Notes
J . Org. Chem., Vol. 66, No. 7, 2001 2505
mixture of E and Z isomers. Methyl thiosalicylate (1 equiv) was
added at 0 °C to the dry methylene chloride including the acid,
DCC (1 equiv), and DMAP (0.7 equiv), and the mixture was
stirred for 2 h at room temperature. The resulting precipitate
was removed from the reaction mixture after stirring for 3 h.
The crude product obtained from the filtrate by concentration
was purified by column chromatography to provide 1a as an oil
of a 1:1 mixture of E and Z isomers (85%). The detailed
procedure of the preparation of 1a and yields of other type 1
compounds and their characterization are given in the Support-
ing Information.
P r oced u r e for th e Electr or ed u ction of th e Th iolester s
1. The electroreduction was performed in DMF (10 or 20 mL)
using 0.5 or 1.0 mmol of a thiolester 1, 1 or 2 mmol of
tetraethylammonium perchlorate (TEAP) as a supporting elec-
trolyte, a graphite plate as a cathode, and an aluminum rod as
an anode in an undivided cell at room temperature under an
atmosphere of nitrogen. A constant current (6 mA) was passed
until the substrate was consumed (determined by TLC). The
electricity passed was 4 F/mol of the substrate 1. The solution
from the electrolysis was transferred to a brine solution (100
mL) and extracted with ether (40 mL × 3). The crude product
obtained after concentration under vacuum was purified by silica
gel column chromatography. Yields of products are given in
Table 1; their characterizations based on the analytical and
spectral data are given below.
examination. Solid, mp 72-74 °C; 1H NMR (CDCl3, 300 MHz) δ
3.36 (1H, q, J ) 7.9, CH2CH), 3.73 [1H, d, J ) 17.0, OCHHC-
(O)], 3.90 (1H, t, J ) 8.5, OCHHCH), 4.01 [1H, d, J ) 17.1,
OCHHC(O)], 4.42 (1H, t, J ) 9.2, OCHHCH), 4.48 [1H, d, J )
7.3, CHPh(Ph)], 7.12-7.34 (10H, m, ArH); 13C NMR (CDCl3, 75.5
MHz) δ 49.7, 50.7, 70.6, 71.3, 76.6, 77.0, 77.4, 126.7, 126.9, 128.0,
128.5, 128.5, 128.7, 141.5, 141.9, 214.5; IR (Nujol method) cm-1
1750.
2-Bip h en ylm eth ylcycloh exa n on e 2f. Solid, mp 98-99 °C;
1H NMR (CDCl3, 300 MHz) δ 1.34-1.46 (1H, m), 1.59-1.71 (1H,
m), 1.73-1.87 (3H, m), 1.99-2.04 (1H, m), 2.35-2.40 (2H, m),
3.31-3.40 (1H, m), 4.31 [1H, d, J ) 10.3, CHPh(Ph)], 7.10-7.29
(10H, m, ArH); 13C NMR (CDCl3, 75.5 MHz) δ 24.5, 29.1, 33.4,
42.5, 50.9, 54.8, 126.1, 126.3, 127.5, 128.3, 128.3, 128.5, 143.0,
143.8, 212.3; IR (Nujol method) cm-1 1700; HRMS calcd for
C
19H20O 264.1514, found 264.1485.
2-(1-P h en yleth yl)cyclop en ta n on e 2g. Yellow oil, obtained
as 6:5 mixture of diastereomers. 1H NMR (CDCl3, 300 MHz
mixture of diastereomers) major isomer δ 1.41 (3H, d, J ) 7.0,
CHCH3), 1.60-2.02 (4H, m), 2.17-2.40 (2H, m), 3.18-3.24 (1H,
m, CHCH3), 7.13-7.33 (5H, m, ArH); minor isomer δ 1.19 (3H,
d, J ) 7.3, CHCH3), 1.60-2.02 (4H, m), 2.17-2.40 (2H, m), 3.39-
3.44 (1H, m, CHCH3), 7.13-7.33 (5H, m, ArH); IR (Nujol method)
cm-1 1736; HRMS calcd for C13H16O 188.1201, found 188.1222.
2-Meth yl-4-p h en ylcyclop en ta n on e 2h . Yellow oil, obtained
as 3.2:1 mixture of cis and trans isomers. Stereochemistry was
determined on the basis of a positive NOE (3%) observed
between 2H and 4H. The major isomer is the cis isomer. 1H NMR
(CDCl3, 300 MHz cis and trans mixture) cis isomer δ 1.17 (3H,
d, J ) 6.7, CHCH3), 1.63 (1H, q, J ) 12.2, CHCHHCH), 2.24-
2.39 (2H, m, CHCHHCH, CHCHHCO), 2.58-2.63 (1H, m,
CHCHHCO), 2.77 (1H, dd, J ) 18.3, 7.3, CH3CH), 3.30-3.37
(1H, m, PhCH), 7.23-7.35 (5H, m, ArH); trans isomer δ 1.17
(3H, d, J ) 6.7, CHCH3), 1.63 (1H, q, J ) 12.2), 2.02-2.09 (1H,
m), 2.42-2.53 (2H, m), 2.68 (1H, d, J ) 7.9, CH3CH), 3.52-3.58
(1H, m, PhCH), 7.23-7.35 (5H, m, ArH); 13C NMR (CDCl3, 75.5
MHz cis and trans mixture) δ 13.9, 39.9, 40.0, 45.3, 45.6, 126.5,
126.6, 126.7, 128.6, 143.0, 219.5; IR (thin film, cis and trans
mixture) cm-1 1740; HRMS calcd for C12H14O 174.1045, found
174.1046.
4-P h en ylbu ta n a l 3i. Yellow oil. 1H NMR (CDCl3, 300 MHz)
δ 1.91-2.01 (2H, m, CH2CH2CH2), 2.45 (2H, td, J ) 7.3, 1.6,
CH2CO), 2.66 (2H, t, J ) 7.3, CH2Ph), 7.13-7.31 (5H, m, ArH),
9.75 (1H, t, J ) 1.6, CHO).
5-P h en ylp en ta n a l 3j. Yellow oil. 1H NMR (CDCl3, 300 MHz),
δ 1.51-1.65 (4H, m, CH2CH2CH2, CH2CH2CH2), 2.38 (2H, t, J
) 7.8, CH2CO), 2.57 (2H, t, J ) 7.0, CH2Ph), 7.08-7.23 (5H, m,
ArH), 9.69 (1H, t, J ) 1.6, CHO).
2-P h en ylm eth ylcyclop en ta n on e 2a . Yellow oil. 1H NMR
(CDCl3, 300 MHz) δ 1.48-1.61 (1H, m), 1.67-1.78 (1H, m), 1.90-
2.01 (1H, m), 2.04-2.17 (2H, m), 2.29-2.39 (2H, m), 2.50 (1H,
dd, J ) 13.6, 9.4, CHHPh), 3.15 (1H, dd, J ) 13.7, 4.0, CHHPh),
7.15-7.30 (5H, m, ArH); 13C NMR (CDCl3, 75.5 MHz) δ 20.5,
29.1, 35.6, 38.2, 51.0, 126.1, 128.4, 128.9, 140.0, 220.3; IR (thin
film) cm-1 1742; HRMS (FAB) calcd for C12H15O 175.1123, found
175.1101.
2-P h en ylm eth ylcycloh exa n on e 2b. Yellow oil. 1H NMR
(CDCl3, 300 MHz) δ 1.18-1.39 (1H, m), 1.43-1.68 (2H, m), 1.71-
1.79 (1H, m), 1.90-2.04 (2H, m), 2.13-2.53 (4H, m, included
CHHPh), 3.16 (1H, dd, J ) 13.7, 4.6, CHHPh), 7.15-7.30 (5H,
m, ArH); 13C NMR (CDCl3, 75.5 MHz) δ 25.1, 28.0, 33.4, 35.4,
42.2, 52.5, 125.9, 128.3, 129.1, 140.3, 212.6.
3-P h en ylm eth yltetr a h yd r ofu r a n -4-on e 2c. Yellow oil. 1H
NMR (CDCl3, 300 MHz) δ 2.65 (1H, dd, J ) 13.7, 10.0, CHHPh),
2.78 (1H, qd, J ) 9.5, 4.3, CHCO), 3.16 (1H, dd, J ) 13.7, 3.9,
CHHPh), 3.84 [1H, d, J ) 17.7, OCHHC(O)], 3.84-3.87 (1H, d,
J ) 8.8, OCHHCH), 4.06 [1H, d, J ) 17.1, OCHHC(O)], 4.30
(1H, t, J ) 8.8, OCHHCH), 7.14-7.32 (5H, m, ArH); 13C NMR
(CDCl3, 75.5 MHz) δ 33.5, 48.8, 71.1, 71.8, 126.7, 128.6, 128.7,
138.5, 219.7; IR (thin film) cm-1 1758.
2-Bip h en ylm eth ylcyclop en ta n on e 2d . Yellow oil. 1H NMR
(CDCl3, 300 MHz) δ 1.60-1.72 (1H, m), 1.74-1.82 (2H, m), 1.87-
1.96 (1H, m), 2.20-2.34 (2H, m), 2.90-2.98 (1H, m), 4.64 [1H,
d, J ) 4.9, CHPh(Ph)], 7.06-7.30 (10H, m, ArH); 13C NMR
(CDCl3, 75.5 MHz) δ 20.5, 27.3, 38.3, 50.0, 53.0, 126.3, 126.3,
128.2, 128.3, 128.3, 129.1, 142.5, 143.4, 219.2; IR (thin film) cm-1
1738.
Su p p or tin g In for m a tion Ava ila ble: Characterization
data (IR, 1H NMR) for thiolesters 1. This material is available
3-Bip h en ylm eth yltetr a h yd r ofu r a n -4-on e 2e. The assign-
ment of 1H NMR spectra was confirmed by 1H-1H COSY
J O001578U