T. Satoh et al. / Tetrahedron 57 +2001) 9689±9696
9695
2-one +6g)Colorless oil >about 4.5:5.5 diastereomeric
mixture); IR >neat) 1682>CO), 1584, 1567, 1088, 1056
80 >100). Calcd for C8H12O2: M, 140.0836. Found: m/z
140.0846.
1
>SO), 750, 696 cm21; H NMR d 4.88 >0.55H, s), 4.91
>0.45H, s), 6.68 >0.55H, s), 6.70 >0.45H, s), 7.13±7.67
>15H, m). MS m/z >%) 380 >M1, trace), 254 >75), 207
>100), 191 >68). Calcd for C22H17ClO2S: M, 380.0638.
Found: m/z 380.0633.
2.6.5. +E)-4-+4-Methoxyphenyl)-3-butenoic acid +9f).
Colorless crystals; mp 101±1038C >hexane), >lit.18 mp
102±1048C). IR >KBr) 2962, 2935, 1723, 1599, 1513,
1
1251, 1174, 1032, 831, 756 cm21; H NMR d 3.27 >2H,
d, J7.0 Hz), 3.81 >3H, s), 6.14 >1H, dt, J15.9, 7.0 Hz),
6.46 >1H, d, J15.9 Hz), 6.85 >2H, d, J8.9 Hz), 7.31 >2H,
d, J8.6 Hz). MS m/z >%) 192>M 1, 68), 147 >100), 91>18).
Calcd for C11H12O3: M, 192.0784. Found: m/z 192.0781.
2.6. Synthesis of b,g-alkenyl carboxylic acids 9 from
g,d-alkenyl a-chloro-b-keto sulfoxides 6
A synthesis of >E)-4-phenyl-3-butenoic acid >9a) is
described. To a suspension of KH >32mg; 0.8 mmol) in
3 mL of dry THF was added dropwise with stirring a
solution of 6a >122 mg; 0.4 mmol) in 1 mL of THF at
08C. The suspension was stirred at 08C for 15 min, then
the solution was cooled to 2788C. t-BuLi >1.6 mmol) was
added the reaction mixture was stirred at 2788C for 10 min,
and at 08C for 10 min. To the reaction mixture were added
5 mL of 5% NaOH and a mixture of ether±benzene
>20 mL). The whole was stirred vigorously with a magnetic
stirrer. The solution was transferred into a separatory funnel
and the aqueous layer was separated. The organic layer was
extracted once with 5% NaOH >5 mL). The combined
aqueous layer was acidi®ed with 10% HCl and extracted
with ether±benzene. The organic layer was washed once
with saturated aqueous NH4Cl and dried over MgSO4.
Evaporation of the solvent gave 9a14,15 >36 mg; 60%) as a
light yellow crystals. Mp 84±868C >AcOEt±hexane); IR
2.6.6. 4,4-Diphenyl-3-butenoic acid +9g). Colorless crys-
tals; mp 115±1168C >hexane), >lit.19 114.5±115.58C). IR
>KBr) 3058, 3025, 1706, 1584, 1567, 1445, 760,
1
698 cm21; H NMR d 3.21 >2H, d, J7.3 Hz), 6.24 >1H,
t, J7.3 Hz), 7.12±7.48 >10H, m). MS m/z >%) 238 >M1,
91), 193 >100), 178 >38), 115 >82). Calcd for C16H14O2: M,
238.0986. Found: m/z 238.0992.
2.6.7. 1-Chloro-4-phenyl-1-+phenylsul®nyl)but-3-yn-2-ol
+16a). Yellow oil; IR >neat) 3262 >OH), 2230, 1489, 1442,
1070, 1028 >SO), 690 cm21; 1H NMR d 3.99 >1H, s, OH),
4.63±4.71 >1H, m), 5.03±5.34 >1H, m), 7.28±7.86 >10H,
m). MS m/z >%) 304 >M1, trace), 290 >18), 226 >24), 126
>100), 125 >65), 115 >90).
2.6.8. 1-Chloro-1-+phenylsul®nyl)non-3-yn-2-ol +16b).
Yellow oil; IR >neat) 3332 >OH), 2232, 1444, 1086, 1041
1
>SO), 749, 689 cm21; H NMR d 0.89 >3H, CH3), 1.24±
>KBr) 3060, 2957, 1704, 1650, 1224, 976, 745, 693 cm21
;
1.58 >6H, CH2), 2.14 >1H, OH), 2.19±2.29 >2H, m), 4.38±
4.69 >2H, m), 7.45±7.87 >5H, m). MS m/z >%) 299 >M1,
trace), 152 >9), 126 >100), 78 >32). Calcd for C15H20ClO2S:
M, 299.0872. Found: m/z 299.0860.
1H NMR d 3.30 >2H, d, J7.1 Hz), 6.28 >1H, dt, J15.7,
7.1 Hz), 6.52>1H, d, J15.7 Hz), 7.22±7.38 >5H, m). MS
m/z >%) 162>M 1, 51), 117 >100), 115 >42), 91 >25). Calcd
for C10H10O2: M, 162.0680. Found: m/z 162.0674.
2.6.9. 1-Chloro-4-phenyl-1-+phenylsul®nyl)but-3-yn-2-
one +17a). Yellow oil >about 2:3 diastereomeric mixture;
IR >neat) 2205, 1672 >CO), 1444, 1286, 1089, 1058 >SO),
2.6.1. +E)-3-Decenoic acid +9b).4 Yellow oil; IR >neat)
1
2928, 1716, 1143, 968, 690, 668 cm21; H NMR d 0,88
1
>3H, t, J7.0 Hz), 1.21±1.40 >8H, m), 2.01±2.05 >2H,
760, 688 cm21; H NMR d 5.20 >0.6H, s), 5.42 >0.4H, s),
m), 3.02>2H, d, J5.8 Hz), 5.48±5.63 >2H, m).
7.39±7.75 >10H, m). MS m/z >%) 302>M 1, 1), 210 >9), 149
>17), 129 >100), 125 >48). Calcd for C16H11ClO2S: M,
302.0169. Found: m/z 302.0158.
2.6.2. +Z)-3,4-Diphenyl-3-butenoic acid +9c). Colorless
crystals; mp 131.5±1338C >hexane), >lit.16 mp 134.5±
1368C). IR >KBr) 3054, 3022, 2920, 1705, 1303, 793, 760,
702, 659 cm21; 1H NMR d 3.52>2H, s), 6.60 >1H, s), 6.95±
7.30 >10H, m). MS m/z >%) 238 >M1, 100), 178 >80), 115
>80). Calcd for C16H14O2: M, 238.0993. Found: m/z
238.1004.
2.6.10. 1-Chloro-1-+phenylsul®nyl)non-3-yn-2-one +17b).
Yellow oil >about 1:1 diastereomeric mixture); IR >neat)
2208, 1681 >CO), 1444, 1090, 1059 >SO), 746, 689 cm21
;
1H NMR d 0.92>3H, t, J7.2Hz), 1.31±1.39 >4H, m),
1.56±1.59 >2H, m), 2.38±2.41 >2H, m), 5.02 >0.5H, s),
5.25 >0.5H, s), 7.53±7.72 >5H, m). MS m/z >%) 296 >M1,
trace), 125 >100), 123 >29). Calcd for C15H17ClO2S: M,
296.0637. Found: m/z 296.0648.
2.6.3. +E)-3-Methyl-4-phenyl-3-butenoic acid +9d). Color-
less crystals; mp 111±1128C >AcOEt±hexane); IR >KBr)
2961, 2867, 1730, 1694, 1667, 1445, 1218, 747, 702
1
cm21; H NMR d 1.97 >3H, s), 3.23 >2H, s), 6.43 >1H, s),
2.6.11. A mixture of acetylene 18a and 19a. Only selected
data can be described. Colorless oil; IR >neat) 2204 >acetyl-
7.20±7.35 >5H, m). MS m/z >%) 176 >M1, 94), 131 >100),
116 >52), 91 >61). Calcd for C11H12O2: M, 176.0830. Found:
m/z 176.0836. Anal. Calcd for C11H12O2: C, 75.03; H, 6.87.
Found: C, 74.66; H, 6.69.
1
ene), 1978 >allene), 1707 >CO), 1173, 758, 687 cm21; H
NMR d 3.58 >s, propargyl-H), 6.03 >d, J6.1 Hz), 6.69 >d,
J6.1 Hz). MS m/z >%) 160 >M1, 50), 122 >61), 115 >96),
105 >100). Calcd for C10H8O2: M, 160.0524. Found: m/z
160.0538.
2.6.4. +1-Cyclohexenyl)acetic acid +9e). Light yellow low
melting solid, >lit.17 mp 34±358C). IR >neat) 2929, 2859,
2838, 1708, 1437, 1408, 1294, 1224, 959, 921, 651 cm21
;
2.6.12. A mixture of acetylene 18b and 19b. Only selected
data can be described. Colorless oil; IR >neat) 2240 >acetyl-
ene), 1958 >allene; lit.20 1955), 1722, 1714 >CO), 1284,
1H NMR d 1.54±1.68 >4H, m), 2.01±2.06 >4H, m), 2.99
>2H, s), 5.61 >1H, s). MS m/z >%) 140 >M1, 21), 81 >39),