K. Okuma et al. / Tetrahedron 63 (2007) 8250–8254
8253
(
dd, 1H, J¼6.8 and 14.0 Hz, CHHSMe), 3.04 (dd, 1H, J¼7.2
3-Methyl-N-methanesulfonylindole 1c: colorless oil; spec-
tral data were identical with the reported value. H NMR
2
2 1
and 16.0 Hz, CHH), 3.73 (dd, 1H, J¼8.4 and 16.0 Hz,
CHH), 4.95 (dt, 1H, J¼6.8 and 8.8 Hz, CH), 6.78 (d, 1H,
J¼8.0 Hz, Ar), 6.85 (dd, 1H, J¼7.6 and 8.0 Hz, Ar), 7.10
(CDCl ) d¼2.30 (s, 3H, CH ), 3.03 (s, 3H, Ms), 7.20 (s, 1H,
3
3
Ar), 7.29–7.40 (m, 2H, Ar), 7.56 (d, 1H, J¼8.0 Hz, Ar), 7.90
1
3
(
dd, 1H, J¼7.6 and 8.0 Hz, Ar), 7.15 (d, 1H, J¼8.8 Hz,
(d, 1H, J¼8.1 Hz, Ar). C NMR (CDCl ) d¼9.89 (Me),
3
1
3
Ar). C NMR (CDCl ) d¼16.52 (SCH ), 35.10 (CH ),
40.42 (Ms), 113.39 (Ar), 119.81 (Ar), 119.91 (Ar), 123.16
(Ar), 123.52 (Ar), 125.12 (Ar), 131.98 (Ar), 135.55 (Ar).
3
3
2
3
9.37 (CH ), 82.14 (CH), 109.50 (Ar), 120.68 (Ar), 125.13
2
(
Ar), 126.39 (Ar), 128.20, 159.33 (Ar).
3
-Methyl-N-p-nitrobenzenesulfonylindole (1d): Mp 132–
ꢀ
1
4.4. Reaction of o-vinyl-N-p-tosylanilide (3a) with
DMTST
134 C. H NMR (CDCl ) d¼2.25 (s, 3H, CH ), 7.23–7.28
3
3
(m, 2H, Ar), 7.34 (dd, 1H, J¼7.6 and 8.0 Hz, Ar), 7.46 (d, 1H,
J¼7.6 Hz, Ar), 8.00 (d, 1H, J¼7.6 Hz, Ar), 8.02 (d, 2H, J¼
1
3
To a solution of DMTST (516 mg, 2.0 mmol) in dichloro-
methane (5 mL) was added a solution of o-vinyl-N-p-tosyl-
anilide 3a (153 mg, 1.0 mmol) in dichloromethane (5 mL)
at rt. After stirring for 8 h, the reaction mixture was
washed with 10% of aq sodium carbonate (10 mL) and
separated. The water layer was extracted with dichlorome-
thane (5 mLꢁ2) and the combined extract was dried over
magnesium sulfate, filtered, and evaporated to give pale yel-
low crystals, which was chromatographed over silica gel
by elution with hexane to afford colorless oil of 3-methyl-
8.4 Hz, p-NO Ar), 8.25 (d, 2H, J¼8.4 Hz, p-NO Ar).
C
2
2
NMR (CDCl ) d¼9.97 (CH ), 119.80 (Ar), 120.05 (Ar),
3
3
120.71 (Ar), 122.71 (Ar), 124.09 (Ar), 124.65 (p-NO Ar),
2
125.49 (Ar), 128.20 (p-NO Ar), 132.24 (Ar), 135.36 (Ar),
2
143.59 (p-NO Ar), 150.72 (p-NO Ar). Anal. found: C,
2
2
56.87; H, 3.88; N, 8.88. Calcd for C H NO S: C, 56.95;
1
5
12
4
H, 3.82; N, 8.86.
4.6. One-pot synthesis of 1b
1
thio-N-tosylindoline (7a) (246 mg, 0.77 mmol). H NMR
To a solution of dimethyl disulfide (0.282 g, 3.0 mmol) in di-
chloromethane (5 mL) was added a solution of methyl triflate
(0.492 g, 3.0 mmol) in one portion. After stirring for 30 min,
3e (0.167 g, 1.0 mmol) in dichloromethane (5 mL) was added
dropwise to this solution at rt. After stirring for 5 h, the reac-
tion mixture was washed with 10% of aq sodium carbonate
(10 mL) and separated. Thewater layer was extracted with di-
chloromethane (5 mLꢁ2) and the combined extract was dried
over magnesium sulfate, filtered, and evaporated to give col-
orless solid, which was chromatographed over silica gel by
elutionwithhexane–dichloromethane(1:1)toaffordcolorless
plates of 3-methyl-N-tosylindole (1b) (259 mg, 0.90 mmol).
(
(
CDCl ) d¼1.72 (s, 3H, SCH ), 2.37 (s, 3H, CH ), 3.90
3
3
3
dd, 1H, J¼9.6 and 15.2 Hz, CHH), 4.18–4.24 (m, 2H, CH
2
and CH), 7.01 (dd, 1H, J¼8.0 and 7.6 Hz, Ar), 7.20–7.27 (m,
5
H, Ts and Ar), 7.66 (d, 1H, J¼8.0 Hz, Ar), 7.70 (d, 2H,
1
3
J¼8.4 Hz, Ts). C NMR (CDCl ) d¼11.89 (SCH ), 21.76
3
3
(
Ts), 43.96 (CH), 56.79 (CH ), 114.78 (Ar), 124.23 (Ar),
2
1
(
25.77 (Ar), 127.59 (Ts), 129.33 (Ar), 129.94 (Ts), 130.93
Ts), 133.96 (Ar), 142.20 (Ar), 144.55 (Ts). Anal. found:
C, 60.23; H, 5.39; N, 4.36. Calcd for C H NO S : C,
1
6
17
2 2
6
0.16; H, 5.36; N, 4.38.
4.5. Reaction of o-isopropenyl-N-p-tosylanilide (3e) with
DMTST
4.7. Reaction of o-vinylbenzanilide with DMTST
To a solution of DMTST (516 mg, 2.0 mmol) in dichloro-
methane (5 mL) was added a solution of o-isopropenyl-
N-p-tosylanilide 3e (167 mg, 1.0 mmol) in dichloromethane
To a solution of DMTST (516 mg, 2.0 mmol) in dichloro-
methane (5 mL) was added a solution of o-vinylbenzanilide
3b (223 mg, 1.0 mmol) in dichloromethane (5 mL) at rt.
After stirring for 8 h, the reaction mixture was washed
with 10% of aq sodium carbonate (10 mL) and separated.
The water layer was extracted with dichloromethane
(5 mLꢁ2) and the combined extract was dried over magne-
sium sulfate, filtered, and evaporated to give colorless solid,
which was chromatographed over silica gel by elution
with hexane–dichloromethane (1:1) to afford colorless crys-
tals of 2-phenyl-4-methylthiomethyl-3,1-benzoxazine (5a)
(
5 mL) at rt. After stirring for 8 h, the reaction mixture
was washed with 10% of aq sodium carbonate (10 mL)
and separated. The water layer was extracted with dichloro-
methane (5 mLꢁ2) and the combined extract was dried over
magnesium sulfate, filtered, and evaporated to give colorless
solid, which was chromatographed over silica gel by elution
with hexane–dichloromethane (1:1) to afford colorless
plates of 3-methyl-N-tosylindole (1b) (265 mg, 0.92 mmol).
ꢀ
20
ꢀ
1
ꢀ
1
Mp 112–114 C (lit. mp 114–115 C). H NMR (CDCl )
3
(255 mg, 0.95 mmol). Mp 51–53 C. H NMR (CDCl )
3
d¼2.22 (s, 3H, CH ), 2.29 (s, 3H, TsMe), 7.16 (d, 2H,
d¼2.10 (s, 3H, SMe), 2.85 (dd, 1H, J¼5.6 and 14.0 Hz,
3
J¼8.0 Hz, Ts), 7.20 (t, 1H, J¼8.4 Hz, Ar), 7.30 (t, 1H, J¼
CH ), 3.05 (dd, 1H, J¼7.6 and 14.0 Hz, CH ), 5.56 (dd, 1H,
2
2
8
8
.0 Hz, Ar), 7.43 (d, 1H, J¼8.0 Hz, Ar), 7.73 (d, 2H, J¼
J¼5.6 and 7.6 Hz, CH), 7.09–7.55 (m, 8H, Ar), 8.18 (dd, 1H,
1
3
13
.0 Hz, Ts), 7.98 (d, 1H, J¼8.4 Hz, Ar). C NMR (CDCl )
J¼1.2 and 8.4 Hz, Ar). C NMR (CDCl ) d¼16.86 (SMe),
3
3
d¼9.91 (Me), 21.74 (TsMe), 113.89 (Ar), 118.83 (Ar),
19.61 (Ar), 123.20 (Ar), 123.29 (Ar), 124.79 (Ar), 126.95
Ts), 130.00 (Ts), 132.02 (Ar), 135.49 (Ar), 135.64 (Ts),
44.88 (Ts).
40.49 (CH ), 75.68 (CH), 124.74, 125.30, 126.60, 128.37,
2
1
(
1
128.51, 129.51, 131.72, 132.74, 139.71 (Ar), 156.56
(C]O). Anal. found: C, 70.64; H, 5.90; N, 5.03. Calcd for
C H NOS: C, 71.34; H, 5.61; N, 5.20.
1
6 15
The following reactions were carried out in a similar
manner.
Other reactions were carried out in a similar manner.
-Methyl-4-methylthiomethyl-3,1-benzoxazine (5b): color-
2
1
2-Phenyl-N-p-toluenesulfonylindole 1a: colorless oil;
spectral data were identical with the reported value.
less oil; H NMR (CDCl ) d¼2.10 (s, 3H, SMe), 2.15 (s,
3
2
1
3H, Me), 2.82 (dd, 1H, J¼5.6 and 13.2 Hz, CH ), 2.97
2