M.-Y. Chang et al. / Tetrahedron Letters 47 (2006) 3641–3644
3643
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7. A representative procedure for olefins 3 is as follows: m-
Chloroperoxybenzoic acid (255 mg, 75%, 1.1 mmol) was
added to a solution of aldehydes 3 (0.5 mmol) and sodium
carbonate (130 mg, 1.2 mmol) in dichloromethane
(10 mL). The reaction mixture was stirred at rt for 3 h.
The total procedure was monitored by TLC until the
reaction was completed. Saturated sodium carbonate
solution (5 mL) was added to the reaction mixture and
the solvent was concentrated under reduced pressure. The
residue was extracted with ethyl acetate (3 · 20 mL). The
combined organic layers were washed with brine, dried,
filtered and evaporated to afford crude product under
reduced pressure. Without further purification, Boron
trifluoride etherate (0.1 mL) was added to a stirring
solution of the resulting crude product in dichloromethane
(10 mL) at rt. The reaction mixture was stirred at rt for
15 min. Saturated sodium bicarbonate solution (5 mL)
was added to the reaction mixture and the solvent was
concentrated under reduced pressure. The residue was
extracted with ethyl acetate (3 · 20 mL). The combined
organic layers were washed with brine, dried, filtered, and
evaporated to afford crude product under reduced
pressure. Purification on silica gel (hexane/ethyl ace-
tate = 10:1) afforded olefins 3. For 3A: 1H NMR
(500 MHz, CDCl3) d 7.77 (d, J = 8.5 Hz, 2H), 7.33–7.27
(m, 7H), 6.01 (t, J = 2.0 Hz, 1H), 4.49 (td, J = 2.0, 4.0 Hz,
2H), 4.31 (td, J = 2.0, 4.0 Hz, 2H), 2.42 (s, 3H); 13C NMR
(125 MHz, CDCl3) d 143.56, 137.34, 134.08, 132.48,
129.83 (2·), 128.68 (2·), 128.43, 127.47 (2·), 125.38 (2·),
118.86, 55.66, 54.90, 21.50; HRMS (ESI) m/z calcd for
C17H18NO2S (M++1) 300.1058, found 300.1058. For 3B:
1H NMR (500 MHz, CDCl3) d 7.77 (d, J = 8.0 Hz, 2H),
7.33 (d, J = 8.0 Hz, 2H), 7.27–7.24 (m, 2H), 7.02 (t,
J = 8.5 Hz, 2H), 5.94 (t, J = 2.0 Hz, 1H), 4.46–4.44
(m, 2H), 4.31–4.28 (m, 2H), 2.42 (s, 3H); 13C NMR
(125 MHz, CDCl3) d 163.59, 161.62, 143.62, 136.28,
133.99, 129.85 (2·), 127.45 (2·), 127.13, 127.06,
118.64, 115.77, 115.59, 55.60, 54.92, 21.50; HRMS (ESI)
m/z calcd for C17H17FNO2S (M++1) 318.0964, found
318.0963.
8. A representative procedure for ketones 4 with one-pot
reaction is as follows: m-Chloroperoxybenzoic acid
(255 mg, 75%, 1.1 mmol) was added to a solution of
olefins 3 (0.8 mmol) in dichloromethane (10 mL). The
reaction mixture was stirred at rt for 3 h. The total
procedure was monitored by TLC until the reaction was
completed. Without further purification, boron trifluoride
etherate (0.1 mL) was added to a stirred solution of the
resulting reaction mixture at 0 ꢁC. The reaction mixture
was stirred at rt for 15 min. Saturated sodium bicarbonate
solution (10 mL) was added to the reaction mixture and
the solvent was concentrated under reduced pressure. The
residue was extracted with ethyl acetate (3 · 20 mL). The
combined organic layers were washed with brine, dried,
filtered, and evaporated to afford crude products under
reduced pressure. Purification on silica gel (hexane/ethyl
acetate = 8:1–4:1) afforded ketones 4. For 4A 1H NMR
(500 MHz, CDCl3) d 7.76 (d, J = 8.0 Hz, 2H), 7.40 (d,
J = 8.0 Hz, 2H), 7.33–7.28 (m, 3H), 7.15 (d, J = 8.0 Hz,
2H), 4.09 (dd, J = 9.0, 10.0 Hz, 1H), 3.83 (d, J = 17.5 Hz,
1H), 3.73 (t, J = 8.5 Hz, 1H), 3.54 (d, J = 17.5 Hz, 1H),
3.49 (dd, J = 9.0, 10.0 Hz, 1H), 2.47 (s, 3H); 13C NMR
(125 MHz, CDCl3) d 207.28, 144.62, 134.16, 131.47,
130.08 (2·), 128.99 (2·), 127.96 (3·), 127.88 (2·), 53.84,
53.57, 51.79, 21.59; HRMS (ESI) m/z calcd for
C17H18NO3S (M++1) 316.1007, found 316.1009. For 4B
1H NMR (500 MHz, CDCl3) d 7.76 (d, J = 8.0 Hz, 2H),
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