3.53–3.57
(m, 1H), 3.82 (s, 3H), 4.95–4.97 (t, J = 6.4 Hz, 1H), 6.37–6.39
(q, 1H), 6.86–6.88 (m, 1H), 6.94–7.02 (m, 1H), 7.21–7.22
(d, J = 8.4 Hz, 2H), 7.27–7.31 (m, 2H), 7.67–7.68 (d, J = 8.4 Hz,
2H), 8.20–8.22 (m, 2H), 8.26–8.28 (m, 2H) ppm. 13C-NMR
(150 MHz, CDCl3): d 21.5, 46.3, 55.8, 70.9, 110.8, 120.9, 123.5,
124.6, 126.5, 127.0, 129.2, 129.6, 130.9, 135.2, 137.3, 143.4,
150.7, 156.0, 163.7 ppm. MS (ESI): Calcd for C23H22N2O7S + Na
for C23H22N2O6S + Na 477.1096, found 477.1093.
Mixture of 3n and 4n. Inseparable white solid (3n:4n =54:46);
mp 137–144ꢀC. 1H-NMR (600 MHz, CDCl3): d 2.21 (s, 3H), 2.30
(s, 3H), 2.31 (s, 3H), 2.39 (s, 3H), 3.41–3.54 (m, 2H), 4.42–4.49
(m, 1H), 4.50–4.52 (m, 1H), 4.73–4.74 (td, J = 7.8, 4.8 Hz, 1H),
5.49–5.52 (t, J = 4.8 Hz, 1H), 5.92–5.93 (d, J = 7.8 Hz, 1H),
5.95–5.97 (m, 1H), 6.90 (s, 1H), 6.98–7.01 (m, 2H), 7.03–7.06
(m, 2H), 7.10–7.13 (t, J = 7.2 Hz, 4H), 7.21–7.23 (m, 3H),
7.56–7.57 (d, J = 8.4 Hz, 2H), 7.69–7.71 (d, J = 8.4 Hz, 2H),
8.06–8.08 (m, J = 8.4 Hz, 2H), 8.14–8.16 (dt, J = 9.0, 2.4 Hz,
2H), 8.18–8.20 (m, 4H) ppm. 13C-NMR (150MHz, CDCl3): d
21.2, 21.4, 21.5, 47.7, 56.9, 67.7, 75.9, 123.4, 127.0, 127.1,
128.8, 129.4, 129.8, 130.9, 134.8, 135.0, 136.4, 136.6, 137.0,
137.4, 138.5, 138.7, 143.4, 143.6, 150.6, 163.8, 164.5ppm. MS
493.1045, found 493.1044.
Mixture of 3t and 4t. Inseparable white solid (3t:4t= 75:25);
1
mp 87–89ꢀC. H-NMR (600 MHz, CDCl3): d 2.27 (s, 3H), 2.38
(s, 3H), 3.47–3.48 (m, 1H), 3.50–3.55 (m, 1H), 3.82 (s, 3H),
3.91 (s, 3H), 4.42–4.43 (m, 2H), 4.64–4.68 (m, 1H), 5.10–5.13
(m, 1H), 5.77–5.78 (d, J = 7.8 Hz, 1H), 5.92–5.95 (m, 1H),
6.37–6.39 (m, 1H), 6.74–6.78 (m, 1H), 6.87–6.93 (m, 1H),
6.93–7.03 (m, 5H), 7.19–7.25 (m, 3H), 7.27–7.31 (m, 3H),
7.52–7.54 (m, 2H), 7.67–7.68 (d, J = 8.4 Hz, 2H), 7.75–7.77
(m, 3H), 8.09–8.11 (d, J = 9.0 Hz, 1H), 8.20–8.26 (m, 6H) ppm.
13C-NMR (150 MHz, CDCl3): d 21.4, 21.5, 47.6, 55.3, 67.7,
75.6, 112.4, 113.9, 118.5, 118.9, 123.5, 127.0, 129.5, 129.8,
130.1, 130.9, 134.8, 137.0, 137.3, 138.0, 138.3, 143.4, 143.7,
150.6, 159.9, 163.7, 164.5 ppm. MS (ESI): Calcd for
(ESI): Calcd for C23H22N2O6S + Na 477.1096, found 477.1091.
2-(4-Methylphenylsulfonamido)-1-p-tolylethyl 4-nitrobenzoate
(3o). White solid; mp 140–142ꢀC. 1H-NMR (600 MHz, CDCl3):
d 2.17 (s, 3H), 2.39 (s, 3H), 3.43–3.52 (m, 1H), 4.42–4.53 (m, 1H),
5.18–5.20 (t, J=6.4Hz, 1H), 5.95–5.97 (dd, J = 6.4, 4.2 Hz, 1H),
7.05–7.08 (m, 2H), 7.14–7.16 (d, J= 7.8 Hz, 2H), 7.21–7.27
(m, 2H), 7.57–7.58 (d, J= 8.4 Hz, 1H), 7.68–7.70 (t, J=8.4Hz,
1H), 8.06–8.08 (d, J = 9.0Hz, 1H), 8.15–8.17 (d, J =9.0Hz, 1H),
8.20–8.22 (q, 2H) ppm. 13C-NMR (150 MHz, CDCl3): d 21.2,
21.5, 47.6, 75.7, 123.5, 126.4, 127.0, 129.6, 129.8, 130.9, 133.4,
135.1, 137.0, 139.0, 143.7, 150.6, 163.8 ppm. MS (ESI): Calcd for
C23H22N2O7S + Na 493.1045, found 493.1047.
2-(4-Methylphenylsulfonamido)-1-(naphthalen-7-yl)ethyl 4-
nitrobenzoate (3u).
White solid; mp 184–186ꢀC. 1H-NMR
(600 MHz, CDCl3): d 2.35 (s, 3H), 3.53–3.63 (m, 2H), 5.36–5.38
(t, 1H), 6.15–6.17 (q, J= 4.2, 3.6 Hz, 1H), 7.15–7.16 (d, J=8.4Hz,
2H), 7.23–7.27 (m, 1H), 7.35–7.41 (dd, J= 8.4, 1.8 Hz, 1H),
7.47–7.49 (m, 2H), 7.50–7.56 (d, J = 8.4 Hz, 1H), 7.65–7.69
(d, J = 8.4 Hz, 2H), 7.76–7.81 (m, 3H), 8.16–8.21 (m, 3H) ppm.
13C-NMR (150MHz, CDCl3): d 21.5, 47.6, 75.9, 123.5, 126.1,
126.7, 126.7, 126.9. 127.7, 128.1, 128.9, 129.4, 129.8, 130.9,
133.0, 133.4, 133.7, 135.0, 136.9, 143.7, 150.6, 163.8 ppm.
C23H22N2O6S + Na 477.1096, found 441.1093.
2-(4-Methylphenylsulfonamido)-1-(2-chlorophenyl)ethyl 4-
nitrobenzoate (3p).
White solid; mp 175–177ꢀC. 1H-NMR
(600 MHz, CDCl3): d 2.28 (s, 3H), 4.42–4.45 (dd, J = 11.4,
4.8 Hz, 1H), 4.56–4.59 (dd, J = 11.4, 7.8 Hz, 1H), 5.22–5.25
(m, 1H), 5.82–5.84 (d, J = 7.8 Hz, 1H), 7.05–7.06 (d, J = 7.8 Hz,
2H), 7.14–7.19 (m, 2H), 7.26–7.33 (m, 2H), 7.59–7.61
(d, J = 8.4 Hz, 2H), 8.04–8.06 (d, J = 8.4 Hz, 2H), 8.21–8.23
(d, J = 8.4 Hz, 2H) ppm. 13C-NMR (150 MHz, CDCl3): d 21.4,
54.4, 66.3, 123.5, 127.0, 127.2, 128.7, 129.5, 129.9, 130.9,
132.5, 134.3, 134.6, 136.9, 143.5, 150.7, 164.5 ppm. MS (ESI):
MS (ESI): Calcd for C26H22N2O6S + Na 513.1096, found 513.1095.
2-(4-Methylphenylsulfonamido)-1-(naphthalen-5-yl)ethyl 4-
nitrobenzoate (3v).
White solid; mp 189–191ꢀC. 1H-NMR
(600 MHz, CDCl3): d 2.37 (s, 3H), 3.62–3.66 (m, 2H), 5.18–5.20
(t, J = 6.4 Hz, 1H), 6.79–6.81 (dd, J = 4.2, 3.6Hz, 1H), 7.19–7.20
(d, J = 8.4 Hz, 2H), 7.42–7.44 (t, J = 7.8 Hz, 1H), 7.52–7.55
(m, 3H), 7.66–7.67 (d, J = 8.4 Hz, 2H), 7.81–7.83 (m, 1H),
7.87–7.88 (m, 1H), 7.98–8.00 (d, J = 8.4 Hz, 1H), 8.22–8.26
(m, 4H) ppm. 13C-NMR (150 MHz, CDCl3): d 21.5, 47.2, 73.3,
122.4, 123.6, 124.0, 125.2, 126.2, 127.0, 127.0, 129.2, 129.5,
129.8, 130.0, 131.0, 132.2, 133.8, 135.0, 137.0, 143.7, 150.7,
163.9 ppm. MS (ESI): Calcd for C26H22N2O6S + Na513.1096,
found 513.1097.
Calcd for C22H19ClN2O6S + Na 497.0550, found 497.0550.
2-(4-Methylphenylsulfonamido)-1-(3-chlorophenyl)ethyl 4-
nitrobenzoate (3q).
White solid; mp 146–148ꢀC. 1H-NMR
(600 MHz, CDCl3): d 2.30 (s, 3H), 3.44–3.48 (m, 1H), 4.42–4.45
(m, 1H), 4.56–4.59 (m, 1H), 6.17–6.18 (d, J= 7.8 Hz, 1H), 7.06–7.07
(d, J= 7.8 Hz, 1H), 7.09–7.13 (m, 2H), 7.16–7.17 (m, 1H), 7.23–7.24
(d, J= 7.8 Hz, 1H), 7.27–7.28 (m, 1H), 7.55–7.57 (m, 1H), 7.68–7.70
(q, 1H), 8.04–8.05 (m, 1H), 8.15–8.17 (q, 3H) ppm. 13C-NMR
(150MHz, CDCl3): d 21.4, 56.4, 674, 124.4, 125.0, 126.9, 127.2,
128.4, 129.5, 129.9, 130.1, 130.9, 134.6, 137.0, 138.8, 143.7,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

294
F. Zang, H. Chang and W. Wei
Vol 52
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B.; Altomare, A. J Org Chem 2009, 74, 6319.
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Crotti, P. J Org Chem 2006, 71, 1696.
[12] Hwang, G. II; Chung, J. H.; Lee, W. K. J Org Chem 1996, 61, 6183.
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B. Org Lett 2002, 4, 497.
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S. J Org Chem 2009, 74, 7958.
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Lee, J. H.; Kang, J. S. Org Lett 2001, 3, 2349.
Mixture of 3w and 4w. Inseparable white solid (3w:4w = 52:48);
mp 152–156ꢀC. 1H-NMR (600 MHz, CDCl3): d 2.32 (s, 3H), 2.40
(s, 3H), 3.46–3.48 (m, 2H), 4.41–4.43 (m, 1H), 4.46–4.49 (m, 1H),
4.71–4.75 (m, 1H), 5.50–5.53 (m, 1H), 5.95–5.96 (m, 1H),
6.02–6.03 (m, 1H), 7.06–7.07 (m, 4H), 7.19–7.22 (t, 2H),
7.24–7.27 (t, 2H), 7.33–7.34 (d, J = 8.4 Hz, 2H), 7.43–7.45
(d, J = 9.0Hz, 2H), 7.54–7.56 (d, J = 7.8 Hz, 2H), 7.66–7.67
(d, J = 7.8Hz, 2H), 8.04–8.05 (d, J = 8.4 Hz, 2H), 8.14–8.16
(d, J = 8.4 Hz, 2H), 8.18–8.21 (dd, J = 9.0, 7.2 Hz, 4H)ppm.
13C-NMR (150MHz, CDCl3): d 122.4, 123.1, 123.5, 126.9,
128.1, 128.5, 129.5, 129.8, 130.9, 131.9, 132.1, 134.5, 134.7,
135.5, 135.9, 136.8, 137.1, 143.7, 150.7, 163.6, 164.4ppm. MS
(ESI): Calcd for C22H19BrN2O6 + Na 541.0045, found 541.0041.
2-(4-Methylphenylsulfonamido)-1-phenylethyl 4-nitrobenzoate
(3x). White solid; mp 143–145ꢀC. 1H-NMR (600 MHz, CDCl3):
d 2.32 (s, 3H), 4.43–4.45 (q, 1H), 4.48–4.51 (q, 1H), 4.76–4.79
(m, 1H), 5.80–5.82 (d, 1H), 7.08–7.13 (m, 3H), 7.19–7.20
(m, 1H), 7.27–7.28 (d, J = 8.4 Hz, 2H), 7.57–7.58 (d, J = 8.4 Hz,
2H), 8.06–8.07 (m, 2H) , 8.20–8.21 (m, 2H) ppm. 13C-NMR
(150MHz, CDCl3): 21.5, 47.7, 56.8, 67.8, 75.9, 123.4, 127.0,
128.8, 128.9, 129.5, 129.8, 130.9, 134.8, 135.0, 136.5, 136.8,
136.9, 137.3, 143.4, 143.7, 150.6, 163.8, 164.4 ppm. MS (ESI):
[19] Xiong, C. Y.; Wang, W.; Cai, C. Z.; Hruby, V. J. J Org Chem
2002, 67, 1399.
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[26] Samanta, K.; Panda, G. Chem Asian J 2011, 6, 189.
[27] Lu, P. F. Tetrahedron 2010, 66, 2549.
Calcd for C22H20N2O6S + Na 463.0940, found 463.0940.
2-(4-Methylphenylsulfonamido)octyl 4-nitrobenzoate (3y). White
1
solid; mp 116–118ꢀC. H-NMR (600 MHz, CDCl3): d 0.82–0.84
(t, J = 7.2 Hz, 3H), 1.13–1.20 (m, 8H), 1.46–1.53 (m, 2H), 2.35
(s, 3H), 3.60–3.63 (dd, J = 7.8, 4.8 Hz, 1H), 4.25–4.28 (m, 2H),
5.18–5.19 (d, J = 8.4 Hz, 1H), 7.20–7.22 (d, J = 7.8 Hz, 2H),
7.74–7.75 (d, J = 7.8 Hz, 2H), 8.11–8.12 (d, J = 9.0 Hz, 2H),
8.21–8.22 (d, J = 8.4 Hz, 2H) ppm. 13C-NMR (150MHz, CDCl3):
d 13.9, 21.4, 22.4, 25.4, 28.8, 31.5, 32.3, 52.9, 67.3, 123.4, 126.9,
129.7, 130.8, 135.0, 138.5, 143.5, 150.6, 164.5 ppm. MS (ESI):
[28] Dureault, A.; Tranchepain, I.; Depezay, J. C. J Org Chem
1989, 54, 5324.
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1990, 55, 4683.
[30] Minakata, S.; Yoneda, Y.; Oderaotoshi, Y.; Komatsu, M. Org
Lett 2006, 8, 967.
Calcd for C22H28N2O6S + Na 471.1566, found 471.1562.
[31] Tanner, D.; He, H. M. Tetrahedron 1992, 48, 6079.
[32] Wu, J.; Hou, X. L.; Dai, L. X. J Org Chem 2000, 65, 1344.
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Tetrahedron Lett 2009, 50, 2815.
[34] Hu, X. E. Tetrahedron 2004, 60, 2701.
[35] Sureshkumar, D.; Koutha, S. M.; Chandrasekaran, S. J Am
Chem Soc 2005, 127, 12760.
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2007, 72, 3859.
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[39] Ghorai, M. K.; Nanaji, Y.; Yadav, A. K. Org Lett 2011,
13, 4256.
2-(4-Methylphenylsulfonamido)cyclopentyl 4-nitrobenzoate
(3z).
White solid; mp 143–145ꢀC. 1H-NMR (600 MHz,
CDCl3): d 1.54–1.58 (m, 1H), 1.70–1.77 (m, 4H), 2.08–2.13
(m, 1H), 2.29 (s, 3H), 3.70–3.74 (m, 1H), 5.13–5.16 (m, 1H),
5.37–5.38 (d, J = 6.4 Hz, 1H), 7.14–7.16 (d, J = 7.8 Hz, 2H),
7.72–7.73 (d, J = 7.8 Hz, 2H), 8.04–8.05 (m, 2H), 8.24–8.26 (m,
2H) ppm. 13C-NMR (150 MHz, CDCl3): d 20.7, 21.4, 29.5, 31.0,
59.6, 81.0, 123.4, 127.1, 129.6, 130.8, 135.2, 137.4, 143.4, 150.6,
164.4 ppm. MS (ESI): Calcd for C19H20N2O6S + Na 427.0940,
found 427.0938.
[40] Minakata, S.; Hotta, T.; Oderaotoshi, Y.; Komatsu, M. J Org
Chem 2006, 71, 7471.
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Van Nieuwenhove, A.; Ha, H. J.; Waroquier, M.; De Kimpe, N.;
Van Speybroeck, V. J Org Chem 2010, 75, 4530.
[43] Minakata, S.; Okada, Y.; Oderaotoshi, Y.; Komatsu, M. Org
Lett 2005, 7, 3509.
Acknowledgment. We appreciate gratefully the Natural Science
Foundation of Shanxi Province (No. 2012021007-2 and No.
2011011010-2) for financial support.
[44] Xu, Y. J.; Lin, L. Q.; Kanai, M.; Matsunaga, S.; Shibasaki, M.
J Am Chem Soc 2011, 133, 5791.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

January 2015
KOH-Oriented Ring Openings of N-Tosylaziridines with Carboxylic Acids
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

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