Hou et al.
On the basis of these findings, a novel and efficient
nonmetallic catalyzed ring-opening reaction of various
aziridines with a wide range of nucleophiles under mild
conditions was developed, which opens the way to a
variety of 1,2-bifunctional products. The further inves-
tigations of the mechanism in detail and the scope of
these reactions are in progress.
(d, J ) 6.5 Hz, 1H), 6.76 (d, J ) 7.8 Hz, 2H), 6.89-6.94 (m,
1
3
1
4
H), 7.19-7.26 (m, 4H), 7.75 ppm (d, J ) 8.0 Hz, 2H); IR (neat)
-
1
+
289, 1600, 1382 cm ; EI-MS m/z (%) 331 (M , 6), 238 (100),
72 (54). Anal. Calcd for C18 : C, 65.23, H; 6.39; N,
.23. Found: C, 65.11; H, 6.50; N, 4.00.
-P h en oxym eth yl-S-4-m eth ylp h en yl-ben zen em eth a n -
H
21NSO
3
1
3
1
su lfon am ide (2cA) an d 2-P h en oxy-S-4-m eth ylph en yl-ben -
1
zen eeth a n su lfon a m id e (3cA). Colorless liquid; H NMR (300
MHz, CDCl
3
, 25 °C, TMS) δ 2.35 (s, 3H), 2.39 (s, 3H), 3.25
(dd, J ) 13.6, 8.9 Hz, 1H), 3.42 (dd, J ) 13.5, 3.8 Hz, 1H),
Exp er im en ta l Section
4.02 (m, 2H), 4.68 (t, J ) 5.3 Hz, 1H), 5.11 (dd, J ) 8.9, 3.8
Hz, 2H), 5.44 (br, 1H), 6.73 (t, J ) 8.3 Hz, 3H), 6.85-6.96 (m,
3H), 7.11-7.17 (m, 3H), 7.20-7.32 (m, 15H), 7.61 (d, J ) 8.3
Hz, 2H), 7.72 ppm (d, J ) 8.3 Hz, 2H); IR (film) ν˜ 3280 (NH),
Gen er a l Exp er im en ta l Con d ition s. All reactions were
performed under an atmosphere of either dry argon or nitrogen
with oven-dried glassware. Solvents were distilled under an
atmosphere of nitrogen before use. THF and toluene were
distilled from sodium benzophenone ketal. Dichloromethane
and acetonitrile were distilled from calcium hydride. The
commercially available reagents were used as received without
-
1
+
+
1599 cm (Ph); EI-MS m/z (%) 367 (1) [M ], 274 (93) [M
PhOH]; HRMS calculated for C21 367.1234, found
367.1240. Anal. Calcd for C21 21NSO : C, 68.64, H, 5.76; N,
-
H
21NSO
3
H
3
3.81. Found: C, 68.63; H, 5.94; N, 3.72.
N-[2-(P h en oxy)cycloh exyl]ben zam ide (2dA). White solid;
1
1
further purification. Melting points are uncorrected. H NMR
mp 162-164 °C; H NMR (CDCl
3
/TMS) δ 1.38-1.61 (m, 5H),
spectra were recorded in CDCl
referenced to CHCl
(δ 7.27 ppm). The chemical shifts of 31
NMR were referenced to external 85% H PO . Chemical shifts
are given in parts per million relative to tetramethylsilane as
3
and the chemical shifts were
1.82-1.85 (m, 1H), 2.15-2.17 (m, 1H), 2.27-2.32 (m, 1H),
4.17-4.30 (m, 2H), 6.11 (d, J ) 5.5 Hz, 1H), 6.93-6.99 (m,
3H), 7.23-7.28 (m, 2H), 7.35-7.45 (m, 3H), 7.60-7.63 ppm
3
P
3
4
-
1
(m, 2H); IR (neat) 3305, 1639, 1601 cm ; EI-MS m/z (%) 296
-
1
+
an internal standard. IR spectra were measured in cm
Gen er a l P r oced u r e of th e Rin g-Op en in g Rea ction of
Azir id in es 1 w ith Nu cleop h iles A-I Ca ta lyzed by Bu P .
To a stirred solution of aziridine 1 (0.5 mmol) and nucleophiles
A-I (0.55 mmol) in the corresponding solvent (2.0 mL) was
added tributylphosphine (0.013 mL, 0.05 mmol) under argon,
and the resulting mixture was stirred at room temperature
.
2
(MH , 2), 202 (30), 105 (100). Anal. Calcd for C19H21NO : C,
77.26; H, 7.17, N, 4.74. Found: C, 77.36; H, 7.15; N, 4.58.
3
N-Boc-2-(p h en oxy)cycloh exyla m in e (2eA). White solid;
1
mp 144-146 °C; H NMR (300 MHz, CDCl , 25 °C, TMS) δ
3
1.25-1.63 (m, 15H), 2.13-2.15 (m, 2H), 3.65-3.72 (m, 1H),
4.04 (dt, J ) 9.1, 3.8 Hz, 1H), 4.53 (d, J ) 6.3 Hz, 1H), 6.90-
6.95 (m, 3H), 7.23-7.29 ppm (m, 2H); IR (film) ν˜ 3329 (NH),
-
1
+
(CH
3
CN) or at reflux (toluene) until complete consumption of
1689 (CdO), 1391 cm (CH ); EI-MS m/z (%) 291 (4) [M ],
3
the substrate (monitored by TLC). The solvent was removed
in a vacuum and the crude product was purified by flash
column chromatography to provide the corresponding product.
N -(2-P h e n oxyl)c yc loh e xyl-4-m e t h ylb e n ze n su lfon -
174 (32), 142 (100); HRMS calculated for C H NO 291.1850,
1
7
25
3
found 291.1862. Anal. Calcd for C H NO : C, 70.07, H; 8.65;
1
7
25
3
N, 4.81. Found: C, 70.15; H, 8.39; N, 4.59.
N-(2-(P h en oxy)cycloh exyl)ben zen em eth an am in e (2fA).
1
1
a m id e (2a A). White solid; mp 146-148 °C; H NMR (300
Yellow solid; mp 42-44 °C; H NMR (300 MHz, CDCl , 25 °C,
3
MHz, CD
3
COCD
3
, 25 °C, TMS) δ 1.25-1.33 (m, 4H), 1.56-
TMS) δ 1.23-1.36 (m, 4H), 1.73-1.75 (m, 2H), 2.11-2.15 (m,
3H), 2.79 (dt, J ) 9.1, 4.4 Hz, 1H), 3.84 (ABq, J ) 13.1 Hz,
2H), 4.09 (dt, J ) 9.0, 4.3 Hz, 1H), 6.91-6.95 (m, 3H), 7.23-
1
3
.75 (m, 2H), 2.02-2.05 (m, 1H), 2.21-2.24 (m, 1H), 2.43 (s,
H), 3.27-3.40 (m, 1H), 4.11-4.25 (m, 1H), 4.76 (d, J ) 3.6
Hz, 1H), 6.67 (d, J ) 8.2 Hz, 2H), 6.94 (t, J ) 7.5 Hz, 1H,),
7
3
7.31 ppm (m, 7H); IR (film) ν˜ 3330 (NH), 1600 cm-1 (CH );
3
.21-7.30 (m, 4H), 7.76 ppm (d, J ) 8.2 Hz, 2H); IR (film) ν˜
EI-MS m/z (%) 281 (17), [M
+
], 188 (53) [M - PhOH], 91 (100);
HRMS calculated for C H23NO 281.1867, found 281.1852.
19
+
-
1
-1
+
297 cm (NH), 1601 cm (Ph); EI-MS m/z (%) 346 (37) [M
+
+
H], 252 (100) [M - PhOH]. Anal. Calcd for C19
H
23NSO
3
:
19
Anal. Calcd for C H23NO: C, 81.10, H; 8.24; N, 4.98. Found:
C, 81.01; H, 8.02; N, 4.88.
C, 66.06; H, 6.71; N, 4.05. Found: C, 65.91; H, 6.81; N, 3.81.
N-[2-(3-Ch lor op h en oxy)cycloh exyl]-4-m eth ylben zen e-
N-(2-P h en ylt h iocycloh exyl)-4-m et h ylb en zen esu lfon -
1
su lfon a m id e (2a B). White solid; mp 122-124 °C; H NMR
1
a m id e (2a D). White solid; mp 130-131 °C; H NMR (300
MHz, CDCl , 25 °C, TMS) δ 1.20-1.50 (m, 4H), 1.50-1.75 (m,
H), 2.00-2.10 (m, 1H), 2.20-2.30 (m, 1H), 2.45 (s, 3H), 2.80-
.00 (m, 2H), 5.10-5.20 (d, J ) 3.6 Hz, 1H), 7.20-7.40 (m,
(
2
1
3
CDCl /TMS) δ 1.26-1.36 (m, 4H), 1,63-1.71 (m, 2H), 2.01-
3
.20 (m, 2H), 2.42 (s, 3H), 3.27-3.30 (m, 1H), 3.95-4.00 (m,
H), 4.89 (d, J ) 5.9 Hz, 1H), 6.58-6.60 (m, 2H), 6.87-6.90
2
3
7
(
m, 1H), 7.09-7.15 (m, 1H), 7.26 (t, J ) 4.2 Hz, 2H), 7.74 ppm
-1
H), 7.75 ppm (d, J ) 8.3 Hz, 2H); IR (film) ν˜ 3265 cm (NH);
-
1
(d, J ) 8.3 Hz, 2H); IR (neat) 3304, 1594, 1382 cm ; EI-MS
+
+
EI-MS m/z (%) 361 (7) [M ], 252 (13) [M - PhS]. Anal. Calcd
for C19 : C, 63.13; H, 6.41; N, 3.87. Found: C, 63.07;
H, 6.48; N, 3.91.
-(P h e n ylt h io)m e t h yl-S -(4-m e t h ylp h e n yl)b e n ze n e -
+
m/z (%) 379 (M , 5), 252 (100), 172 (21). Anal. Calcd for C19
ClNSO : C, 60.07; H, 5.84; N, 3.69. Found: C, 60.35; H, 5.99;
N, 3.67. Anal. Calcd for C19 SO : C, 58.45; H, 5.68; N,
.17. Found: C, 58.37; H, 5.49; N, 6.94.
N-[2-(4-Meth ylp h en oxy)cycloh exyl]-4-m eth ylben zen e-
22
H -
H
2 2
23NO S
3
H
23
N
2
5
1
7
m eth a n su lfon yla m id e a n d 2-P h en ylth io-S-(4-m eth ylp h e-
n yl)ben zen eeth a n su lfon yla m id e (2cD a n d 3cD). Colorless
1
su lfon a m id e (2a C). White solid; mp 127-128 °C; H NMR
1
liquid; H NMR (CDCl
3
(
2
3
/TMS) δ 2.35 (s, 3H), 2.42 (s, 3H), 3.18-
(CDCl /TMS) δ 1.26-1.34 (m, 4H), 1.57-1.70 (m, 2H), 2.02-
3
.22 (m, 2H), 3.34-3.39 (m, 2H), 4.13 (t, J ) 7.2 Hz, 1H), 4.30
q, J ) 6.7 Hz, 1H), 4.74 (br, 1H), 5.33 (br, 1H), 7.08-7.27 (m,
4H), 7.50 (d, J ) 8.2 Hz, 2H), 7.64 ppm (d, J ) 8.2 Hz, 2H);
IR (neat) 3290, 3059, 1599 cm ; EI-MS m/z (%) 383 (M , 1.67),
60 (100), 199 (78). Anal. Calcd for C21 : C, 65.76;
2
3
1
.05 (m, 1H), 2.17-2.24 (m, 1H), 2.27 (s, 3H), 2.42 (s, 3H),
.20-3.23 (m, 1H), 3.94-3.97 (m, 1H), 4.88 (d, J ) 4.6 Hz,
H), 6.62 (d, J ) 8.4 Hz, 2H), 7.03 (d, J ) 8.6 Hz, 2H), 7.28 (d,
-1
+
J ) 8.4 Hz, 2H), 7.76 ppm (d, J ) 8.2 Hz, 2H); IR (neat) 3323,
2
2 2
H21NO S
-
1
+
1
(
615, 1383 cm ; EI-MS m/z (%) 359 (M , 10), 252 (100), 155
46). Anal. Calcd for C20 : C, 66.82; H, 7.01; N, 3.90.
Found: C, 66.85; H, 7.08; N, 3.88.
N -(2-P h e n oxy)cyclop e n t yl-4-m e t h ylb e n ze n e su lfon -
H, 5.52; N, 3.65. Found: C, 65.66; H, 5.75; N, 3.58.
N-[2-(P h en ylth io)cycloh exyl]ben za m id e (2d D). White
H25NSO
3
1
solid; mp 126-128 °C; H NMR (CDCl
3
/TMS) δ 1.10-1.50 (m,
4
2
1
3
2
H), 1.60-1.75 (m, 2H), 2.05-2.20 (m, 1H), 2.25-2.40 (m, 1H),
1
3
a m id e (2bA). White solid; mp 115-117 °C; H NMR (CDCl /
.90-3.10 (m, 1H), 3.75-3.90 (m, 1H), 6.20 (d, J ) 6.6 Hz,
H), 7.10-7.50 (m, 8H), 7.60 ppm (d, J ) 8.6 Hz, 2H); IR (film)
TMS) δ 1.40-1.47 (m, 1H), 1.71-1.81 (m, 3H), 1.98-2.09 (m,
2
H), 2.38 (s, 3H), 3.66-3.72 (m, 1H), 4.49-4.52 (m, 1H), 4.91
-1
+
302, 2933, 1637 cm ; EI-MS m/z (%) 311 (M , 1), 273 (6),
10 (27), 190 (100). Anal. Calcd for C19H21NOS: C, 73.31; H,
(13) Dalko, P. I.; Moisan, L. Angew. Chem., Int. Ed. 2001, 40, 3726.
6.75; N, 4.50. Found: C, 73.16; H, 6.87; N, 4.33.
5
298 J . Org. Chem., Vol. 67, No. 15, 2002