An efficient method for opening N -tosylaziridines with silylated nucleophiles by using polystyrene-supported 1,5,7-triazabicyclo[44.0]dec-5-ene as a reusable organocatalyst

Article abstract of DOI:10.1055/s-0033-1339378

Polystyrene-supported 1,5,7-triazabicyclo[4.4.0]dec-5-ene (PS-TBD) catalyzes the ring opening of N-tosylaziridines with trimethylsilyl cyanide, trimethylsilyl azide, or trimethylsilyl halides to give the corresponding products in high yields. PS-TBD can b

Full text of DOI:10.1055/s-0033-1339378

PRACTICAL SYNTHETIC PROCEDURES
▌2959
pArancticEal sfyfnithceitiec nprotceMdureesthod for Opening N-Tosylaziridines with Silylated Nucleo-
philes by Using Polystyrene-Supported 1,5,7-Triazabicyclo[4.4.0]dec-5-ene as
a Reusable Organocatalyst
Catalytic Ring Cleavage of N-Tosylaziridines
Satoru Matsukawa,* Kumiko Tsukamoto, Shiori Yasuda, Takeru Harada
Department of Science Education, Faculty of Education, Ibaraki University,
2-1-1 Bunkyo, Mito, Ibaraki, 310-8512, Japan
Fax +81(29)228 8234; E-mail: smatsuka@mx.ibaraki.ac.jp
PSP
Received: 14.06.2013; Accepted: 21.06.2013
No258
Abstract: Polystyrene-supported 1,5,7-triazabicyclo[4.4.0]dec-5-ene (PS-TBD) catalyzes the ring opening of N-tosylaziridines with tri-
methylsilyl cyanide, trimethylsilyl azide, or trimethylsilyl halides to give the corresponding products in high yields. PS-TBD can be easily
recovered and reused without significant loss of catalytic activity.
Keywords: catalysis, polymers, ring opening, heterocycles, aziridines, sulfonamides
N
N
N
NHTs
NTs
NTs
PS-TBD
Nu = CN, 80 °C, 4 h, 94%
Nu = N3, r.t., 8 h, 94%
Nu = Cl, r.t., 2 h, 97%
Nu = Br, r.t., 2 h, 97%
H
Nu
(5 mol%)
TMSNu
TMSNu
+
+
H
DMF
PS-TBD
(5 mol%)
NHTs
Nu = CN, 80 °C, 4 h, 91%
Nu = N3, r.t., 8 h, 95%
Nu = Cl, r.t., 2 h, 90%
Nu
n-Hex
n-Hex
DMF
Scheme 1 Ring opening of N-tosylaziridines catalyzed by PS-TBD
Aziridines, as small-ring heterocycles, are very useful in- ability.7 1,5,7-Triazabicyclo[4,4,0]dec-5-ene functional-
termediates for the synthesis of many nitrogen-containing ized polystyrene (PS-TBD) is a polymer-supported
biologically active compounds.1 Consequently, numerous organobase catalyst that consists of a bicyclic guanidine
ring-opening reactions of activated or nonactivated aziri- moiety {1,5,7-triazabicyclo[4.4.0]dec-5-ene (1,3,4,6,7,8-
dines have been reported.2 Among these approaches, ring hexahydro-2H-pyrimido[1,2-a]pyrimidine)} anchored on
cleavage with silylated nucleophiles, such as silyl cya- polystyrene. This catalyst has been used to mediate the al-
nides, azides, or halides, is an important reaction for the kylation of phenols, amines, active methylene com-
preparation of highly functionalized compounds. Ring- pounds, and thiols; the esterification of carboxylic acids;
opening reactions with silylated nucleophiles catalyzed the dehalogenation of organic halides; and the high-
by Lewis acids,3 fluoride ion,4 Lewis bases,5 or N-hetero- throughput syntheses of aryl triflates and aryl nonaflates.8
cyclic carbenes6 have been developed to realize high PS-TBD is also a good catalyst for the Henry reaction and
yields and high selectivities. In search of a broadly appli- for the addition of dialkyl phosphites to a variety of car-
cable and environmentally friendly reaction, we planned bonyl compounds and imines.9 Recently, PS-TBD cata-
to use a polymer-supported organobase as a recyclable lyzed ring-opening reactions of epoxides, aldol-type
Lewis base catalyst.
condensations, and Michael additions have also been re-
ported.10 We have reported the use of PS-TBD as a base
catalyst for the cyanosilylation of carbonyl compounds
and imines.11 Here, we present a practical procedure for
ring cleavage of aziridines with silylated nucleophiles by
using polystyrene-supported TBD as a reusable organo-
catalyst (Scheme 1).12
Polymer-supported catalysts have attracted considerable
attention in recent decades because of their inherent ad-
vantages in synthetic chemistry; these include simplifica-
tion of reaction procedures, easy recovery of the catalyst
by filtration, applicability in automated systems, and reus-
First, we examined the ring-opening reaction of 7-tosyl-7-
azabicyclo[4.1.0]heptane (1a) with trimethylsilyl cyanide
in the presence of 5 mol% of PS-TBD in N,N-dimethyl-
formamide at 80 °C. The desired sulfonamide 2a was ob-
SYNTHESIS 2013, 45, 2959–2965
Advanced online publication: 12.08.2013
DOI: 10.1055/s-0033-1339378; Art ID: SS-2013-Z0410-PSP
© Georg Thieme Verlag Stuttgart · New York
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X

2960
S. Matsukawa et al.
PRACTICAL SYNTHETIC PROCEDURES
tained in 95% yield after four hours. The catalytic
activities of polystyrene-supported 4-(N,N-dimethylami-
no)pyridine (PS-DMAP), triphenylphosphine (PS-PPh3),
and N,N-diisopropylethylamine (PS-DIPEA) were inferi-
or to those of PS-TBD (Table 1, entries 1, 3, 4 and 5; Fig-
ure 1). Product 2a was obtained in a low yield when other
solvents such as tetrahydrofuran, dichloromethane, aceto-
nitrile, or toluene were used (entries 3–5). We also exam-
ined the reaction in under solvent-free conditions (entry
6), but the yield was unsatisfactory because N-tosylaziri-
dine is a solid substrate and is difficult to mix without a
solvent.
NHTs
PS-TBD
NTs
H
CN
(5 mol%)
TMSCN
+
H
DMF
80 °C, 4 h
1a
2a
Run
1st
Yield (%)
95
96
90
91
92
2nd
3rd
4th
5th
Scheme 2 Reuse of recovered PS-TBD
Table 1 Optimization of the Reaction Conditions
polymer-supported
organobase
NHTs
NTs
washed, dried, and reused. The catalyst retained its cata-
lytic activity after four further runs.
H
CN
(5 mol%)
TMSCN
+
H
solvent
temp, 4 h
To clarify the scope of this reaction, we examined the re-
actions of several N-tosylaziridines in the presence of 5
mol% PS-TBD (Table 2). The ring-opening reactions of
both 2-substituted N-tosylaziridines and 2,3-disubstituted
N-tosylaziridines all occurred smoothly to afford the cor-
responding products in good to excellent yields. In the
case of 2-substituted N-tosylaziridines, the reaction pro-
ceeded smoothly when 1 mol% of PS-TBD was used. Al-
most complete regioselectivity (> 98:2) was observed
with both phenyl- and alkyl-substituted N-tosylaziridines.
Unfortunately, in the case of the less-reactive trans-2,3-
diphenyl-1-tosylaziridine (1i), the yield was unsatisfacto-
ry.
1a
2a
Entry Base
Solvent
Temp (°C)
Yield (%)
1
2
PS-TBD
PS-TBD
DMF
DMF
DMF
DMF
DMF
THF
80 °C
r.t.
95
11
3
PS-DMAP
PS-PPh3
PS-DIPEA
PS-TBD
PS-TBD
PS-TBD
PS-TBD
PS-TBD
80 °C
80 °C
80 °C
45
4
51
5
12
6
66 °C (reflux)
82 °C (reflux)
40 °C (reflux)
80 °C
trace
15
7
MeCN
CH2Cl2
toluene
–
A gram-scale synthesis of the ring-opening reaction of N-
tosylaziridine 1c with trimethylsilyl cyanide was per-
formed to examine the synthetic potential of the reaction.
In the presence of 1 mol% of PS-TBD, 15 mmol of N-to-
sylaziridine 1c reacted with 20 mmol of trimethylsilyl cy-
anide to give the corresponding product 2c in 88% yield
(Scheme 3).
8
trace
trace
48
9
10
80 °C
NTs
n-Hex
N
N
1c
N
N
N
(15 mmol)
NHTs
PS-TBD
(1 mol%)
Me
CN
PS-TBD
PS-DMAP
+
n-Hex
DMF
80 °C, 14 h
2c
88% yield (4.07 g)
TMSCN
(20 mmol)
N
P
Scheme 3 Scaled-up version of the ring-opening reaction
PS-DIPEA
PS-PPh3
We found that the TBD-catalyzed reaction was also appli-
cable to other silylated nucleophiles: trimethylsilyl azide
and trimethylsilyl halides (Table 3). The reaction proceed-
ed smoothly at room temperature to give the correspond-
ing products in high yields from both 2-substituted
aziridines and 2,3-disubstituted aziridines. In this case, the
less-reactive 2,3-diphenylaziridine 1i also gave good re-
sults. A high level of regioselectivity (>95:5) was ob-
Figure 1
We then examined the recovery and reuse of PS-TBD in
the reaction of aziridine 1a with trimethylsilyl cyanide
(Scheme 2). When the reaction was completed, ethyl ace-
tate was added to the reaction mixture and the catalyst was
recovered by filtration. The recovered catalyst was
Synthesis 2013, 45, 2959–2965
© Georg Thieme Verlag Stuttgart · New York

PRACTICAL SYNTHETIC PROCEDURES
Catalytic Ring Cleavage of N-Tosylaziridines
2961
Table 3 PS-TBD-Catalyzed Ring-Opening of Aziridines with Other
Silylated Nucleophilest
Table 2 PS-TBD-Catalyzed Ring-Opening Reactions of Various
Aziridines with Trimethylsilyl Cyanide
H
PS-TBD
(5 mol%)
TsHN
TsHN
H
Nu
TBD
NTs
NTs
H
H
(5 mol%)
H
H
H
H
R1
H
R2
R2
TMSCN
+
R1
R2
NHTs
4a–i
R1
R1
+
H
TMSNu
R1
DMF
80 °C, time
DMF
r.t., time
R2
1a–i
Nu
3a–i
R2
1a–i
CN
2a–i
Entry Aziridine
Product
Time (h) Yielda (%)
Entry Aziridine Nu
Major product
Time (h) Yielda (%)
NTs
NTs
NTs
NTs
H
CN
H
N3
1
4
85
89
H
1
1a
N3
8
94
H
1a
2a
3a
NTs
NTs
H
H
Cl
CN
H
2
12
2
3
1a
1a
Cl
Br
2
2
97
97
H
1b
2b
3a′
NTs
NTs
NTs
NTs
CN
3
4
12
91
85
H
n-Hex
Br
n-Hex
4b
1c
H
2c
NTs
3a′′
CN
n-Bu
5
4
4
4
4
95
95
94
87
n-Bu
NTs
H
1d
2d
N3
H
4
5
1b
1b
N3
Cl
12
2
88
95
NTs
NTs
Ph
Ph
CN
6
3b
1e
2e
NTs
H
NTs
NTs
Cl
H
CN
Ph
7
8
9
Ph
1f
3b′
2f
NTs
NTs
NTs
N3
CN
4-Tol
6
7
8
1c
1c
1d
N3
Cl
N3
8
2
8
95
90
82
n-Hex
4-Tol
1g
3c
2g
NTs
NTs
NTs
Cl
CN
4-ClC6H4
n-Hex
4-ClC6H4
4
81
12
1h
3c′
2h
NTs
NTs
H
NTs
H
Ph
N3
CN
H
n-Bu
Ph
H
10c
12
Ph
Ph
3d
NTs
NTs
NTs
1i
2i
Ph
N3
Cl
a Isolated yield.
9
10
11
1e
1e
1e
N3
Cl
Br
8
1
1
92
98
98
b 1 mol% PS-TBD.
3e
c The reaction was carried out at 100 °C.
Ph
3e′
served when using alkyl-substituted aziridines as
substrates, whereas the phenyl-substituted aziridine 1f
showed poor regioselectivity in its reactions with trimeth-
ylsilyl azide and with trimethylsilyl chloride. Although
the reason for this is unclear, we suspect that electronic ef-
fects might provide a possible explanation.
Ph
Br
3e′′
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 2959–2965

2962
S. Matsukawa et al.
PRACTICAL SYNTHETIC PROCEDURES
Table 3 PS-TBD-Catalyzed Ring-Opening of Aziridines with Other
Silylated Nucleophilest (continued)
or 80 °C. When the reaction was complete (TLC), EtOAc (5 mL)
was added to the mixture and the PS-TBD was separated by filtra-
tion. The filtrate was concentrated under vacuum and purified by
column chromatography [silica gel, EtOAc–hexane (1:3)] to give
the corresponding product. The recovered catalyst was reusable af-
ter washing with acetone and H2O, and drying in vacuo.
TsHN
H
Nu
TBD
NTs
H
(5 mol%)
H
H
H
R2
R1
R2
NHTs
4a–i
R1
+
H
TMSNu
R1
DMF
r.t., time
R2
1a–i
Nu
3a–i
N-(trans-2-Cyanocyclohexyl)tosylamide (2a)4
By following the general procedure, the reaction of aziridine 1a
(251 mg, 1 mmol) with TMSCN (167 μL, 1.25 mmol) gave color-
less cubes; yield: 264 mg (95%); mp 67–70 °C.
Entry Aziridine Nu
Major product
Time (h) Yielda (%)
IR (KBr): 3250, 2250, 1620 cm–1.
N3
1H NMR (500 MHz, CDCl3): δ = 1.20–1.38 (m, 3 H), 1.51–1.67 (m,
3 H), 1.86–1.94 (m, 1 H), 1.97–2.04 (m, 1 H), 2.43 (s, 3 H), 2.66 (br
s, 1 H), 3.35 (dq, J = 4.6, 8.0 Hz, 1 H), 5.32 (d, J = 8.0 Hz, 1 H),
7.32 (d, J = 8.5 Hz, 2 H), 7.80 (d, J = 8.5 Hz, 2 H).
13C NMR: (125 MHz, CDCl3): δ = 21.5, 22.6, 22.9, 27.1, 31.4, 34.4,
52.7, 120.2, 127.2, 129.8, 137.1, 143.9.
NTs
Ph
12
13
1f
1f
N3
Cl
12
2
97b
91c
4f
Cl
NTs
Ph
HRMS (FAB): m/z [M + H]+ calcd for C14H19N2O2S: 279.1167;
4f′
NTs
found: 279.1169.
H
Ph
N3
H
N-(trans-2-Cyanocyclopentyl)tosylamide (2b)4
By following the general procedure, the reaction of aziridine 1b
(237 mg, 1 mmol) with TMSCN (167 μL, 1.25 mmol) gave color-
less plates; yield: 235 mg (89%); mp 109–111 °C.
14d
15d
1i
1i
N3
Cl
8
80
75
Ph
3i′
NTs
IR (KBr): 3260, 2250, 1600 cm–1.
H
Ph
Cl
H
1H NMR (500 MHz, CDCl3): δ = 1.40–1.48 (m, 1 H), 1.64–1.73 (m,
2 H), 1.74–1.85 (m, 1 H), 1.86–1.96 (m, 1 H), 2.00–2.07 (m, 1 H),
2.41 (s, 3 H), 2.83 (dt, J = 6.0, 8.5 Hz, 1 H), 3.69–3.75 (m, 1 H),
5.71 (d, J = 7.0 Hz, 1 H), 7.30 (d, J = 8.0 Hz, 2 H), 7.77 (d, J = 8.0
Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.4, 22.6, 28.9, 32.5, 35.6, 58.6,
121.1, 127.2, 129.9, 136.5, 144.0.
12
Ph
3i′′
a Isolated yield; product 3 was obtained exclusively unless otherwise
noted.
b Regioisomer ratio 3f/4f = 22:78.
c Regioisomer ratio 3f′/4f′ = 10:90.
d The reaction was carried out at 30 °C.
HRMS (FAB): m/z [M + H]+ calcd for C13H17N2O2S: 265.1011;
found: 265.1021.
N-[1-(Cyanomethyl)heptyl]tosylamide (2c)4
By following the general procedure, the reaction of aziridine 1c
(281 mg, 1 mmol) with TMSCN (167 μL, 1.25 mmol) gave a color-
less oil; yield: 257 mg (91%).
IR (neat): 3310, 2250, 1600 cm–1.
1H NMR (500 MHz, CDCl3): δ = 0.81 (t, J = 7.5 Hz, 3 H), 1.07–
1.20 (m, 8 H), 1.47–1.58 (m, 2 H), 2.41 (s, 3 H), 2.54 (dd, J = 3.5,
In conclusion, we have shown that ring-opening reactions
of N-tosylaziridines with trimethylsilyl cyanide, trimethyl
azide, or trimethylsilyl halides are catalyzed by 5 mol% of
PS-TBD under mild conditions. Furthermore, PS-TBD
can be easily recovered and reused with minimal loss of
activity after five runs. These reactions provide a simple
and environmentally friendly method for the synthesis of 16.5 Hz, 1 H), 2.64 (dd, J = 6.0, 16.5 Hz, 1 H), 3.38–3.41 (m, 1 H),
4.83 (d, J = 8.0 Hz, 1 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.75 (d, J = 8.0
Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 14.0, 21.5, 22.4, 25.0, 25.2, 28.4,
highly functionalized β-amino acids, 1,2-diamines, or 1,3-
diamines.
31.4, 33.9, 50.0, 116.7, 127.0, 129.9, 137.0, 144.0.
HRMS (FAB): m/z [M + H]+ calcd for C16H25N2O2S: 309.1637;
found: 309.1628.
All reactions were performed under argon in oven-dried glassware.
Flash column chromatography was performed on silica gel (Wakogel
C-200). Preparative TLC was carried out on silica gel (Wakogel B-
5F). Anhyd DMF, THF, toluene, and MeCN were purchased from
N-[1-(Cyanomethyl)pentyl]tosylamide (2d)4
Wako Pure Chemical Industries, Ltd. (Osaka). Other commercially
By following the general procedure, the reaction of aziridine 1d
available reagents were used as received without further purifica-
(253 mg, 1 mmol) with TMSCN (167 μL, 1.25 mmol) gave a color-
less oil; yield: 266 mg (95%).
IR (neat): 3270, 2240, 1600 cm–1.
1H NMR (500 MHz, CDCl3): δ = 0.82 (t, J = 7.5 Hz, 3 H), 1.08–
1.24 (m, 4 H), 1.47–1.58 (m, 2 H), 2.41 (s, 3 H), 2.55 (dd, J = 4.0,
16.5 Hz, 1 H), 2.65 (dd, J = 6.0, 16.5 Hz, 1 H), 3.38–3.42 (m, 1 H),
4.80–4.83 (m, 1 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.75 (d, J = 8.0 Hz, 2
H).
13C NMR (125 MHz, CDCl3): δ = 14.1, 21.7, 25.1, 28.8, 31.4, 33.4,
50.5, 116.6, 127.2, 129.8, 137.5, 143.9.
tion. The aziridines were prepared according to a literature proce-
dure.13 Yields refer to isolated compounds, estimated to be >95%
pure, as determined by 1H NMR spectroscopy. IR spectra were re-
corded on a Jasco FT/IR-430 spectrometer. 1H and 13C NMR spec-
tra were recorded for solns in CDCl3 with TMS as internal standard
on a Bruker Avance III instrument. HRMS data were measured on
a JEOL JMS-700 mass spectrometer.
PS-TBD Catalyzed Ring Cleavage of Aziridines with Silylated
Nucleophiles; General Procedure
The aziridine (1.0 mmol) and the silylated nucleophile (1.25 mmol)
were added to a soln of PS-TBD (0.05mmol) in DMF (1 mL) at r.t.
Synthesis 2013, 45, 2959–2965
© Georg Thieme Verlag Stuttgart · New York

PRACTICAL SYNTHETIC PROCEDURES
Catalytic Ring Cleavage of N-Tosylaziridines
2963
HRMS (FAB): m/z [M + H]+ calcd for C14H21N2O2S: 281.1324;
found: 281.1336.
1H NMR (500 MHz, CDCl3): δ = 2.44 (s, 3 H), 4.27 (s, 1 H), 4.98
(br s, 1 H), 7.02 (d, J = 7.6 Hz, 2 H), 7.07–7.13 (m, 3 H), 7.25–7.42
(m, 7 H), 7.81 (d, J = 7.6 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.4, 70.1, 126.4, 127.3, 127.4,
127.7, 128.1, 128.4, 129.3, 135.4, 136.9, 137.0, 142.9.
N-(1-Benzyl-2-cyanoethyl)tosylamide (2e)5a
By following the general procedure, the reaction of aziridine 1e
(287 mg, 1 mmol) with TMSCN (167 μL, 1.25 mmol) gave a color-
less solid; yield: 298 mg (95%); mp 90–92 °C.
Anal. Calcd for C22H20N2O2S: C, 70.19; H, 5.35; N, 7.44. Found: C,
69.90; H, 5.20; N, 7.79.
IR (KBr): 3270, 2250, 1600 cm–1.
1H NMR (500 MHz, CDCl3): δ = 2.42 (s, 3 H), 2.54 (dd, J = 4.0,
14.0 Hz, 1 H), 2.64 (dd, J = 6.0, 14.0 Hz, 1 H), 2.74 (dd, J = 8.0, 4.0
Hz, 1 H), 2.88 (dd, J = 7.5, 14.0 Hz, 1 H), 3.57–3.64 (m, 1 H), 4.82–
4.88 (m, 1 H), 6.97 (d, J = 7.6 Hz, 2 H), 7.18–7.20 (m, 5 H), 7.53
(d, J = 8.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.5, 24.1, 39.7, 51.3, 116.7,
126.9, 127.3, 128.9, 129.0, 129.8, 135.0, 136.3, 143.8.
N-(trans-2-Azidocyclohexyl)tosylamide (3a)4
By following the general procedure, the reaction of aziridine 1a
(251 mg, 1 mmol) with TMSN3 (166 μL, 1.25 mmol) gave a color-
less oil; yield: 277 mg (94%).
IR (KBr): 3300, 2940, 2090, 1600 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.12–1.33 (m, 4 H), 1.54–1.68 (m,
2 H), 1.92–2.00 (m, 2 H), 2.39 (s, 3 H), 2.91–2.95 (m, 1 H), 3.07–
3.10 (m, 1 H), 5.29 (d, J = 8.0 Hz, 1 H), 7.28 (d, J = 8.0 Hz, 2 H),
7.78 (d, J = 8.0 Hz, 2 H).
HRMS (FAB): m/z [M + H]+ calcd for C17H19N2O2S: 315.1167;
found: 315.1166.
13C NMR (125 MHz, CDCl3): δ = 21.5, 23.6, 23.8, 30.2, 32.4, 56.7,
63.5, 127.0, 129.5, 137.5, 143.3.
HRMS (FAB): m/z [M + H]+ calcd for C13H19N4O2S: 295.1229;
found: 295.1235.
N-(2-Cyano-1-phenylethyl)tosylamide (2f)4
By following the general procedure, the reaction of aziridine 1f (273
mg, 1 mmol) with TMSCN (167 μL, 1.25 mmol) gave a white solid;
yield: 282 mg (94%); mp 120–122 °C.
IR (KBr): 3280, 2250, 1590 cm–1.
N-(trans-2-Chlorocyclohexyl)tosylamide (3a′)4
By following the general procedure, the reaction of aziridine 1a
(251 mg, 1 mmol) with TMSCl (159 μL, 1.25 mmol) gave a color-
less solid; yield: 278 mg (97%); mp 98–100 °C.
1H NMR (500 MHz, CDCl3): δ = 2.39 (s, 3 H), 2.87 (dd, J = 7.0,
17.0 Hz, 1 H), 2.93 (dd, J = 5.0, 17.0 Hz, 1 H), 4.55 (dt, J = 5.5, 7.0
Hz, 1 H), 5.16 (d, J = 8.5 Hz, 1 H), 7.10 (d, J = 8.0 Hz, 2 H), 7.20–
7.28 (m, 5 H), 7.65 (d, J = 8.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.5, 26.2, 54.1, 116.3, 126.2,
127.1, 129.0, 129.2, 129.8, 136.4, 144.1.
IR (KBr): 3270, 2860, 1920, 1600 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.22–1.28 (m, 3 H), 1.55–1.67 (m,
3 H), 2.10–2.15 (m, 2 H), 2.39 (s, 3 H), 3.05–3.10 (m, 1 H), 3.66–
3.69 (m, 1 H), 5.20 (d, J = 6.0 Hz, 1 H), 7.26 (d, J = 8.0 Hz, 2 H),
7.75 (d, J = 8.0 Hz, 2 H).
HRMS (FAB): m/z [M + H]+ calcd for C16H17N2O2S: 301.1011;
found: 301.1003.
13C NMR (125 MHz, CDCl3): δ = 21.5, 23.4, 24.3, 32.4, 34.9, 58.7,
62.1, 127.3, 129.6, 137.2, 143.4.
HRMS (FAB): m/z [M + H]+ calcd for C13H19ClNO2S: 288.0825;
found: 288.0833.
N-[2-Cyano-1-(4-tolyl)ethyl]tosylamide (2g)4
By following the general procedure, the reaction of aziridine 1g
(287 mg, 1 mmol) with TMSCN (167 μL, 1.25 mmol) gave a pale-
yellow solid; yield: 273 mg (87%); mp 120–124 °C.
1H NMR (500 MHz, CDCl3): δ = 2.27 (s, 3 H), 2.39 (s, 3 H), 2.85
(dd, J = 7.6, 16.8 Hz, 1 H), 2.91 (dd, J = 5.1, 16.8 Hz, 1 H), 4.46–
4.51 (m, 1 H), 5.32 (d, J = 6.9 Hz, 1 H), 6.98 (d, J = 8.2 Hz, 2 H),
7.05 (d, J = 8.0 Hz, 2 H), 7.22 (d, J = 8.0 Hz, 2 H), 7.64 (d, J = 8.2
Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.0, 21.5, 26.2, 53.9, 116.5,
126.1, 127.1, 129.7, 129.8, 134.2, 139.0, 144.0.
N-(trans-2-Bromocyclohexyl)tosylamide (3a′′)4
By following the general procedure, the reaction of aziridine 1a
(251 mg, 1 mmol) with TMSBr (165 μL, 1.25 mmol) gave a white
solid; yield: 321 mg (97%); mp 78–80 °C.
IR (KBr): 3270, 2870, 1900, 1610 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.23–1.30 (m, 3 H), 1.58–1.64 (m,
2 H), 1.71–1.79 (m, 1 H), 2.18–2.28 (m, 2 H), 2.40 (s, 3 H), 3.14–
3.19 (m, 1 H), 3.80–3.88 (m, 1 H), 5.11 (d, J = 5.5 Hz, 1 H), 7.28
(d, J = 8.0 Hz, 2 H), 7.76 (d, J = 8.0 Hz, 2 H).
HRMS (FAB): m/z [M + H]+ calcd for C17H19N2O2S: 315.1167;
found: 315.1152.
N-[1-(4-Chlorophenyl)-2-cyanoethyl]tosylamide (2h)4
By following the general procedure, the reaction of aziridine 1h
(307 mg, 1 mmol) with TMSCN (167 μL, 1.25 mmol) gave a white
solid; yield: 270 mg (81%); mp 110–112 °C.
1H NMR (500 MHz, CDCl3): δ = 2.38 (s, 3 H), 2.82 (dd, J = 7.0,
16.8 Hz, 1 H), 2.88 (dd, J = 5.8, 16.8 Hz, 1 H), 4.56 (dd, J = 7.1, 7.2
Hz, 1 H), 5.70 (d, J = 7.6 Hz, 1 H), 7.03 (d, J = 8.5 Hz, 2 H), 7.18
(d, J = 8.5 Hz, 2 H), 7.20 (d, J = 8.0 Hz, 2 H), 7.59 (d, J = 8.0 Hz,
2 H).
13C NMR (125 MHz, CDCl3): δ = 21.5, 23.4, 25.3, 32.8, 35.7, 55.0,
58.6, 127.3, 129.6, 137.1, 143.5.
HRMS (FAB): m/z [M + H]+ calcd for C13H19BrNO2S: 332.0320;
found: 332.0323.
N-(trans-2-Azidocyclopentyl)tosylamide (3b)4
By following the general procedure, the reaction of aziridine 1b
(237 mg, 1 mmol) with TMSN3 (166 μL, 1.25 mmol) gave a color-
less oil; yield: 246 mg (88%).
IR (KBr): 3260, 2960, 2100, 1600 cm–1.
13C NMR (125 MHz, CDCl3): δ = 21.5, 26.2, 53.5, 116.2, 127.1,
1H NMR (500 MHz, CDCl3): δ = 1.31–1.39 (m, 1 H), 1.51–1.65 (m,
3 H), 1.81–1.92 (m, 2 H), 2.40 (s, 3 H), 3.36 (dt, J = 5.0, 7.0 Hz, 1
H), 3.65–3.71 (m, 1 H), 5.54 (d, J = 8.0 Hz, 1 H), 7.28 (d, J = 8.0
Hz, 2 H), 7.76 (d, J = 8.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 20.8, 21.5, 26.9, 29.0, 30.8, 59.7,
66.9, 126.7, 129.6, 137.0, 143.5.
127.7, 129.2, 129.8, 134.8, 135.6, 144.2.
HRMS (FAB): m/z [M + H]+ calcd for C16H16ClN2O2S: 334.0543;
found: 334.0565.
N-(-2-Cyano-1,2-diphenylethyl)tosylamide (2i)5a
By following the general procedure, the reaction of aziridine 1i (175
mg, 0.5 mmol) with TMSCN (83 μL, 0.63 mmol) gave a white sol-
id; yield: 45 mg (12%); mp 78–80 °C.
HRMS (FAB): m/z [M + H]+ calcd for C12H17N4O2S: 281.1072;
found: 281.1075.
IR (KBr): 3270, 2960, 2100, 1600 cm–1.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 2959–2965

2964
S. Matsukawa et al.
PRACTICAL SYNTHETIC PROCEDURES
N-(trans-2-Chlorocyclopentyl)tosylamide (3b′)4
By following the general procedure, the reaction of aziridine 1b
(237 mg, 1 mmol) with TMSCl (159 μL, 1.25 mmol) gave a color-
less solid; yield: 278 mg (97%); mp 88–90 °C.
1H NMR (500 MHz, CDCl3): δ = 1.37–1.50 (m, 2 H), 1.66–1.78 (m,
2 H), 2.04–2.13 (m, 2 H), 2.39 (s, 3 H), 3.53–3.57 (m, 1 H), 4.01–
4.12 (m, 1 H), 5.64–5.71 (br s, 1 H), 7.27 (d, J = 8.0 Hz, 2 H), 7.74
(d, J = 8.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.5, 38.4, 53.7, 54.3, 126.8,
127.2, 128.6, 128.7, 129.1, 129.6, 136.1, 136.7, 143.4.
HRMS (FAB): m/z [M + H]+ calcd for C16H19N4O2S: 331.1229;
found: 331.1236.
N-(1-Benzyl-2-chloroethyl)tosylamide (3e′)6
By following the general procedure, the reaction of aziridine 1e
(287 mg, 1 mmol) with TMSCl (159 μL, 1.25 mmol) gave a color-
less oil; yield: 316 mg (98%).
13C NMR (125 MHz, CDCl3): δ = 20.7, 21.4, 30.3, 33.3, 62.6, 63.6,
127.1, 129.7, 137.0, 143.5.
IR (neat): 3270, 2890, 1600 cm–1.
1H NMR (500 MHz, CDCl3): δ = 2.40 (s, 3 H), 2.75 (dd, J = 6.5,
13.5 Hz, 1 H), 2.87 (dd, J = 7.5, 13.5 Hz, 1 H), 3.43 (dd, J = 5.5,
11.5 Hz, 1 H), 3.47 (dd, J = 3.0, 11.5 Hz, 1 H), 3.64–3.71 (m, 1 H),
4.88 (d, J = 7.0 Hz, 1 H), 7.03 (d, J = 7.5 Hz, 2 H), 7.17–7.22 (m, 5
H), 7.61 (d, J = 8.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.5, 38.2, 46.8, 55.1, 126.9,
127.0, 128.7, 128.8, 129.1, 129.7, 136.1, 137.2, 143.5.
HRMS (FAB): m/z [M + H]+ calcd for C12H17ClNO2S: 274.0669;
found: 274.0681.
N-[1-(Azidomethyl)heptyl]tosylamide (3c)4
By following the general procedure, the reaction of aziridine 1c
(281 mg, 1 mmol) with TMSN3 (166 μL, 1.25 mmol) gave a pale-
yellow oil; yield: 308 mg (95%).
IR (neat): 3280, 2940, 2100, 1600 cm–1.
HRMS (FAB): m/z [M + H]+ calcd for C16H19ClNO2S: 324.0825;
found: 324.0830.
1H NMR (500 MHz, CDCl3): δ = 0.82 (t, J = 7.0 Hz, 3 H), 1.10–
1.50 (m, 10 H), 2.41 (s, 3 H), 3.26–3.30 (m, 3 H), 4.80 (d, J = 7.0
Hz, 1 H), 7.28 (d, J = 8.0 Hz, 2 H), 7.74 (d, J = 8.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 14.0, 21.5, 22.4, 25.3, 28.8, 31.6,
32.6, 53.2, 55.0, 127.0, 129.7, 137.7, 143.6.
HRMS (FAB): m/z [M + H]+ calcd for C15H25N4O2S: 325.1698;
found: 325.1698.
N-(1-Benzyl-2-bromoethyl)tosylamide (3e′′)6
By following the general procedure, the reaction of aziridine 1e
(287 mg, 1 mmol) with TMSBr (165 μL, 1.25 mmol) gave a white
solid; yield: 360 mg (98%); mp 32–34 °C.
IR (KBr): 3250, 2850, 1590 cm–1.
1H NMR (500 MHz, CDCl3): δ = 2.39 (s, 3 H), 2.73 (dd, J = 5.5,
14.0 Hz, 1 H), 2.87 (dd, J = 8.0, 14.0 Hz, 1 H), 3.31 (dd, J = 5.5,
11.0 Hz, 1 H), 3.34 (dd, J = 5.0, 11.0 Hz, 1 H), 3.57–3.62 (m, 1 H),
5.02 (d, J = 8.0 Hz, 1 H), 7.01–7.08 (m, 2 H), 7.15–7.22 (m, 5 H),
7.62 (d, J = 8.5 Hz, 2 H).
N-[1-(Chloromethyl)heptyl]tosylamide (3c′)4
By following the general procedure, the reaction of aziridine 1c
(281 mg, 1 mmol) with TMSCl (159 μL, 1.25 mmol) gave a color-
less oil; yield: 285 mg (90%).
IR (neat): 3280, 2840, 1610 cm–1.
13C NMR (125 MHz, CDCl3): δ = 21.4, 37.4, 41.1, 54.6, 126.9,
1H NMR (500 MHz, CDCl3): δ = 0.81 (t, J = 7.5 Hz, 3 H), 1.10–
1.25 (m, 8 H), 1.39–1.47 (m, 1 H), 1.51–1.57 (m, 1 H), 2.40 (s, 3 H),
3.40–3.52 (m, 3 H), 4.91 (d, J = 8.5 Hz, m, 1 H), 7.28 (d, J = 8.0
Hz, 2 H), 7.75 (d, J = 8.0 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 14.0, 21.5, 22.4, 225, 25.2, 28.7,
31.4, 32.3, 48.1, 53.8, 127.0, 129.7, 137.8, 143.6.
127.0, 128.6, 129.1, 129.5, 129.8, 136.0, 137.1, 143.4.
HRMS (FAB): m/z [M + H]+ calcd for C16H19BrNO2S: 368.0320;
found: 368.0318.
N-(2-Azido-2-phenylethyl)tosylamide (4f)4 and N-(2-Azido-1-
phenylethyl)tosylamide (3f)
By following the general procedure, the reaction of aziridine 1f (273
mg, 1 mmol) with TMSN3 (166 μL, 1.25 mmol) gave a white solid;
yield: 306 mg (97%, 78:22 mixture of regioisomers 4f and 3f).
HRMS (FAB): m/z [M + H]+ calcd for C15H25ClNO2S: 318.1295;
found: 318.1301.
IR (KBr): 3280, 2100, 1590 cm–1.
N-[1-(Azidomethyl)pentyl]tosylamide (3d)4
By following the general procedure, the reaction of aziridine 1d
(253 mg, 1 mmol) with TMSN3 (166 μL, 1.25 mmol) gave a color-
less oil; yield: 243 mg (82%).
IR (neat): 3280, 2100, 1600 cm–1.
1H NMR: (500 MHz, CDCl3): δ = 0.74 (t, J = 7.0 Hz, 3 H), 1.04–
1.50 (m, 6 H), 2.40 (s, 3 H), 3.24–3.29 (m, 3 H), 5.00 (br s, 1 H),
7.28 (d, J = 8.0 Hz, 2 H), 7.74 (d, J = 8.2 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 13.7, 21.5, 22.1, 27.5, 32.2, 53.2,
54.9, 126.9, 129.6, 137.6, 143.4.
HRMS (FAB): m/z [M + H]+ calcd for C13H21N4O2S: 297.1385;
found: 297.1386.
1H NMR (500 MHz, CDCl3): δ (4f) = 2.43 (s, 3 H), 3.06 (ddd,
J = 5.0, 8.0, 13.5 Hz, 1 H), 3.21 (ddd, J = 5.0, 7.5, 13.5 Hz, 1 H),
4.60 (dd, J = 5.5, 9.0 Hz, 1 H), 5.11 (dd, J = 5.5, 7.5 Hz, 1 H), 7.18
(d, J = 8.0 Hz, 2 H), 7.18–7.38 (m, 5 H), 7.72 (d, J = 8.0 Hz, 2 H);
δ (3f) = 2.37 (s, 3 H), 3.53 (d, J = 6.5 Hz, 2 H), 4.47 (dd, J = 6.0,
16.5 Hz, 1 H), 5.62 (d, J = 8.0 Hz, 1 H), 7.10 (d, J = 8.0 Hz, 2 H),
7.18–7.38 (m, 5 H), 7.60 (d, J = 8.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ (4f) = 21.5, 48.0, 65.4, 126.9,
127.0, 128.9, 129.0, 129.8, 136.2, 136.7, 143.7; δ (3f) = 21.4, 55.9,
57.1, 126.7, 127.0, 128.1, 128.6, 129.4, 137.0, 137.5, 143.4.
HRMS (FAB): m/z [M + H]+ calcd for C15H17N4O2S: 317.1072;
found: 317.1075 (mixture of regioisomers 4f and 3f).
N-(2-Azido-1-benzylethyl)tosylamide (3e)6
By following the general procedure, the reaction of aziridine 1e
(287 mg, 1 mmol) with TMSN3 (166 μL, 1.25 mmol) gave a color-
less oil; yield: 304 mg (92%).
N-(2-Chloro-2-phenylethyl)tosylamide (4f′)4 and N-(2-Chloro-
1-phenylethyl)tosylamide (3f′)
By following the general procedure, the reaction of aziridine 1f (273
mg, 1 mmol) with TMSCl (159 μL, 1.25 mmol) gave a white solid;
yield: 281 mg (91%; 90:10 mixture of regioisomers 4f′ and 3f′);
mp 62–65 °C.
IR (neat): 3270, 2090, 1600 cm–1.
1H NMR (500 MHz, CDCl3): δ = 2.39 (s, 3 H), 2.68 (dd, J = 7.0,
14.0 Hz, 1 H), 2.75 (dd, J = 7.5, 14.0 Hz, 1 H), 3.28 (dd, J = 4.0,
12.0 Hz, 1 H), 3.31 (dd, J = 6.5, 12.0 Hz, 1 H), 3.45–3.54 (m, 1 H),
4.92 (d, J = 8.0 Hz, 1 H), 6.98 (d, J = 8.5 Hz, 2 H), 7.10–7.35 (m, 5
H), 7.60 (d, J = 8.5 Hz, 2 H).
IR (KBr): 3260, 2100, 1600 cm–1.
1H NMR (400 MHz, CDCl3): δ (4f′) = 2.41 (s, 3 H), 3.36–3.47 (m,
2 H), 4.86 (dd, J = 6.1, 8.2 Hz, 1 H), 5.20 (dd, J = 6.5, 6.7 Hz, 1 H),
7.28–7.32 (m, 7 H), 7.71 (d, J = 8.3 Hz, 2 H); δ (3f) = 2.39 (s, 3 H),
Synthesis 2013, 45, 2959–2965
© Georg Thieme Verlag Stuttgart · New York

PRACTICAL SYNTHETIC PROCEDURES
Catalytic Ring Cleavage of N-Tosylaziridines
2965
3.67 (dd, J = 5.8, 11.4 Hz, 1 H), 3.71 (dd, J = 6.4, 11.4 Hz, 1 H),
4.55 (q, J = 6.7 Hz, 1 H), 5.39 (t, J = 6.6 Hz, 1 H), 7.25–7.35 (m, 7
H), 7.59 (d, J = 8.3 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ (4f′) = 21.4, 50.2, 61.6, 126.9,
127.1, 128.8, 128.9, 129.7, 136.9, 137.8, 143.6; δ (3f) = 21.4, 47.8,
58.4, 126.8, 127.0, 128.5, 128.7, 129.7, 136.4, 137.3, 143.5.
G.; Singh, V. K. Tetrahedron Lett. 2000, 41, 4677. (g) Shin,
S.-H.; Han, E. Y.; Park, C. S.; Lee, W. K.; Ha, H.-J.
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Reddy, L. R.; Bhanumathi, N.; Rao, K. R. Chem. Lett. 2001,
246. (i) Chandrasekhar, M.; Sekar, G.; Singh, V. K.
Tetrahedron Lett. 2000, 41, 10079. (j) Yadav, J. S.; Reddy,
B. V. S.; Kumar, G. M.; Murhty, V. S. R. Synth. Commun.
2002, 32, 1797. (k) Mita, T.; Fujimori, I.; Wada, R.; Wen, J.;
Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2005, 127,
11252. (l) Fukuta, Y.; Mita, T.; Fukuda, N.; Kanai, M.;
Shibasaki, M. J. Am. Chem. Soc. 2006, 128, 6312.
(m) Fujimori, I.; Mita, T.; Maki, K.; Shiro, M.; Sato, A.;
Furusho, S.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc.
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J. R.; RajanBabu, T. V. Angew. Chem. Int. Ed. 2009, 48,
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1475.
HRMS (FAB): m/z [M + H]+ calcd for C15H17ClNO2S: 310.0669;
found: 310.0655 (mixture of regioisomers 4f′ and 3f′).
N-(-2-Azido-1,2-diphenylethyl)tosylamide (3i′)5e
By following the general procedure, the reaction of aziridine 1i (175
mg, 0.5 mmol) with TMSN3 (83 μL, 0.63 mmol) gave a white solid;
yield: 157 mg (80%); mp 62–65 °C.
IR (KBr): 3270, 2960, 2100, 1600 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.31 (s, 3 H), 4.48–4.51 (m, 1 H),
4.69 (d, J = 6.5 Hz, 1 H), 5.53 (br s, 1 H), 6.94 (d, J = 7.0 Hz, 2 H),
7.01 (d, J = 8.0 Hz, 2 H), 7.05–7.15 (m, 5 H), 7.20–7.24 (m, 3 H),
7.38 (d, J = 8.0 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 21.4, 62.3, 70.2, 126.9, 127.4,
127.5, 127.8, 128.1, 128.6, 129.2, 135.4, 136.9, 137.0, 143.0.
HRMS (FAB): m/z [M + H]+ calcd for C21H21N4O2S: 393.1385;
found: 393.1377.
(4) Wu, J.; Hou, X.-L.; Dai, L.-X. J. Org. Chem. 2000, 65, 1344.
(5) (a) Minakata, S.; Okada, Y.; Oderaotoshi, Y.; Komatsu, M.
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(e) Matsukawa, S.; Takahasi, H.; Harada, T. Synth.
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N-(-2-Chloro-1,2-diphenylethyl)tosylamide (3i′′)
By following the general procedure, the reaction of aziridine 1i (175
mg, 0.5 mmol) with TMSCl (80 μL, 0.63 mmol) gave product 3i′′
as a white solid; yield: 144 mg (97%); mp 72–74 °C.
IR (KBr): 3250, 2960, 2880, 1600 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.32 (s, 3 H), 4.72 (t, J = 6.5 Hz,
1 H), 5.00 (d, J = 6.5 Hz, 1 H), 5.39 (d, J = 6.0 Hz, 1 H), 6.90 (d,
J = 7.0 Hz, 2 H), 7.02–7.06 (m, 4 H), 7.08–7.15 (m, 2 H), 7.16–7.21
(m, 4 H), 7.38 (d, J = 7.0 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 21.5, 63.8, 66.8, 127.1, 127.9,
128.0, 128.3, 128.7, 129.2, 136.5, 136.9, 136.9, 143.2.
(6) Wu, J.; Sun, X.; Shengqing, Y.; Sun, W. Tetrahedron Lett.
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Bradley, M. Chem. Rev. 2002, 102, 3275. (b) Benaglia, M.;
Puglisi, A.; Cozzi, F. Chem. Rev. 2003, 103, 3401. (c) Cozzi,
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Weck, M. Coord. Chem. Rev. 2007, 251, 860. (e) Kwong, C.
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(g) Wang, Z.; Chen, G.; Ding, K. Chem. Rev. 2009, 109,
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583. (i) Lu, J.; Toy, P. H. Chem. Rev. 2009, 109, 815.
(j) Kristensen, T. E.; Hansen, T. Eur. J. Org. Chem. 2010,
3179.
HRMS (FAB): m/z [M + H]+ calcd for C21H21ClNO2S: 386.0982;
found: 386.0988.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.SnuIomprifgtooatrinSugpIoi
n
nfomartit
(8) (a) Tomoi, M.; Kato, Y.; Kakiuchi, H. Makromol. Chem.
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