) 6.33 Hz, 2H), 5.23 (m, 1H), 5.56 (m, 1H), 7.30-7.68 (m, 15H);
13C NMR (50 MHz, CDCl3) δ 19.6, 20.3, 26.9, 27.9, 60.2, 65.1,
124.1, 127.7, 129.2, 129.6, 130.9, 133.9, 135.6, 144.0; MS (EI,
m/z) 405 (M+ - C4H9).
Br om oh yd r in 5b: liquid; 1H NMR (200 MHz, CDCl3) δ 1.24
(d, J ) 6.36 Hz, 3H), 1.76 (d, J ) 6.36 Hz, 3H), 2.44 (m, 1H),
2.59 (dd, J ) 12.72, 8.14 Hz, 1H), 3.04 (dd, J ) 12.72, 3.82 Hz,
1H), 3.19 (dd, J ) 6.11, 3.82 Hz, 1H), 4.26 (m, 1H), 7.50-7.68
(m, 5H); 13C NMR (50 MHz, CDCl3) δ 17.5, 23.4, 34.8, 54.8, 60.8,
77.7, 124.2, 129.3, 131.2, 144.3; MS (EI, m/z) 304, 286.
Br om oh yd r in 5c: solid; mp 160-162 °C; 1H NMR (200 MHz,
CDCl3) δ 1.33 (d, J ) 6.33 Hz, 3H), 2.61 (dd, J ) 13.16, 8.86 Hz,
1H), 2.89 (dd, J ) 13.16, 3.80 Hz, 1H), 3.05 (m, 1H), 4.25 (dd, J
) 8.86, 2.0 Hz, 1H), 4.80 (d, J ) 8.86, 1H), 7.34 (bs, 5H), 7.45-
7.58 (m, 5H); 13C NMR (50 MHz, CDCl3) δ 14.3, 30.0, 65.3, 66.0,
76.0, 124.0, 127.0, 128.4, 128.5, 129.3, 131.1, 141.6, 144.0; MS
(FAB, m/z) 366, 348, 271.
Su lfoxid e (3b): liquid; 1H NMR (200 MHz, CDCl3) δ 1.10 (d,
J ) 7.10 Hz, 3H), 1.72 (d, J ) 7.10 Hz, 3H), 2.48 (dd, J ) 12.94,
10.60 Hz, 1H), 2.81 (dd, J ) 12.94, 4.71 Hz, 1H), 3.20 (m, 1H),
5.22 (m, 1H), 5.62 (m, 1H), 7.43-7.62 (m, 5H); 13C NMR (50
MHz, CDCl3) δ 12.8 20.0, 27.0, 65.7, 124.0, 124.3, 129.0, 130.6,
133.1, 144.5; MS (EI, m/z) 208 (M+), 145, 131.
Su lfoxid e (4b): liquid; 1H NMR (200 MHz, CDCl3) δ 1.20 (d,
J ) 7.0 Hz, 3H), 1.61 (d, J ) 7.0 Hz, 3H), 2.51 (dd, J ) 12.68,
9.86 Hz, 1H), 2.80 (dd, J ) 12.68, 6.76 Hz, 1H), 3.06 (m, 1H),
5.20 (m, 1H), 5.40 (m, 1H), 7.42-7.62 (m, 5H); 13C NMR (50
MHz, CDCl3) δ 13.0, 20.9, 27.2, 66.3, 123.7, 125.7, 129.0, 130.6,
132.8, 145.1; MS (EI, m/z) 208 (M+), 145, 131.
Br om oh yd r in 5d a n d Regioisom er (In sep a r a ble Mix-
tu r e): liquid; 1H NMR (200 MHz, CDCl3) δ 1.05-1.28 (m, 12
H), 2.60-3.0 (m, 3H), 3.80-4.15 (m, 4H), 7.35-7.68 (m, 15H).
Br om oh yd r in 6a : liquid; 1H NMR (200 MHz, CDCl3) δ 1.02
(d, J ) 6.70 Hz, 3H), 1.06 (s, 9H), 2.39 (m, 1H), 2.92 (dd, J )
13.10, 3.81 Hz, 1H), 3.10 (dd, J ) 13.10, 3.81 Hz, 1H), 3.66 (d,
J ) 8.57 Hz, 1H), 3.94-4.15 (m, 3H), 7.33-7.52 (m, 9H), 7.58-
7.70 (m, 6H); 13C NMR (50 MHz, CDCl3) δ 17.3, 19.8, 26.9, 34.7,
57.9, 61.2, 65.5, 72.4, 124.2, 127.9, 129.3, 129.9, 131.1, 133.7,
135.6, 144.0; MS (FAB, m/z) 559, 501.
Br om oh yd r in 6b: liquid; 1H NMR (200 MHz, CDCl3) δ 1.03
(d, J ) 6.70 Hz, 3H), 1.77 (d, J ) 6.70 Hz, 3H), 2.33 (m, 1H),
2.84-3.08 (m, 2H), 3.53 (bs, 1H), 4.26 (m, 1H), 7.46-7.62 (m,
5H); 13C NMR (100 MHz, CDCl3) δ 16.9, 23.1, 34.2, 55.2, 61.7,
78.4, 124.0, 129.3, 131.1, 144.2; MS (EI, m/z) 304, 286.
Br om oh yd r in 6c: liquid; 1H NMR (200 MHz, CDCl3) δ 1.18
(d, J ) 6.33 Hz, 3H), 2.77 (dd, J ) 10.13, 8.0 Hz, 1H), 2.89-
3.07 (m, 2H), 4.72 (d, J ) 8.10, 1H), 4. 82 (d, J ) 8.10, 1H),
7.31-7.60 (m, 10H); 13C NMR (50 MHz, CDCl3) δ 15.4, 29.7, 64.1,
64.2, 76.0, 123.9, 127.0, 128.5, 128.6, 129.4, 131.1, 141.5, 143.7;
MS (FAB, m/z) 366, 348, 271.
Su lfoxid e (3c): solid; mp 83-84 °C; 1H NMR (200 MHz,
CDCl3) δ 1.25 (d, J ) 6.45 Hz, 3H), 2.65 (dd, J ) 12.90, 9.68 Hz,
1H), 2.90 (dd, J ) 12.90, 5.38 Hz, 1H), 3.05 (m, 1H), 6.12 (dd, J
) 15.48, 8.17 Hz, 1H), 6.59 (d, J ) 15.48, 1H), 7.20-7.40 (m,
5H), 7.45-7.68 (m, 5H); 13C NMR (50 MHz, CDCl3) δ 20.8, 32.8,
65.8, 123.8, 126.2, 127.3, 128.4, 129.1, 130.8, 130.9, 132.0, 136.9,
144.9; MS (FAB, m/z) 271 (M+ + H), 221, 193.
Su lfoxid e (4c): liquid; 1H NMR (200 MHz, CDCl3) δ 1.38 (d,
J ) 6.60 Hz, 3H), 2.67 (dd, J ) 13.10, 10.48 Hz, 1H), 2.94-3.14
(m, 2H), 6.12 (dd, J ) 16.60, 9.52 Hz, 1H), 6.41(d, J ) 16.60,
1H), 7.20-7.40 (m, 5H), 7.45-7.70 (m, 5H); 13C NMR (50 MHz,
CDCl3) δ 19.4, 32.1, 65.1, 123.9, 126.0, 127.4, 128.4, 129.2, 129.8,
130.9, 132.7, 136.8, 144.2; MS (FAB, m/z) 271 (M++ H).
Su lfoxid e (3d ): liquid; 1H NMR (200 MHz, CDCl3) δ 1.06 (s,
9H), 1.14 (d, J ) 6.40 Hz, 3H), 2.53 (dd, J ) 12.72, 8.91 Hz,
1H), 2.80 (dd, J ) 12.72, 5.08 Hz, 1H), 2.82 (m, 1H), 4.20 (m,
2H), 5.70 (m, 2H), 7.30-7.70 (m, 15H); 13C NMR (50 MHz,
CDCl3) δ 19.3, 19.4, 26.9, 32.1, 64.0, 65.9, 123.9, 127.6, 129.2,
129.6, 130.9, 133.9, 135.5, 145.0; MS (EI, m/z) 405 (M+ - C4H9),
229, 199.
Gen er a l P r oced u r e for th e P r ep a r a tion of Br om oh y-
d r in s 5/6. To a stirred solution of the unsaturated sulfoxide 3/4
(0.25 mmol) in toluene (1 mL) at room temperature was added
water (8 µL, 1.7 equiv) followed by NBS (54 mg, 1.2 equiv) in
one portion. The solution was stirred until TLC examination
showed consumption of the starting material. The reaction
mixture was diluted with ether and the organic phase washed
with saturated NaHCO3, water, and brine, and dried (Na2SO4).
The solvent was evaporated to afford a residue, which was
purified by column chromatography using EtOAc/petroleum
ether as the eluent.
Ack n ow led gm en t. S.R. is thankful to Dr. J . S.
Yadav, Head, Organic Division I, and Dr. K. V. Ragha-
van, Director, I.I.C.T, for their constant support and
encouragement. S.R is thankful to DST for financial
assistance. K.A.T. and Ch.N.K. are thankful to CSIR
(N. Delhi) for fellowships. A.K.V. thanks the CSIR (01/
1570/99/EMR-II) for a fellowship. A.N. and A.K.V. thank
the DST for the National Diffractometer facility in the
University of Hyderabad.
Br om oh yd r in 5a : liquid; 1H NMR (200 MHz, CDCl3) δ 1.06
(s, 9H), 1.55 (d, J ) 6.30 Hz, 3H), 2.41 (m, 1H), 2.61 (dd, J )
12.60, 7.04 Hz, 1H), 3.22 (dd, J ) 12.60, 4.03 Hz, 1H), 3.57 (d,
J ) 8.80 Hz, 1H), 3.86-4.12 (m, 3H), 7.40-7.58 (m, 9H), 7.63-
7.72 (m, 6H); 13C NMR (50 MHz, CDCl3) δ 16.6, 19.2, 26.8, 34.7,
57.9, 62.4, 65.6, 73.2, 124.1, 127.9, 129.3, 130.0, 131.0, 133.2,
135.5, 135.6, 144.3; MS (FAB, m/z) 559, 501.
Su p p or tin g In for m a tion Ava ila ble: Experimental de-
tails for compounds 1, 2a -d , 7, and 9 and crystallographic
data for 3c and 5c. This material is available free of charge
J O015921M
J . Org. Chem, Vol. 67, No. 16, 2002 5841