5640
F. Ye et al. / Tetrahedron 59 (2003) 5635–5643
129.0, 130.5, 132.4, 132.8, 133.1, 133.4, 134.5, 135.2,
137.5, 138.9, 143.5, 159.9, 191.9. HRMS (EI): calcd for
378.0926, found: 378.0892.
subjected to column chromatography to furnish 1p (70 mg,
91%).
4.2.1. 1-(4-Methoxyphenylethynyl)-2-phenylethynyl-
1
benzene (1a). Liquid. H NMR (500 MHz, CDCl3) d 3.80
4.1.8. 3-[2-(4-Methoxyphenyl)-2-(phenylsulfonyl)vinyl]-
benzaldehyde (4h). 93:7. Geometry E or Z was not
determined. H NMR (500 MHz, CDCl3) d 3.82 (s, 3H),
6.87–8.05 (m, 14H), 9.80, 10.04 (s, 1H); 13C NMR
(75 MHz, acetone-d6) d 55.7, 114.4, 115.3, 123.5, 128.7,
129.2, 129.3, 129.6, 129.8, 130.0, 130.1, 130.9, 131.0,
132.2, 132.4, 132.8, 134.0, 134.3, 135.1, 135.2 135.9, 136.2,
136.4, 137.0, 137.7, 137.8, 140.0, 140.5, 144.4, 161.5,
192.2, 192.7. HRMS (EI): calcd for 378.0926, found:
378.0901.
(s, 3H), 6.86 (d, J¼8.9 Hz, 2H), 7.26–7.36 (m, 5H), 7.48–
7.58 (m, 6H); 13C NMR (125 MHz, CDCl3) d 55.3, 87.1,
88.5, 93.4, 93.7, 114.0, 115.4, 123.4, 125.6, 126.2, 127.6,
128.0, 128.3, 131.5, 131.6, 131.7, 133.1, 159.8. HRMS (EI)
calcd for 308.1201; found: 308.1204.
1
4.2.2. 1-(4-Fluorophenylethynyl)-2-(4-methoxyphenyl-
ethynyl)benzene (1b). Liquid. 1H NMR (500 MHz,
CDCl3) d 3.81 (s, 3H), 6.86 (d, J¼8.9 Hz, 2H), 7.03 (d,
J¼8.7 Hz, 2H), 7.23–7.30 (m, 2H), 7.47–7.55 (m, 6H); 13C
NMR (125 MHz, CDCl3) d 55.3, 87.0, 88.1, 88.2, 92.3,
93.7, 114.1, 115.4, 115.6, 115.7, 119.4, 119.5, 125.4, 126.2,
127.6, 128.0, 131.5, 131.6, 133.1, 133.4, 133.5, 159.8,
161.6, 163.6. HRMS (EI) calcd 326.1107; found: 326.1107.
4.1.9. 4-[2-(4-Methoxyphenyl)-2-(phenylsulfonyl)vinyl]-
benzaldehyde (4i). 88:12. Geometry E or Z was not
determined. 1H NMR (500 MHz, acetone-d6) d 3.81 (s, 3H),
6.80–7.97 (m, 14H), 9.92, 10.04 (s, 1H); 13C NMR
(125 MHz, CDCl3) d 55.1, 55.2, 113.6, 114.4, 122.3,
125.9, 128.0, 128.5, 128.6, 128.7, 129.0, 129.5, 129.6,
130.8, 131.1, 131.8, 133.1, 133.3, 135.7, 136.4, 138.2,
138.8, 139.2, 139.8, 140.3, 144.2, 145.3, 160.2, 160.4,
191.3, 191.7. HRMS (EI): calcd for 378.0926, found:
378.0955.
4.2.3. 1-(4-Bromophenylethynyl)-2-(4-methoxyphenyl-
ethynyl)benzene (1c). Mp 117–1198C: 1H NMR
(500 MHz, CDCl3) d 3.83 (s, 3H), 6.87 (d, J¼8.9 Hz, 2H),
7.26–7.32 (m, 2H), 7.39–7.42 (m, 2H), 7.44–7.49 (m, 4H),
7.52–7.54 (m, 2H); 13C NMR (125 MHz, CDCl3) d 55.3,
87.0, 89.6, 92.3, 93.9, 114.1, 115.3,122.4, 122.6, 126.2,
126.3, 127.7, 128.2, 131.5, 131.6, 131.7, 133.0, 133.1,
159.9. Elemental analysis calcd (%) for C23H15BrO: C
71.33, H 3.90; found: C 71.61, H 3.51.
4.1.10. 4-[2-Phenyl-2-(phenylsulfonyl)vinyl]-2,5-
dimethylbenzaldehyde (4j). 67:33. Geometry E or Z was
not determined. 1H NMR (500 MHz, CDCl3) d 2.25, 2.22 (s,
3H), 2.45, 2.68 (s, 3H), 6.62–8.14 (m, 13H), 10.13, 10.27 (s,
1H); 13C NMR (75 MHz, acetone-d6) d 128.0, 128.3, 128.4,
128.5, 128.8, 129.1, 129.2, 129.8, 130.4, 130.6, 132.4,
132.5, 133.1, 133.2, 133.4, 133.5, 133.7, 133.9, 134.8,
135.1, 135.9, 137.1, 137.2, 137.3, 138.4, 139.2, 139.6,
139.9, 144.7, 146.0, 192.1, 192.3. HRMS (EI): calcd for
376.1133, found: 376.1119.
4.2.4. 1-(4-Methoxyphenylethynyl)-3-phenylethynyl-
benzene (1d). Mp 118–1208C: 1H NMR (300 MHz,
CDCl3) d 3.83 (s, 3H), 6.88 (d, J¼8.8 Hz, 2H), 7.28–7.36
(m, 4H), 7.45–7.55 (m, 6H), 7.69 (s, 1H); 13C NMR
(125 MHz, CDCl3) d 55.3, 87.3, 88.6, 89.9, 90.0, 114.0,
115.1, 123.0, 123.6, 124.0, 128.36, 128.40, 128.41, 130.9,
131.1, 131.6, 133.1, 134.4, 159.7. Elemental analysis calcd
(%) for C23H16O: C 89.58, H 5.23; found: C 89.18, H 5.07.
4.1.11. 4-[2-(4-Methoxyphenyl)-2-(phenylsulfonyl)-
vinyl]-2,5-dimethylbenzaldehyde (4k). 81:19. Geometry
1
E or Z was not determined. H NMR (500 MHz, CDCl3) d
4.2.5. 1-(3-Fluorophenylethynyl)-3-(4-methoxyphenyl-
1
ethynyl)benzene (1e). Mp 86–888C: H NMR (300 MHz,
2.30, 2.20 (s, 3H), 2.42, 2.67 (s, 3H), 3.77, 3.84 (s, 3H),
6.69–8.09 (m, 12H), 10.14, 10.26 (s, 1H); 13C NMR
(75 MHz, acetone-d6) d 18.8, 18.9, 19.3, 19.4, 55.2, 55.3,
113.7, 114.0, 122.3, 126.9, 128.0, 128.5, 128.8, 131.3,
132.0, 132.4, 132.5, 132.6, 133.1, 133.2, 133.3, 133.6,
133.7, 133.9, 135.0, 135.8, 137.2, 137.4, 137.6, 138.6,
139.1, 139.5, 140.1, 144.5, 145.5, 160.2, 160.3, 192.2,
192.4. HRMS (EI): calcd for 406.1239, found: 406.1246.
CDCl3) d 3.83 (s, 3H), 6.89 (d, J¼8.8 Hz, 2H), 7.01–7.08
(m, 1H), 7.20–7.25 (m, 1H), 7.30–7.35 (m, 3H), 7.44–7.49
(m, 4H), 7.70 (s, 1H); 13C NMR (75 MHz, CDCl3) d 55.3,
87.2, 88.5, 88.6, 89.5, 90.2, 114.0, 115.1, 115.6, 115.9,
118.2, 118.5, 123.1, 124.1, 124.8, 125.0, 127.5, 127.6,
128.5, 129.9, 130.0, 131.0, 131.4, 133.1, 134.5, 159.8,
160.8, 164.0. Elemental analysis calcd (%) for C23H15FO: C
84.64, H 4.63; found: C 84.32, H 4.44.
4.2. General procedure for the preparation of
compounds 1
4.2.6. 1-(4-Fluorophenylethynyl)-3-(4-methoxyphenyl-
ethynyl)benzene (1f). Mp 105–1078C: 1H NMR
(300 MHz, CDCl3) d 3.83 (s, 3H), 6.88 (d, J¼8.6 Hz, 2H),
7.05 (t, J¼8.6 Hz, 2H), 7.31 (t, J¼7.8 Hz, 1H), 7.43–7.53
(m, 6H), 7.68 (s, 1H); 13C NMR (75 MHz, CDCl3) d 55.3,
87.2, 88.3, 88.4, 88.8, 90.1, 114.0, 115.1, 115.5, 115.8,
119.1,119.2, 123.4, 124.0, 128.4, 130.9, 131.2, 133.1, 133.5,
133.6, 134.4, 159.8, 160.9, 164.2. Elemental analysis calcd
(%) for C23H15FO: C 84.64, H 4.63; found: C 84.42, H 4.52.
To a THF solution (5 mL) of p-methoxybenzyl phenyl
sulfone (2i) (79 mg, 0.30 mmol) was added BuLi (1.60 M,
0.21 mL, 0.35 mmol), and the mixture was stirred for 0.5 h.
A THF solution (3 mL) of 4c (87 mg, 0.25 mmol) was
added, and the mixture was stirred for 1 h. At 2788C,
ClP(O)(OEt)2 (0.05 mL, 0.30 mmol) was added, and the
mixture was stirred at room temperature for 2 h. t-BuOK
(421 mg, 3.75 mmol) was added at 2788C, and the mixture
was stirred at 2788C for 1 h and at room temperature for
2 h. After usual workup with ethyl acetate and NH4Claq,
drying over MgSO4 and evaporation, the residue was
4.2.7. 1-(3-Bromophenylethynyl)-3-(4-methoxyphenyl-
ethynyl)benzene (1g). Mp 121–1238C: 1H NMR
(500 MHz, CDCl3) d 3.83 (s, 3H), 6.89 (d, J¼8.9 Hz, 2H),