Mukai et al.
133.3, 129.6, 129.5, 129.2, 128.5, 127.6, 69.2, 63.9, 41.1, 29.3;
MS m/z 366 (M+, 8.7). HRMS calcd for C21H18O4S 366.0926, found
366.0925. Anal. Calcd for C21H18O4S: C, 68.83; H, 4.95. Found:
C, 68.53; H, 5.04. 7a: colorless needles, mp 216-218 °C (AcOEt);
IR 1680, 1304, 1151 cm-1; 1H NMR δ 7.92-7.90 (m, 2H), 7.61-
7.52 (m, 3H), 7.45-7.36 (m, 3H), 7.28-7.24 (m, 2H), 4.60 (t, 2H,
J ) 3.2 Hz), 3.92 (t, 2H, J ) 4.9 Hz), 3.70 (t, 2H, J ) 3.2 Hz),
2.69 (t, 2H, J ) 4.9 Hz); 13C NMR δ 148.5, 147.4, 141.2, 139.9,
132.94, 132.88, 129.7, 129.1, 128.9, 127.6, 127.5, 122.7, 70.5, 68.9,
36.3, 33.5; MS m/z 338 (M+, 79.4). HRMS calcd for C20H18O3S
338.0977, found 338.0977. Anal. Calcd for C20H18O3S: C, 70.98;
H, 5.36. Found: C, 70.70; H, 5.46.
General Procedure for Ring-Closing Reaction of Allenynes
under an Atmosphere of N2. To a solution of allenyne (0.10 mmol)
in toluene was added xylene or mesitylene (1 mL) with refluxed
under a N2 atmosphere until the starting material completely
disappeared (monitored by TLC). Solvent was evaporated off, and
the residual oil was chromatographed with hexane-AcOEt to afford
cyclized products. Chemical yields are summarized in Tables 1-4
and Schemes 3-5 and 9.
N-(4-Methylbenzenesulfonyl)-2-(phenylsulfonyl)-8-(trimethyl-
silyl)-5-azabicyclo[5.2.0]nona-1,7-diene (7e): colorless plates, mp
134-136 °C (AcOEt); IR 1666, 1350, 1306, 1159 cm-1; 1H NMR
δ 7.83-7.82 (m, 2H), 7.63-7.53 (m, 5H), 7.26-7.25 (m, 2H), 3.96
(br s, 2H), 3.39 (t, 2H, J ) 5.0 Hz), 3.26 (br s, 2H), 2.66 (t, 2H,
J ) 5.0 Hz), 2.42 (s, 3H), 0.16 (s, 9H); 13C NMR δ 160.5, 151.9,
149.2, 143.7, 140.7, 135.5, 133.1, 129.8, 129.2, 127.7, 127.0, 121.8,
49.6, 48.6, 37.9, 32.2, 21.5, -2.2; MS m/z 487 (M+, 2.0). HRMS
calcd for C24H29NO4S2Si 487.1307, found 487.1303. Anal. Calcd
for C24H29NO4S2Si: C, 59.10; H, 5.99; N, 2.87. Found: C, 58.77;
H, 6.08; N, 2.86.
7.13-7.11 (m, 2H), 5.32-5.31 (m, 2H), 4.27 (s, 2H), 3.42-3.38
(m, 2H), 2.80-2.77 (m, 2H), 2.34 (s, 3H), 2.01 (s, 3H); 13C NMR
δ 143.6, 142.1, 139.1, 138.8, 137.1, 135.6, 133.3, 131.6, 129.6,
129.3, 128.5, 128.3, 128.1, 127.7, 123.2, 122.1, 85.6, 82.0, 46.6,
38.2, 26.7, 21.7, 21.4; MS m/z 519 (M+, 0.6). HRMS calcd for
C29H29NO4S2 519.1538, found 519.1541.
9-Phenyl-2-(phenylsulfonyl)-6-oxabicyclo[6.2.0]deca-1,8-di-
ene (15a): colorless needles, mp 175-176.5 °C (AcOEt); IR 1302,
1
1150 cm-1; H NMR δ 7.92-7.91 (m, 2H), 7.59-7.56 (m, 1H),
7.54-7.51 (m, 2H), 7.45-7.42 (m, 2H), 7.40-7.37 (m, 1H), 7.34-
7.32 (m, 2H), 4.55 (t, 2H, J ) 3.1 Hz), 3.75 (t, 2H, J ) 3.1 Hz),
3.70 (t, 2H, J ) 6.1 Hz), 2.62-2.60 (m, 2H), 1.77-1.72 (m, 2H);
13C NMR δ 151.3, 148.4, 141.8, 139.5, 133.0, 132.7, 129.8, 129.1,
128.9, 127.9, 127.6, 123.4, 69.0, 65.4, 37.1, 28.0, 24.5; MS m/z
352 (M+, 0.1). HRMS calcd for C21H20O3S 352.1133, found
352.1134.
N-(4-Methylbenzenesulfonyl)-9-phenyl-2-(phenylsulfonyl)-6-
azabicyclo[6.2.0]deca-1,8-diene (15b): colorless needles, mp
1
198.5-200 °C (AcOEt); IR 1346, 1304, 1157 cm-1; H NMR δ
7.89-7.86 (m, 2H), 7.69-7.29 (m, 12H), 4.28-4.26 (m, 2H),
3.70-3.69 (m, 2H), 3.26 (t, 2H, J ) 5.9 Hz), 2.58-2.54 (m, 2H),
2.42 (s, 3H), 1.79-1.70 (m, 2H); 13C NMR δ 153.0, 148.3, 143.7,
141.3, 135.3, 134.6, 132.9, 132.5, 130.2, 129.8, 129.1, 129.0, 127.8,
127.6, 127.2, 122.8, 46.3, 45.4, 37.3, 28.2, 24.3, 21.5; MS m/z 505
(M+, 0.5). Anal. Calcd for C28H27NO4S2: C, 66.51; H, 5.38; N,
2.77. Found: C, 66.24; H, 5.56; N, 2.86.
4,4-Bis(methoxycarbonyl)-9-phenyl-2-(phenylsulfonyl)bicyclo-
[6.2.0]deca-1,8-diene (15c): pale yellow plates, mp 183-185 °C
1
(AcOEt); IR 1728, 1306, 1151 cm-1; H NMR δ 7.87-7.86 (m,
2H), 7.59-7.36 (m, 8H), 3.80 (s, 6H), 3.64 (s, 2H), 3.20 (s, 2H),
2.67-2.64 (m, 2H), 2.27-2.24 (m, 2H), 1.68-1.66 (m, 2H); 13C
NMR δ 171.4, 155.3, 151.6, 141.8, 140.9, 133.4, 132.7, 129.7,
129.1, 128.8, 127.7, 127.4, 117.9, 57.9, 52.8, 36.7, 30.7, 28.0, 24.3,
22.6; MS m/z 466 (M+, 0.2). Anal. Calcd for C26H26O6S: C, 66.93;
H, 5.62. Found: C, 66.69; H, 5.81.
4,4-Bis(methoxycarbonyl)-8-(trimethylsilyl)-2-(phenylsulfonyl)-
bicyclo[5.2.0]nona-1,7-diene (7f): colorless needles, mp 133-
1
135 °C (AcOEt); IR 1734, 1304, 1155 cm-1; H NMR δ 7.93-
7.90 (m, 2H), 7.61-7.52 (m, 3H), 3.58 (s, 6H), 3.27-3.25 (m,
2H), 2.97 (s, 2H), 2.50-2.43 (m, 2H), 2.24-2.19 (m, 2H), 0.14
(s, 9H); 13C NMR δ 170.7, 160.3, 155.7, 151.0, 141.2, 132.8, 129.0,
127.8, 117.9, 57.3, 52.7, 37.7, 36.1, 30.9, 25.1, -2.0; MS m/z 448
(M+, 10.4). HRMS calcd for C22H28O6SSi 448.1376, found
448.1376. Anal. Calcd for C22H28O6SSi: C, 58.90; H, 6.29.
Found: C, 58.53; H, 6.38.
N-(4-Methylbenzenesulfonyl)-2-(phenylsulfonyl)-7-propyl-4-
azabicyclo[4.2.0]octa-1,6-diene (17e): a colorless oil; IR 1350,
1
1306, 1159 cm-1; H NMR δ 7.87-7.83 (m, 2H), 7.67-7.46 (m,
5H), 7.20-7.17 (m, 2H), 4.07 (s, 2H), 3.95-3.94 (m, 2H), 3.02
(s, 2H), 2.40 (s, 3H), 2.21-2.15 (m, 2H), 1.56-1.42 (m, 2H), 0.96-
0.90 (m, 3H); 13C NMR δ 155.1, 146.9, 143.6, 140.5, 134.54,
134.49, 133.3, 129.5, 129.3, 127.6, 127.4, 114.0, 42.8, 41.8, 38.5,
32.6, 21.5, 19.8, 14.0; MS m/z 443 (M+, 0.4). HRMS calcd for
C23H25NO4S2 443.1225, found 443.1218.
9-Methyl-N-(4-methylbenzenesulfonyl)-8-phenyl-2-(phenylsul-
fonyl)-5-azabicyclo[5.2.0]nona-1,7-diene (9): colorless plates, mp
1
205.5-207 °C (AcOEt); IR 1344, 1304, 1153 cm-1; H NMR δ
7.86 (d, 2H, J ) 7.6 Hz), 7.64-7.60 (m, 3H), 7.56-7.53 (m, 2H),
7.48-7.39 (m, 3H), 7.31 (d, 2H, J ) 7.6 Hz), 7.27-7.25 (m, 2H),
4.37-4.26 (m, 2H), 4.09-4.07 (m, 1H), 3.52-3.48 (m, 1H), 3.42-
3.38 (m, 1H), 2.74-2.69 (m, 1H), 2.63-2.58 (m, 1H), 2.41 (s,
3H), 1.59 (d, 3H, J ) 6.6 Hz); 13C NMR δ 155.2, 152.3, 143.7,
140.7, 135.5, 134.3, 133.1, 131.6, 129.9, 129.13, 129.05, 127.8,
127.5, 127.0, 121.2, 48.6, 48.2, 43.9, 32.5, 21.5, 17.4; MS m/z 505
(M+, 3.5). Anal. Calcd for C28H27NO4S2: C, 66.51; H, 5.38; N,
2.77. Found: C, 66.29; H, 5.50; N, 2.73.
4,4-Bis(methoxycarbonyl)-7-butyl-2-(phenylsulfonyl)bicyclo-
[4.2.0]nona-1,6-diene (17f): a colorless oil; IR 1736, 1306, 1155
1
cm-1; H NMR δ 7.88-7.87 (m, 2H), 7.61-7.58 (m, 1H), 7.55-
7.52 (m, 2H), 3.49 (s, 6H), 3.28 (br s, 2H), 2.89 (s, 2H), 2.70 (br
s, 2H), 2.33 (t, 2H, J ) 7.3 Hz), 1.55 (quin, 2H, J ) 7.3 Hz), 1.37
(sex, 2H, J ) 7.3 Hz), 0.93 (t, 3H, J ) 7.3 Hz); 13C NMR δ 170.1,
155.8, 148.4, 140.8, 137.5, 132.7, 128.9, 127.8, 113.6, 55.5, 52.8,
38.2, 30.3, 29.2, 28.4, 28.0, 22.5, 13.7; MS m/z 418 (M+, 87.2).
HRMS calcd for C22H26O6S 418.1450, found 418.1438.
9-Methyl-N-(4-methylbenzenesulfonyl)-2-[(Z)-phenylmethyl-
ene]-7-(phenylsulfonyl)-4-azabicyclo[5.2.0]non-1(9)-ene (11): col-
orless needles, mp 153-154 °C (AcOEt); IR 1360, 1157, 1146
8-Methyl-N-(4-methylbenzenesulfonyl)-2-(phenylsulfonyl)-7-
(trimethylsilyl)-4-azabicyclo[4.2.0]octa-1,6-diene (19): colorless
1
plates, mp 119-120 °C (AcOEt); IR 1346, 1306, 1157 cm-1; H
1
cm-1; H NMR δ 7.88-7.84 (m, 2H), 7.66-7.20 (m, 12H), 6.47
NMR δ 7.89-7.86 (m, 2H), 7.71-7.57 (m, 3H), 7.39-7.36 (m,
2H), 7.16-7.13 (m, 2H), 4.23-4.13 (m, 2H), 4.02-3.96 (m, 1H),
3.86 (dd, 1H, J ) 17.3, 3.5 Hz), 3.58-3.54 (m, 1H), 2.39 (s, 3H),
1.12 (d, 3H, J ) 6.9 Hz), 0.12 (s, 9H); 13C NMR δ 164.0, 153.1,
148.3, 143.6, 140.2, 135.0, 133.6, 129.6, 129.4, 127.6, 127.4, 114.7,
48.0, 42.9, 42.7, 21.4, 17.5, -1.8; MS m/z 487 (M+, 1.6). HRMS
calcd for C24H29NO4S2Si 487.1307, found 487.1311. Anal. Calcd
for C24H29NO4S2Si: C, 59.10; H, 5.99; N, 2.87. Found: C, 58.79;
H, 6.05; N, 2.87.
(s, 1H), 4.98 (d, 1H, J ) 16.8 Hz), 4.17-4.08 (m, 2H), 3.74-3.63
(m, 1H), 2.75-2.69 (m, 1H), 2.53 (d, 1H, J ) 14.9 Hz), 2.39 (s,
3H), 2.16-2.04 (m, 2H), 1.60 (s, 3H); 13C NMR δ 143.0, 142.9,
138.8, 137.5, 136.1, 135.8 134.3, 133.8, 129.6, 129.5, 128.9, 128.8,
128.5, 128.4, 127.5, 126.9, 68.8, 50.0, 49.9, 42.6, 34.0, 21.4, 15.2;
MS m/z 519 (M+, 0.7). Anal. Calcd for C29H29NO4S2: C, 67.02;
H, 5.62; N, 2.70. Found: C, 66.81; H, 5.67; N, 2.66.
N-[(E)-5-Methyl-3-(phenylsulfonyl)hexa-3,5-dienyl]-N-(3-phenyl-
2-propynyl)-(4-methylbenzene)sulfonamide (12): colorless plates,
1-(4-Methylbenzenesulfonyl)-5-(phenylsulfonyl)-4-(1-propen-
2-yl)-3-[(Z)-(trimethylsilyl)methylene]-1,2,3,6-tetrahydropyri-
dine (21): colorless plates, mp 144-145.5 °C (AcOEt); IR 1352,
mp 102-103.5 °C (AcOEt); IR 1599, 1491, 1348, 1306, 1161 cm-1
;
1H NMR δ 7.89-7.87 (m, 2H), 7.73-7.71 (m, 2H), 7.58-7.55
(m, 1H), 7.48-7.44 (m, 2H), 7.40 (s, 1H), 7.32-7.23 (m, 5H),
1
1308, 1161, 1153 cm-1; H NMR δ 7.88-7.85 (m, 2H), 7.69-
4460 J. Org. Chem., Vol. 72, No. 12, 2007