44.9 (d), 48.4 (d), 77.2 (d), 124.5 (d), 126.7 (d), 126.8 (d), 128.5
(d), 129.3 (d), 129.8 (d), 133.5 (d), 134.2 (s), 136.8 (s), 150.0 (s).
Rh2(OAc)4 (0.1-0.2 mol %) in acetonitrile (10 mL) was stirred
at 20 °C for 96 h. The solvent and excess cyclooctene were
removed (30 °C, 10 Torr), and the reaction residue was flash-
chromatographed (silica gel, CH2Cl2) to afford 4d as colorless
needles (142 mg, 42%). Mp: 135-136 °C (CHCl3-petroleum
ether). IR (KBr): 2960 cm-1, 2880, 1615, 1510, 1460, 1320, 1310,
1300, 1290, 1225, 1205, 1190, 1140, 1120, 1090, 1045, 1020, 830.
1H NMR (200 MHz, CDCl3): δ 0.53-0.70 (m, 1H), 1.34-1.95 (m,
11H), 2.37 (s, 3H), 2.39 (s, 3H), 2.51-2.64 (m, 1H), 2.90-3.00
(m, 1H), 4.30 (d, J ) 5.8 Hz, 1H), 6.94 (d, J ) 7.8 Hz, 1H), 7.12
(d, J ) 7.8 Hz, 1H), 7.22 κRι 7.54 (ΑΑ′ΒΒ′ system, 4H), 7.53 (s,
1H). 13C NMR (50 MHz, CDCl3): δ 20.9 (+), 21.2 (+), 23.3 (-),
23.8 (-), 26.4 (-), 26.5 (-), 35.4 (-), 35.6 (-), 44.1 (+), 47.1 (+),
77.6 (+), 124.0 (+), 127.2 (+), 129.5 (+), 129.9 (+), 130.5 (+),
133.6, 134.1, 137.1, 144.9, 147.1. HRMS [CI (NH3)]: calcd for
+
HRMS [CI (NH3)]: calcd for C18H18O2S NH4 [Μ + NH4]+,
316.1371, found 316.1370.
Syn th esis of 4b. A suspension of the iodonium ylide 2a (0.50
g, 1.00 mmol), 1-methylcyclopentene (3b; 328 mg, 4.00 mmol),
and Rh2(OAc)4 (0.1-0.2 mol %) in acetonitrile (3 mL) was heated
at 70 °C for 2 h. The solvent and excess 1-methylcyclopentene
were removed (50 °C, 10 Torr), and the residue was flash-
chromatographed (silica gel, CH2Cl2) to afford benzo-2-phenyl-
sulfonyl-5-methylbicyclo[3.3.0]oct-3-ene (4b) as a colorless oil (98
mg, 31%). IR (neat): 3130 cm-1, 3000, 2910, 1505, 1470, 1325,
1
1235, 1160, 1145, 1100, 1035, 835. H NMR (400 MHz, CDCl3):
δ 0.93 (s, 3H), 1.16-1.32 (m, 1H), 1.47-1.64 (m, 3H), 1.67-1.73
(m, 1H), 1.96-2.05 (m, 1H), 2.68-2.72 (m, 1H), 4.40 (d, J ) 3.0
Hz, 1H), 7.06 (d, J ) 7.7 Hz, 1H), 7.19-7.23 (m, 1H), 7.31-7.35
(m, 1H), 7.40-7.44 (m, 3H), 7.54-7.58 (m, 1H), 7.64 (dd, J )
1.2, 8.4 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ 25.7 (t), 27.6
(q), 35.7 (t), 42.9 (t), 51.4 (d), 55.6 (s), 77.8 (d), 123.4 (d), 126.2
(d), 126.9 (d), 128.7 (d), 129.5 (d), 129.9 (d), 133.5 (d), 133.7 (s),
+
C23H28O2S NH4 [Μ + NH4]+ 386.2154, found 386.2151.
Syn th esis of 5. Na2HPO4 (0.36 g) and sodium amalgam (2.50
g) were added to a solution of the cycloadduct 4a (152 mg, 0.51
mmol) in methanol (10 mL). The reaction mixture was stirred
at 20 °C for 40 h, the solvent was removed (40 °C, 10 Torr), and
the residue was dissolved in dichloromethane (30 mL) and
washed with brine (2 × 50 mL). After drying (MgSO4), the
solvent was removed (20 °C, 10 Torr) to afford benzobicyclo[3.3.0]-
oct-3-ene (5a ) as a colorless oil (74 mg, 92%). IR (neat): 3130
+
136.9 (s), 153.8 (s). HRMS [CI (NH3)]: calcd for C19H20O2S NH4
[Μ + NH4]+ 330.1528, found 330.1533.
Syn th esis of 4c. A suspension of the iodonium ylide 2a (0.50
g, 1.00 mmol), trans-cyclooctene (3b; 0.50 g, 4.50 mmol), and
Rh2(OAc)4 (0.1-0.2 mol %) in acetonitrile (10 mL) was stirred
at 20 °C for 128 h. The solvent and excess cyclooctene were
removed (30 °C, 10 Torr), and the reaction residue was flash-
chromatographed (silica gel, CH2Cl2) to afford benzo-2-phen-
ylsulfonylbicyclo[6.3.0]undec-3-ene (4c) as colorless needles (157
mg, 46%). Mp:152-153 °C (CHCl3-petroleum ether). IR (KBr):
2950 cm-1, 2910, 2890, 2860, 2840, 1590, 1575, 1560, 1575, 1560,
1325, 1170, 1105, 1090, 1050, 1035, 1005, 980, 950, 930, 885,
850. 1H NMR (400 MHz, CDCl3): δ 0.54-0.60 (m, 1H), 1.37-
1.78 (m, 9H), 1.82-1.95 (m, 2H), 2.56-2.63 (m, 1H), 2.97-3.03
(m, 1H), 4.37 (d, J ) 5.7 Hz, 1H), 7.05 (d, J ) 7.3 Hz, 1H), 7.24-
7.31 (m, 2H), 7.39-7.43 (m, 2H), 7.53-7.57 (m, 1H), 7.63-7.66
(m, 2H), 7.73 (d, J ) 7.5 Hz, 1H). 13C NMR (100 MHz, CDCl3):
δ 23.7 (t), 24.2 (t), 26.8 (t), 26.9 (t), 35.4 (t), 35.9 (t), 44.0 (d),
47.6 (d), 77.7 (d), 124.0 (d), 126.5 (d), 127.0 (d), 128.6 (d), 129.3
(d), 129.6 (d), 133.1 (d), 133.5 (s), 136.5 (s), 149.6 (s). Anal. Calcd
for C21H24O2S (340.5): C, 74.08; H, 7.10; S, 9.42. Found: C,74.26;
H, 6.91; S, 9.34.
1
cm-1, 3080, 2980, 2910, 1505, 1470, 1230, 1180, 1035. H NMR
(400 MHz, CDCl3): δ 1.35-1.63 (m, 3H), 1.73-1.80 (m, 1H),
1.84-1.92 (m, 1H), 1.99-2.11 (m, 1H), 2.71 (dd, J ) 3.3, 16.5
Hz, 1H), 2.85-2.94 (m, 1H), 3.24 (dd, J ) 8.8, 16.5 Hz, 1H), 3.66
(ddd, J ) 3.3, 8.8, 12.5 Hz, 1H), 7.11-7.19 (m, 4H).13C NMR
(100 MHz, CDCl3): δ 26.1 (t), 34.1 (t), 34.9 (t), 39.6 (t), 42.0 (d),
50.3 (d), 124.4 (d), 124.5 (d), 126.1 (d), 126.4 (d), 143.5 (s), 148.0
(s). HRMS (EI): calcd for C12H14 [Μ+] 158.1095, found 158.109.
Ack n ow led gm en t. We thank the Deutsche Fors-
chungsgemeinschaft and the Fonds der Chemischen
Industrie for generous funding. E.P.G. also thanks
INTERREG II (Prof. Dr. M. Karayiannis, University of
Ioannina) and DAAD for research scholarships.
Su p p or tin g In for m a tion Ava ila ble: 1H and 13C spectra
of 4a -d and 5a . This material is available free of charge via
the Internet at http://pubs.acs.org.
Syn th esis of 4d . A suspension of the iodonium ylide 2b
(0.526 g, 1.00 mmol), cis-cyclooctene (3b; 0.50 g, 4.50 mmol) and
J O035362E
9158 J . Org. Chem., Vol. 68, No. 23, 2003