9622
M.-Y. Chang et al. / Tetrahedron 69 (2013) 9616e9624
(400 MHz, CDCl3):
d
8.40 (d, J¼8.4 Hz, 1H), 7.70 (dd, J¼2.0, 8.4 Hz,
143.26, 142.44, 138.17, 138.11, 135.85, 132.47, 132.34, 131.16, 130.56,
129.18, 128.84, 128.73 (2ꢁ), 128.43 (2ꢁ), 128.00, 127.95, 127.68 (2ꢁ),
127.58, 126.64, 126.26, 126.06, 125.40, 114.45 (2ꢁ), 55.32, 21.32.
1H), 7.54 (d, J¼9.2 Hz, 2H), 7.36 (d, J¼2.0 Hz, 1H), 7.26 (d, J¼8.4 Hz,
2H), 7.07 (d, J¼8.0 Hz, 2H), 6.97 (d, J¼8.8 Hz, 2H), 6.68 (d, J¼8.0 Hz,
1H), 6.52 (dd, J¼1.6, 8.0 Hz, 1H), 6.42 (d, J¼1.6 Hz, 1H), 5.97 (s, 2H),
3.84 (s, 3H), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
160.13,
4.2.34. Compound (6l). Yield¼43% (88 mg); colorless gum; HRMS
(ESI, Mþþ1) calcd for C23H18FO2S2 409.0732, found 409.0736; 1H
147.10, 146.63, 145.06, 143.38, 141.96, 138.29, 138.18, 131.92, 131.14,
130.65,129.18,128.85 (2ꢁ),128.40 (2ꢁ),127.77 (2ꢁ), 125.28,123.78,
114.42 (2ꢁ), 110.54, 107.16, 100.98, 55.33, 21.44.
NMR (400 MHz, CDCl3):
d
8.50 (d, J¼8.0 Hz, 1H), 7.75 (dd, J¼2.0,
8.4 Hz, 1H), 7.53 (d, J¼2.0 Hz, 1H), 7.45e7.36 (m, 2H), 7.31e7.25 (m,
4H), 7.21 (dd, J¼1.2, 3.6 Hz, 1H), 7.12e7.08 (m, 1H), 7.06 (d, J¼8.0 Hz,
2H), 7.02 (dd, J¼3.6, 5.2 Hz, 1H), 2.34 (s, 3H); 13C NMR (100 MHz,
4.2.29. Compound (6g). Yield¼26% (62 mg); colorless gum; HRMS
(ESI, Mþþ1) calcd for C30H23O4S 479.1317, found 479.1321; 1H NMR
CDCl3):
d
163.15 (d, J¼245.6 Hz), 144.11, 143.56, 140.85 (d, J¼7.6 Hz),
(400 MHz, CDCl3):
d
8.49 (d, J¼8.0 Hz, 1H), 8.07 (d, J¼1.2 Hz, 1H),
140.17, 137.41, 137.36, 135.01, 132.52, 130.96, 130.60 (d, J¼8.3 Hz),
129.79, 129.02 (2ꢁ), 127.74 (2ꢁ), 127.11, 126.67, 126.58, 123.01 (d,
J¼3.0 Hz), 115.51 (d, J¼21.2 Hz), 114.28 (d, J¼21.8 Hz), 21.53.
7.93e7.85 (m, 4H), 7.72 (dd, J¼2.0, 8.4 Hz, 1H), 7.55e7.51 (m, 3H),
7.30 (d, J¼8.0 Hz, 2H), 7.09 (d, J¼8.0 Hz, 2H), 6.71 (d, J¼8.4 Hz, 1H),
6.58 (dd, J¼1.6, 8.4 Hz, 1H), 6.48 (d, J¼1.6 Hz, 1H), 5.99 (s, 2H), 2.37
(s, 3H); 13C NMR (100 MHz, CDCl3):
d
147.17, 146.68, 145.38, 143.47,
4.2.35. Compound (6m). Yield¼38% (77 mg); mp¼138e139 ꢀC
(recrystallized from hexanes and EtOAc); HRMS (ESI, Mþþ1) calcd
for C24H21O2S2 405.0983, found 405.0986; 1H NMR (400 MHz,
142.08, 138.95, 138.18, 136.04, 133.43, 133.08, 131.47, 129.24, 128.88
(2ꢁ), 128.77, 128.30, 127.80 (2ꢁ), 127.73, 127.63, 127.61 (2ꢁ), 126.55,
126.13, 124.92, 123.83, 110.56, 107.21, 101.01, 21.45.
CDCl3):
d
8.47 (d, J¼8.4 Hz, 1H), 7.75 (dd, J¼1.6, 8.0 Hz, 1H), 7.55 (d,
J¼1.6 Hz, 1H), 7.50 (d, J¼8.0 Hz, 2H), 7.29e7.25 (m, 5H), 7.21 (dd,
4.2.30. Compound (6h). Yield¼24% (62 mg); colorless gum; HRMS
(ESI, Mþþ1) calcd for C29H27O7S 519.1478, found 519.1482; 1H NMR
J¼1.6, 8.0 Hz, 1H), 7.06 (d, J¼8.4 Hz, 2H), 7.02 (dd, J¼3.6, 5.2 Hz, 1H),
2.40 (s, 3H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3):
d 145.42,
(400 MHz, CDCl3):
d
8.41 (d, J¼8.4 Hz, 1H), 7.71 (dd, J¼2.0, 8.4 Hz,
143.39, 139.17, 138.73, 137.74, 137.64, 135.69, 134.75, 132.26, 130.78,
129.75 (2ꢁ), 129.68, 128.97 (2ꢁ), 127.70 (2ꢁ), 127.13 (2ꢁ), 126.91,
126.58, 126.30, 21.51, 21.14; Anal. Calcd for C24H20O2S2: C, 71.25; H,
4.98. Found: C, 71.52; H, 5.27.
1H), 7.34 (d, J¼2.0 Hz, 1H), 7.25 (d, J¼8.4 Hz, 2H), 7.07 (d, J¼8.0 Hz,
2H), 6.76 (s, 2H), 6.68 (d, J¼8.0 Hz, 1H), 6.52 (dd, J¼1.6, 8.0 Hz, 1H),
6.42 (d, J¼1.6 Hz, 1H), 5.97 (s, 2H), 3.90 (s, 6H), 3.88 (s, 3H), 2.35 (s,
3H); 13C NMR (100 MHz, CDCl3):
d
153.59 (2ꢁ), 147.16, 146.65,
145.56, 143.48, 141.95, 138.88, 138.10, 134.63, 131.68, 131.06, 129.87,
129.12, 128.86 (2ꢁ), 127.74 (2ꢁ), 125.86, 123.79, 110.51, 107.17,
104.59 (2ꢁ), 101.01, 60.88, 56.22 (2ꢁ), 21.43.
4.2.36. Compound (6n). Yield¼36% (76 mg); mp¼115e116 ꢀC
(recrystallized from hexanes and EtOAc); HRMS (ESI, Mþþ1) calcd
for C24H21O3S2 421.0932, found 421.0938; 1H NMR (400 MHz,
CDCl3):
d
8.45 (d, J¼8.4 Hz, 1H), 7.72 (dd, J¼2.0, 8.4 Hz, 1H), 7.54 (d,
4.2.31. Compound (6i). Yield¼23% (55 mg); mp¼202e204 ꢀC
(recrystallized from hexanes and EtOAc); HRMS (ESI, Mþþ1) calcd
for C28H27O5S 475.1579, found 475.1574; 1H NMR (400 MHz, CDCl3):
J¼8.8 Hz, 2H), 7.52 (d, J¼2.0 Hz, 1H), 7.29e7.27 (m, 1H), 7.26 (d,
J¼8.4 Hz, 2H), 7.58 (dd, J¼1.2, 3.6 Hz,1H), 7.05 (d, J¼8.0 Hz, 2H), 7.01
(dd, J¼3.6, 5.2 Hz, 1H), 6.97 (d, J¼8.4 Hz, 2H), 3.84 (s, 3H), 2.33 (s,
d
8.48 (d, J¼8.4 Hz, 1H), 7.78 (dd, J¼2.0, 8.4 Hz, 1H), 7.63e7.61 (m,
3H); 13C NMR (100 MHz, CDCl3):
d 160.20, 145.03, 143.36, 138.76,
2H), 7.48e7.38 (m, 4H), 7.20 (d, J¼8.4 Hz, 2H), 7.04 (d, J¼8.0 Hz, 2H),
137.77, 137.67, 134.74, 131.90, 130.90, 130.74, 129.69, 128.96 (2ꢁ),
128.43 (2ꢁ), 127.66 (2ꢁ), 126.87, 126.57, 125.91, 114.46 (2ꢁ), 55.34,
21.49; Anal. Calcd for C24H20O3S2: C, 68.54; H, 4.79. Found: C, 68.85;
H, 4.58.
6.20 (s, 2H), 3.91 (s, 3H), 3.69 (s, 6H), 2.33 (s, 3H); 13C NMR
(100 MHz, CDCl3):
d
152.04 (2ꢁ), 145.53, 143.18, 142.22, 138.85,
138.79, 138.03, 137.43, 133.18, 130.74, 129.00 (2ꢁ), 128.94, 128.81
(2ꢁ), 128.59, 127.88 (2ꢁ), 127.27 (2ꢁ), 125.91, 107.43 (2ꢁ), 60.90,
55.77 (2ꢁ), 21.35; Anal. Calcd for C28H26O5S: C, 70.86; H, 5.52.
Found: C, 70.96; H, 5.74. Single-crystal X-ray diagram: crystal of
compound 6i was grown by slow diffusion of EtOAc into a solution
of compound 6i in CH2Cl2 to yield colorless prisms. The compound
crystallizes in the triclinic crystal system, space group Pꢂ1,
4.2.37. Compound (6o). Yield¼40% (88 mg); mp¼169e170 ꢀC
(recrystallized from hexanes and EtOAc); HRMS (ESI, Mþþ1) calcd
for C27H21O2S2 441.0983, found 441.0982; 1H NMR (400 MHz,
CDCl3):
d
8.53 (d, J¼8.4 Hz, 1H), 8.07 (d, J¼2.0 Hz, 1H), 7.94e7.84 (m,
4H), 7.72 (dd, J¼1.6, 8.4 Hz, 1H), 7.69 (d, J¼2.0 Hz, 1H), 7.55e7.50 (m,
2H), 7.30 (dd, J¼0.8, 3.6 Hz, 1H), 7.28 (d, J¼8.4 Hz, 2H), 7.24 (dd,
J¼1.2, 5.2 Hz, 1H), 7.07 (d, J¼8.0 Hz, 2H), 7.04 (dd, J¼3.6, 5.2 Hz, 1H),
3
ꢀ
ꢀ
ꢀ
ꢀ
a¼9.918(3) A, b¼11.088(3) A, c¼11.599(3) A, V¼1166.7(5) A , Z¼2,
dcalcd¼1.351 g/cm3, F(000)¼500, 2
q
range 1.91e26.39ꢀ, R indices (all
data) R1¼0.0544, wR2¼0.1623.
2.35 (s, 3H); 13C NMR (100 MHz, CDCl3):
d 145.44, 143.48, 139.60,
137.70, 137.62, 135.90, 134.93, 133.47, 133.17, 132.75, 130.92, 129.80,
129.03 (2ꢁ), 128.87, 128.37, 127.76 (2ꢁ), 127.69, 127.01, 126.82,
126.73 (2ꢁ), 126.67 (2ꢁ), 124.95, 21.54; Anal. Calcd for C27H20O2S2:
C, 73.61; H, 4.58. Found: C, 73.75; H, 4.67.
4.2.32. Compound (6j). Yield¼20% (55 mg); colorless gum; HRMS
(ESI, Mþþ1) calcd for C34H31O5S 551.1892, found 551.1899; 1H NMR
(400 MHz, CDCl3):
d
8.47 (d, J¼8.4 Hz, 1H), 7.75 (dd, J¼2.0, 8.4 Hz,
1H), 7.65e7.62 (m, 2H), 7.52e7.41 (m, 6H), 7.19 (d, J¼8.4 Hz, 2H),
7.13 (d, J¼8.4 Hz, 2H), 6.99 (d, J¼8.0 Hz, 2H), 6.79 (s, 2H), 3.92 (s,
3H), 3.91 (s, 3H), 3.89 (s, 3H), 2.34 (s, 3H); 13C NMR (100 MHz,
4.2.38. Compound (6p). Yield¼30% (72 mg); colorless gum; HRMS
(ESI, Mþþ1) calcd for C25H25O5S2 481.1144, found 481.1145; 1H NMR
CDCl3):
d
153.67 (2ꢁ), 153.02, 145.67, 143.42, 142.20, 140.68, 140.60,
(400 MHz, CDCl3):
d
8.47 (d, J¼8.4 Hz, 1H), 7.73 (dd, J¼2.0, 8.4 Hz,
138.79, 138.72, 137.18, 134.69, 130.93, 130.51 (2ꢁ), 129.22, 128.90
(2ꢁ), 127.83 (2ꢁ), 127.57, 127.05 (2ꢁ), 125.96 (2ꢁ), 125.94 (2ꢁ),
105.85, 104.67 (2ꢁ), 60.95, 56.29 (2ꢁ), 21.53.
1H), 7.50 (d, J¼2.0 Hz, 1H), 7.29 (dd, J¼1.6, 5.2 Hz, 1H), 7.25 (d,
J¼8.0 Hz, 2H), 7.21 (dd, J¼0.8, 3.6 Hz,1H), 7.05 (d, J¼8.0 Hz, 2H), 7.03
(dd, J¼3.6, 5.2 Hz, 1H), 6.76 (s, 2H), 3.91 (s, 6H), 3.88 (s, 3H), 2.34 (s,
3H); 13C NMR (100 MHz, CDCl3):
d
153.65 (2ꢁ), 145.58, 143.46,
4.2.33. Compound (6k). Yield¼32% (74 mg); colorless gum; HRMS
(ESI, Mþþ1) calcd for C30H25O3S 465.1524, found 465.1532; 1H NMR
139.49, 137.57, 135.51, 134.75, 134.44, 132.35, 130.86, 129.65, 128.98
(2ꢁ), 127.67 (2ꢁ), 127.00, 126.63, 126.54, 104.66 (2ꢁ), 60.92, 56.27
(2ꢁ), 21.50.
(400 MHz, CDCl3):
d
8.47 (d, J¼8.1 Hz, 1H), 7.87 (d, J¼7.6 Hz, 1H),
7.78e7.73 (m, 2H), 7.61e7.47 (m, 6H), 7.30e7.27 (m, 2H), 7.06 (d,
J¼8.4 Hz, 2H), 6.97 (d, J¼8.8 Hz, 2H), 6.77 (d, J¼8.4 Hz, 2H), 3.84 (s,
4.2.39. Compound (6q). Yield¼33% (83 mg); colorless gum; HRMS
(ESI, Mþþ1) calcd for C30H28FO4S 503.1692, found 503.1695; 1H
3H), 2.23 (s, 3H); 13C NMR (100 MHz, CDCl3):
d 160.13, 145.09,