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M. A. Franks et al. / Bioorg. Med. Chem. 13 (2005) 2221–2233
J = 14.4 Hz, 1H), 6.57 (dd, J = 17.9 Hz, J = 10.9 Hz,
1H), 7.42 (m, 5H). 13C NMR (75.4 MHz, CDCl3 d):
24.10, 81.83, 123.49, 127.23, 129.41, 129.61, 129.87
137.37, 144.53.
mide (9.17 mL of a 1.0 M solution, 9.17 mmol). The
reaction was performed using the procedure described
above. The reaction yielded 34 (0.418 g, 1.86 mmol,
40%) as a brown oil. HRMS (m/z): [M+H]+ calcd for
C11H9F1S1O2, 224.0307; found, 224.0308. 1H NMR
(300 MHz, CDCl3 d): 5.43 (m, 2H), 5.51 (d,
J = 11.0 Hz, 1H), 5.78 (d, J = 14.4 Hz, 1H), 6.46 (dd,
J = 11.0 Hz, J = 17.8 Hz, 1H) 7.08, (m, 2H), 7.39 (m,
2H). 13C NMR (75.4 MHz, CDCl3 d): 81.62, 116.49
(d, J = 21.8 Hz), 123.65, 124.63, 126.78, 131.42 (d,
J = 8.5 Hz), 139.32, 145.16, 164.61. 19F NMR
(282.4 MHz, CDCl3 d): ꢀ111.09 (s).
5.16. 4-Allyl-3-phenyl-[1,2]-oxathiol-3-en-2-oxide (31)
3-Phenyl-2-butyn-1-ol (2.0 g, 15.13 mmol) in THF
(50 mL) was treated with allyl magnesium bromide
(25 mL of a 2.0 M solution, 50 mmol). The reaction
was performed and worked up as described above.
The reaction yielded 31 (2.38 g, 10.80 mmol, 71%) as a
yellow oil. Anal. Calcd for C12H12S1O2: C, 65.43; H,
1
5.49. Found: C, 65.93; H, 5.66. H NMR (300 MHz,
5.20. 3-[20-Fluorophenyl]-4-vinyl-[1,2]-oxathiol-3-en-2-
oxide (35)
CDCl3 d): 3.13 (t, J = 6.3 Hz, 2H), 5.17 (d,
J = 11.4 Hz, 1H), 5.18 (d, J = 15.4 Hz, 1H), 5.24 (d,
J = 15.4 Hz, 1H), 5.62 (d, J = 15.1 Hz, 1H), 5.83 (m,
1H), 7.64 (m, 5H). 13C NMR (75.4 MHz, CDCl3 d):
30.66, 76.37, 83.93, 118.81, 128.42, 128.83, 128.99
129.25, 132.79, 141.88.
3-[20-Fluorophenyl]-2-propyn-1-ol
9.99 mmol) in THF (50 mL) was treated with vinyl mag-
nesium bromide (32.0 mL of 1.0 M solution,
(20)
(1.50 g,
a
32.0 mmol). The reaction was performed using the pro-
cedure described above. The reaction yielded 35
(0.919 g, 4.10 mmol, 41%) as a brown oily product.
Anal. Calcd for C11H9F1S1O2: C, 58.92; H, 4.05. Found
C, 58.89; H, 4.21. H NMR (300 MHz, CDCl3 d): 5.49
(m, 2H), 5.58 (d, J = 11.0 Hz, 1H), 5.85 (d,
J = 14.4 Hz, 1H), 6.39 (ddd, J = 2 Hz, J = 11.0 Hz,
J = 17.8 Hz, 1H), 7.20 (m, 2H), 7.41 (m, 2H). 13C
NMR (75.4 MHz, CDCl3 d): 81.32, 116.34 (d,
5.17. 3-[40-Methoxyphenyl]-4-vinyl-[1,2]-oxathiol-3-en-2-
oxide (32)
3-(40-Methoxyphenyl)-2-propyn-1-ol (23) in THF
(25 mL) was treated with vinyl magnesium bromide
(20 mL of a 1.0 M solution, 20 mmol). The reaction
was performed using the procedure described above.
The reaction yielded 32 (1.15 g, 4.87 mmol, 79%) as a
yellow oil. HRMS (m/z): [M+H]+ calcd for
C12H12S1O3, 236.0507; found, 236.0507. 1H NMR
(300 MHz, CDCl3 d): 3.82 (s, 3H), 5.45 (m, 2H), 5.54
(d, J = 11.0 Hz, 1H), 5.82 (d, J = 13.5 Hz, 1H), 6.55
(dd, J = 11.1 Hz, J = 14.1 Hz, 1H), 6.94 (d, J = 8.7 Hz,
2H), 7.38 (d, J = 9.0 Hz, 2H). 13C NMR (75.4 MHz,
CDCl3 d): 55.60, 81.68, 114.73, 120.70, 122.83, 127.17,
130.82, 137.84, 145.75, 160.73.
J = 21.3 Hz),
123.63,
124.88,
126.15,
131.88
(d, J = 14.5 Hz), 134.91, 140.78, 141.63, 159.18, 160.17
(d, J = 249.9 Hz). 19F NMR (282.4 MHz, CDCl3 d):
ꢀ112.02 (s).
5.21. 3-[20-Thiophenyl]-4-vinyl-[1,2]-oxathiol-3-en-2-
oxide (36)
3-[20-Thiophenyl]-2-propyn-1-ol (22) (0.753 g, 5.29
mmol) in THF (25 mL) was treated with vinyl magne-
sium bromide (17 mL of a 1.0 M solution, 17 mmol).
The reaction was performed using the procedure de-
scribed above. The reaction yielded 36 (0.700 g,
3.27 mmol, 63%) as a brown solid mp 107–109 ꢁC. Anal.
Calcd for C9H8S2O2: C, 50.92; H, 3.80. Found C, 51.00;
5.18. 3-[20-Methoxyphenyl]-4-vinyl-[1,2]-oxathiol-3-en-2-
oxide (33)
3-[20-Methoxyphenyl]-2-propyn-1-ol
(22)
(0.100 g,
0.617 mmol) in THF (25 mL) was treated with vinyl
magnesium bromide (1.98 mL of a 1.0 M solution,
1.98 mmol). The reaction was performed using the pro-
cedure described above. The reaction yielded 33
(0.122 g, 0.516 mmol, 84%) as a clear oil. HRMS (m/
z): [M+H]+ calcd for C12H12S1O3, 236.0507; found,
236.0499. 1H NMR (300 MHz, CDCl3 d): 3.84 (s,
3H), 5.38 (d, J = 14.1 Hz, 1H), 5.41 (d, J = 17.9 Hz,
1H), 5.47 (d, J = 11.1 Hz, 1H), 5.82 (d, J = 14.0 Hz,
1H), 6.46 (dd, J = 11.0 Hz, J = 17.9 Hz, 1H), 6.94 (d,
J = 8.5 Hz, 1H), 7.00 (t, J = 7.5 Hz, 1H), 7.31
(dd, J = 7.5 Hz, J = 1.7 Hz, 1H), 7.39 (dt, J = 7.5 Hz,
J = 1.7 Hz, 1H). 13C NMR (75.4 MHz, CDCl3 d):
55.85, 80.69, 111.26, 117.41, 121.18, 122.15, 127.61,
131.50, 132.64, 139.40, 144.95, 157.59.
1
H, 3.93. H NMR (300 MHz, CDCl3 d): 5.56 (m, 2H),
5.62 (d, J = 11.0 Hz, 1H), 5.85 (d, J = 14.4 Hz, 1H),
6.88 (dd, J = 11.0 Hz, J = 17.6 Hz, 1H), 7.12 (dd,
J = 3.6 Hz, J = 5.1 Hz, 1H), 7.33 (d, J = 3.6 Hz, 1H),
7.47 (dd, J = 1.0 Hz, J = 5.1 Hz, 1H). 13C NMR
(75.4 MHz, CDCl3 d): 82.21, 123.70, 126.95, 128.15,
128.83, 129.32, 129.73, 137.24, 139.96.
5.22. 3-[40-Acetylphenyl]-4-vinyl-[1,2]-oxathiol-3-en-2-
oxide (37)
3-(40-Methyl-[1,3]-dioxolanylphenyl)-2-propyn-1-ol (20)
(0.819 g, 3.81 mmol) in THF (25 mL) was treated with
vinyl magnesium bromide (12.02 mL of a 1.0 M solu-
tion, 12.02 mmol). The reaction was performed and
worked up as described above. The reaction yielded 37
(0.260 g, 1.05 mmol, 28%) as a white solid mp 55–
56 ꢁC. HRMS (m/z): [M+H]+ calcd for C13H12S1O3,
5.19. 3-[40-Fluorophenyl]-4-vinyl-[1,2]-oxathiol-3-en-2-
oxide (34)
1
3-[40-Fluorophenyl]-2-propyn-1-ol (0.700 g, 4.66 mmol)
in THF (25 mL) was treated with vinyl magnesium bro-
248.0507; found, 248.0501. H NMR (300 MHz, CDCl3
d): 2.62 (s, 3H), 5.54 (d, J = 14.5 Hz, 1H), 5.54 (d,