7516
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Dichloromethane (9 mL) was added and the solution was
stirred for 1 h at 0°C then 8 h at 25°C. The reaction
mixture was cooled to 0°C and a solution of the 11 (2.37
g, 5.85 mmol) and pyridine (4.60 g, 4.7 mL, 58 mmol) in
dichloromethane (4 mL) was added dropwise. The reac-
tion mixture was warmed to 25°C and stirred for 3 h. The
reaction was quenched by the successive addition of ethyl
acetate (10 mL) and H2O (5 mL). The biphasic mixture
was poured into ethyl acetate (25 mL) and H2O (10 mL).
The phases were separated and the aqueous layer
extracted with ethyl acetate (15 mL). The combined
organic extracts were washed with saturated brine (2×15
mL), dried over MgSO4, and concentrated under reduced
pressure. Purification by flash chromatography on silica
gel, eluting with 10% ethyl acetate in hexanes, gave 7 as
1
a clear oil (1.78 g, 63%). [h]D +15.04° (c 1.3, CHCl3); H
NMR (CDCl3, 300 MHz) l 7.17–7.65 (m, 15H), 4.62–466
(m, 1H), 4.57–4.60 (br s, 2H), 3.77–3.89 (m, 2H), 2.65–
2.75 (m, 2H), 1.94–2.05 (m, 2H), 1.09 (s, 9H); 13C NMR
(CDCl3, 75 MHz) l 141.7, 136.4, 136.3, 130.4, 130.3,
128.8, 128.7, 128.2, 128.1, 126.4, 73.6, 70.9, 35.7, 31.4,
27.4, 19.7.
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28. 6 and 12: To a solution of 7 (0.832 g, 1.75 mmol) in
dichloromethane (11.2 mL), were sequentially added
Mg2O (2.07 g, 51.6 mmol), PhI(OAc)2 (0.586 g, 1.82
mmol), and of Rh2(OAc)4 (0.107 g, 0.243 mmol). The
suspension was heated at 40°C with vigorous stirring for
3 h. The reaction mixture was then cooled to 25°C,
diluted with dichloromethane (28 mL) and filtered
through a pad of Celite. The filter cake was washed with
dichloromethane (2×21 mL) and the combined filtrates
were evaporated under reduced pressure. The residue was
purified by flash chromatography on silica gel, eluting
with 5% ethyl acetate in hexanes to give 6 (614 mg, 73%
yield) and 12 (68 mg, 8% yield) as white solids. 6: mp
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15. It should be noted that the designation of the absolute
stereochemistry may change depending on the C6-sub-
stituent R. For R=-CH3 and other simple aliphatics, the
C6 stereochemistry of 2 and 3 is designated as R and S,
respectively, while for entries c and d the assignment is
reversed.
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1
43–8°C; [h]D=−1.46° (c 1.46, CHCl3); H NMR (CDCl3,
19. Nechev, L. V.; Kozekov, I.; Harris, C. M.; Harris, T. M.
300 MHz) l 7.26–7.67 (m, 15H), 4.95–4.78 (m, 2H), 4.14
(1H, d, J=9.4 Hz), 3.86 (2H, d, J=4.3 Hz), 2.04–2.10
(m, 2H), 1.03 (s, 9H); 13C NMR (CDCl3, 75 MHz) l
138.4, 136.0, 135.9, 133.1, 133.0, 130.4, 129.6, 129.3,
128.3, 126.7, 83.7, 65.6, 58.3, 32.5, 27.2, 19.7; 12: mp
40–42°C; [h]D=+24.06° (c 0.3, CHCl3); 1H NMR
(CDCl3, 300 MHz) l 7.35–7.65 (m, 15H), 4.85–4.72 (m,
2H), 4.43 (1H, d, J=8.5), 4.14 (m, 2H), 2.30–2.34 (m,
2H), 1.07 (s, 9H); 13C NMR (CDCl3, 75 MHz) l 135.9,
130.5, 129.4, 128.9, 128.3, 126.7, 82.7, 63.7, 55.5, 30.1,
27.2, 19.6.
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27. 7: Sulfamoyl chloride was prepared by the dropwise
addition of formic acid (0.793, 650 mL, 17.2 mmol) to
neat chlorosulfonyl isocyanate (2.44 g, 1.5 mL, 17.2
mmol) at 0°C with rapid stirring. Gas was evolved during