8898 J . Org. Chem., Vol. 65, No. 26, 2000
Watanabe et al.
123.0, 128.3, 131.5; MS m/z 178 (M+); HRMS calcd for C10H10
-
Rea ction of Alk en ylselen on iu m Sa lt 2c w ith Sod iu m
Isop r op oxid e in MeCN. To a stirred solution i-PrOH (10 mg,
0.17 mmol) in dry MeCN (5 mL) was added 60% NaH (7 mg,
0.17 mmol) at room temperature. After the mixture was stirred
at the same temperature for 30 min, alkenylselenonium salt
2c (94 mg, 0.15 mmol) was added to it at room temperature.
The mixture was stirred at the same temperature for 1 h,
poured into water, and extracted with ethyl acetate. The
extracts were washed with brine and dried over MgSO4. After
the solvent was evaporated under reduced pressure, the
residue was separated by preparative TLC (hexane/AcOEt,
100:1) to give 4 (28 mg, 80%) and 10h (36 mg, 79%).
OS (M+) 178.0452, found 178.0442.
Rea ction of Alk yn ylselen on iu m Sa lt
1 w ith 1,2-
Eth a n ed ith iol Mon osod iu m Sa lt. The reaction was con-
ducted using 1,2-ethanedithiol and equimolar NaH. The crude
products were separated by preparative TLC (hexane/AcOEt,
5:1) to give 7 (14 mg, 48%) as colorless oil and 4 (39 mg, 83%).
1
7: IR cm-1 (neat) 2167; H NMR(400 MHz, CDCl3) δ 3,20 (s,
4 H), 7.27-7.34 (m, 6 H), 7.38-7.43 (m, 4 H); 13C NMR (100
MHz, CDCl3) δ 35.1, 77.8, 94.2, 123.0, 128.3, 131.6; MS m/z
294 (M+); HRMS calcd for C18H14S2 (M+) 294.0537, found
294.0524.
Rea ction of Alk en ylselen on iu m Sa lt 2a w ith Lith iu m
P h en yleth yn ylid e. To a stirred solution of 98% phenylethyne
(25 mg, 0.24 mmol) in dry THF (2 mL) was added 1.4 mol/L
n-BuLi (0.17 mL, 0.24 mmol) at -78 °C. After being stirred at
the same temperature for 30 min, the mixture was added to a
THF solution (7 mL) of alkenylselenonium salt 2a (119 mg,
0.20 mmol) at -78 °C. The whole mixture was stirred at the
same temperature for 5 h, after which ether was added to it.
The resulting mixture was washed with brine and dried over
MgSO4. After the solvent was evaporated under reduced
pressure, the residue was separated by preparative TLC
(hexane/AcOEt, 5:1) to give 10a (46 mg, 74%) as white powder
and 4 (36 mg, 77%). 10a : mp 107-108 °C; IR cm-1 (neat) 2191;
1H NMR(400 MHz, CDCl3) δ 6.32 (s, 1 H), 7.04 (t, J ) 8 Hz, 1
H), 7.11 (t, J ) 8 Hz, 2 H), 7.18-7.24 (m, 5 H), 7.26-7.30 (m,
3 H), 7.44 (dd, J ) 8 Hz, 3 Hz, 2 H), 7.52 (dd, J ) 8 Hz, 3 Hz,
2 H); 13C NMR (100 MHz, CDCl3) δ 87.6, 98.3, 112.2, 123.3,
126.3, 127.9, 128.2, 128.3, 128.6, 130.4, 131.6, 134.4, 138.3,
147.1; MS m/z 312 (M+). Anal. Calcd for C22H16S: C, 84.57; H,
5.16. Found: C, 84.56; H, 5.35.
Rea ction of Alk en ylselen on iu m Sa lt 2a w ith Sod iu m
4-Meth ylben zen eth iola te. To a stirred solution of 4-meth-
ylbenzenethiol (21 mg, 0.17 mmol) in dry i-PrOH (3 mL) was
added 60% NaH (7 mg, 0.17 mmol) at room temperature. After
the mixture was stirred at the same temperature for 30 min,
alkenylselenonium salt 2a (89 mg, 0.15 mmol) was added to
it at room temperature. The resulting mixture was stirred at
the same temperature for 1.5 h, poured into water, and
extracted with ethyl acetate. The extracts were washed with
brine and dried over MgSO4. After the solvent was evaporated
under reduced pressure, the residue was separated by pre-
parative TLC (hexane) to give 10d (38 mg, 76%) as colorless
oil and 4 (31 mg, 89%). 10d : IR cm-1 (neat) 1581, 1540, 1490,
1440; 1H NMR(270 MHz, CDCl3) δ 2.34 (s, 3 H), 7.06 (t, J ) 8
Hz, 1 H), 7.15-7.26 (m, 10 H), 7.39 (d, J ) 8 Hz, 2 H), 7.53 (d,
J ) 8 Hz, 2 H); 13C NMR (67.5 MHz, CDCl3) δ 21.1, 125.8,
126.7, 127.5, 128.2, 128.3, 128.5, 128.8, 130.0, 131.0, 131.6,
134.8, 137.6, 137.8, 138.8; MS m/z 334 (M+). Anal. Calcd for
Rea ction of Alk en ylselen on iu m Sa lt 2a w ith Lith iu m
(-)-Men th oxid e. To a stirred solution of (-)-menthol (94 mg,
0.22 mmol) in dry THF (2 mL) was added 0.85 mol/L PhLi
(0.26 mL, 0.22 mmol) at room temperature. After the mixture
was stirred at the same temperature for 160 min, it was added
to the THF solution (3 mL) of alkenylselenonium salt 2a (119
mg, 0.20 mmol) at room temperature. The resulting mixture
was stirred at the same temperature for 1.5 h, poured into
water, and extracted with ethyl acetate. The extracts were
washed with brine and dried over MgSO4. After the solvent
was evaporated under reduced pressure, the residue was
purified by column chromatography (chloroform) to give 10k
(41 mg, 56%) as white powder and 4 (34 mg, 73%). 10k : mp
53-57 °C; [R]22 -2.0 (c 0.80, CHCl3); IR cm-1 (neat) 1616,
D
1196; 1H NMR(400 MHz, CDCl3) δ 0.73 (d, J ) 7 Hz, 3 H),
0.81-0.5 (m, 4 H), 0.85-1.04 (m, 4 H), 1.14 (q, J ) 12 Hz, 1
H), 1.35-1.45 (m, 2 H), 1.64-1.69 (m, 2 H), 1.93-2.06 (m, 2
H), 3.67 (dt, J ) 11 Hz, 4 Hz, 1 H), 7.02 (t, J ) 7 Hz, 1 H),
7.10-7.18 (m, 4 H), 7.20-7.27 (m, 4 H), 7.50 (d, J ) 7 Hz, 2
H); 13C NMR (100 MHz, CDCl3) δ 16.2, 20.6, 22.0, 23.4, 25.5,
31.6, 34.0, 41.6, 47.2, 84.0, 108.2, 117.0, 124.7, 126.4, 127.0,
128.2, 128.4, 137.1, 138.5, 151.8; FABMS m/z 367 (M+ + H);
HRFAB MS calcd for C24H31OS (M+ + H) 367.2096, found
367.2087.
Rea ction of Alk en ylselen on iu m Sa lt 2g w ith Sod iu m
Hyd r id e. To a stirred solution of alkenylselenonium salt 2g
(91 mg, 0.15 mmol) in dry MeCN (5 mL) was added 60% NaH
(6 mg, 0.15 mmol) at 0 °C. The mixture was stirred at the same
temperature for 24 h, poured into water, and extracted with
ethyl acetate. The extracts were washed with brine and dried
over MgSO4. After the solvent was evaporated under reduced
pressure, the residue was purified by preparative TLC (hexane/
AcOEt, 100:1) to give 5a (8 mg, 17%) as colorless oil and 4 (26
mg, 88%). 5a : IR cm-1 (neat) 1469, 1215; 1H NMR(400 MHz,
CDCl3) δ 5.82 (s, 1 H), 6.94-7.02 (m, 3 H), 7.08-7.14 (m, 1
H), 7.30-7.40 (m, 3 H), 7.59 (d, J ) 7 Hz, 2 H); 13C NMR (100
MHz, CDCl3) δ 94.3, 117.6, 119.6, 124.2, 124.9, 126.6, 127.9,
128.5, 128.6, 133.3, 150.0, 152.0; MS m/z 226 (M+); HRMS
calcd for C14H10OS (M+) 226.0452, found 226.0456.
C
21H18S2: C, 75.40; H, 5.42. Found: C, 75.27; H, 5.61.
Rea ction of Alk en ylselen on iu m Sa lt 2c w ith Sod iu m
Isop r op oxid e in i-P r OH. The reaction was conducted using
sodium isopropoxide prepared from dry i-PrOH and NaH. The
products were separated by preparative TLC (hexane/AcOEt,
100:1) to give 10h (39 mg, 86%) as colorless oil and 4 (32 mg,
92%). 10h : IR cm-1 (neat) 1614, 1202; 1H NMR(400 MHz,
CDCl3) δ 1,29 (d, J ) 6 Hz, 6 H), 4.16-4.26 (m, 1 H), 7.06 (s,
1 H), 7.10 (d, J ) 9 Hz, 2 H), 7.14 (d, J ) 9 Hz, 2 H), 7.17 (t,
J ) 7 Hz, 1 H), 7.25 (t, J ) 7 Hz, 2 H), 7.47 (d, J ) 7 Hz, 2 H);
13C NMR (100 MHz, CDCl3) δ 22.5, 76.6, 108.8, 126.5, 126.7,
128.4, 128.57, 128.63, 130.7, 135.4, 137.9, 151.1; MS m/z 304
(M+); HRMS calcd for C17H17ClOS (M+) 304.0689, found
304.0682.
Ack n ow led gm en t. This work was supported in part
by a Grant-in-Aid for Scientific Research (no. 11771388)
from the Ministry of Education, Science, Sports and
Culture, J apan.
Su p p or tin g In for m a tion Ava ila ble: Spectroscopic data
and experimental details of 2b-i, 2k , 5c, 5d , 10b, 10c, 10e-
g, 10i, and 10j. This material is available free of charge via
the Internet at http://pubs.acs.org.
J O000640K