K. L. Chandra et al. / Tetrahedron 58 (2002) 1369±1374
1373
chromatography on silica gel using ethyl acetate±petroleum
ether as eluent to give the pure product.
1.1.6. 3,4-Dicarbomethoxy cyclopentenyl-1-acetate
(entry 19). Yield 90% as a viscous liquid; R 0.60 (25%
f
EtOAc in petroleum ether); IR (neat) 1735, 1710,
1250 cm ; H NMR (CDCl , 400 MHz) d 2.09 (s, 3H),
2
1
1
Method B. To a solution of Cu(OTf) (10 mg, 2.5 mol%) in
2
3
acetic acid (2 mL) was added an alcohol (1 mmol) at rt. The
reaction mixture was stirred at 658C, and monitored by tlc.
After completion, the solution was poured on water, diluted
with CH Cl (15 mL), and stirred for few minutes. The
2.16±2.21 (m, 4H), 3.74 (s, 6H), 4.16 (m, 2H), 5.19 (m,
1H). Anal. calcd for C H O : C, 54.09; H, 6.56. Found:
C, 54.56; H, 6.46.
1
1
16
6
2
2
resulting organic layer was separated and washed with
water, brine, and dried over sodium sulfate. Solvent removal
and puri®cation over silica gel column using EtOAc±
petroleum ether as eluent gave the pure product.
1.1.7. 1-Acetoxy-2-phenyl cyclohexane (entries 20 and
21). Yield 99% as a liquid; R 0.45 (5% EtOAc in
2
4
f
petroleum ether); IR (neat) 3010, 2960, 1730, 1250, 830,
750 cm ; H NMR (CDCl , 400 MHz) d 1.25±2.12 (bm,
2
1 1
3
8
H), 1.75 (s, 3H), 2.65 (ddd, J12.2, 11.0, 3.9 Hz, 1H), 4.97
Method C. A mixture of Ac O (3mmol) and Cu(OTf)
2
(ddd, J10.5, 4.4 Hz, 1H), 7.24 (m, 5H, aromatics); MS (EI,
2
1
m/z): 218 (M ), 175, 158 (base peak).
(
3.6 mg, 1 mol%) was stirred at rt for 10 min. The ¯ask
was cooled to 2258C and an alcohol was added drop by
drop. The reaction mixture was stirred at the same tempera-
ture till completion of the reaction (by tlc). The reaction
mixture was quenched at the same temperature by the
addition of aq. NaHCO . It was diluted with CH Cl and
7
1.1.8. Linalyl acetate (entry 22). Yield 83% (based on
recovered linalool) as a colorless liquid; R 0.60 (5%
f
EtOAc in petroleum ether); IR (neat) 3010, 1720,
1250 cm ; H NMR (CDCl , 400 MHz) d 1.54 (s, 3H),
2
1
1
3
2
2
3
organic layer was separated. It was washed with water,
brined, and dried. The resulting crude product was puri®ed
by column chromatography on silica gel using ethyl
acetate±petroleum ether as eluent to give the pure product.
1.59 (s, 3H), 1.64 (s, 3H), 1.76 (m, 2H), 1.86 (m, 2H),
2.00 (s, 3H), 4.58 (m, 0.085H, 8.5%, rearranged isomer),
5.13(m, 3H ), 5.96 (dd, J11, 5.6 Hz, 0.915H, 91.5%).
1.1.9. 1-Allyl-4-tert-butyl-1-cyclohexyl acetate (entry 23).
Yield 85% as a liquid; R 0.60 (5% EtOAc in petroleum
1.1.1. 4-tert-Butyl cyclohexylacetate (entries 11 and 12).
Yield 98% as a viscous liquid; R 0.90 (10% EtOAc in
f
1
ether); H NMR (CDCl , 400 MHz) d 0.85 (s, 9H), 0.99
f
3
2
petroleum ether); IR (neat) 1720, 1250 cm ; H NMR
1
1
(m, 2H), 1.2 (m, 3H), 1.56 (m, 2H), 1.99 (s, 3H), 2.38 (m,
2H), 2.62 (d, J7.6 Hz, 2H), 5.03(d, J3.4 Hz, 1H), 5.06
(s, 1H), 5.76 (m, 1H). Anal. calcd for C H O : C, 75.63; H,
(
(
CCl , 400 MHz) d 0.85 (s, 9H), 0.95±1.34 (m, 5H), 1.81
4
m, 2H), 1.99 (m, 2H), 2.02 (s, 3H), 4.62 (tt, J11.2, 4.4 Hz,
1
5
26
2
1
C, 72.86; H, 11.20.
H). Anal. calcd for C H O : C, 72.73; H, 11.11. Found:
2
10.92. Found: C, 75.46; H, 11.02.
1
2
22
1.1.10. 1-Phenyl ethynyl-1-cyclohexyl acetate (entry 24).
Yield 70% as a liquid; R 0.60 (5% EtOAc in petroleum
1
9
.1.2. (2)-(1R)-Methyl acetate (entries 13 and 14). Yield
7% as a colorless liquid; R 0.90 (10% EtOAc in petroleum
f
1
ether); H NMR (CDCl , 400 MHz) d 1.28 (m, 1H), 1.67
f
3
2
5
7b
20
ether); [a]D 2117.7 (c 1.0, CHCl ) {lit. [a]D
(m, 7H), 2.02 (s, 3H), 2.47 (d, J11 Hz, 2H), 7.3(m, 5H),
3
1
3
2
80.58 (c 8.0, benzene)}.
C NMR (CDCl , 100 MHz) d 22.0, 25.2, 36.1, 82.3, 124.4,
3
126.8, 128.1, 145.5, 169.4. Anal. calcd for C H O : C,
79.34; H, 7.44. Found: C, 79.26; H, 7.52.
1
6
18
2
1.1.3. (1) Methyl (S)-a-acetoxy phenylacetate (entries 15
and 16). Yield 97% as a colorless liquid; R 0.85 (20%
f
2
5
EtOAc in petroleum ether); [a]D 1134.2 (c 2.4,
1.1.11. TADDOL diacetate (entry 25). Yield 86% as a
2
CHCl ); IR (neat) 2960, 1735, 1250, 830, 760 cm ; H
1
1
25
white solid; mp 172±1758C, [a]D 2105.1 (c 1.0,
3
NMR (CDCl , 400 MHz) d 2.18 (s, 3H), 3.69 (s, 3H),
3
CHCl ); R 0.80 (20% EtOAc in petroleum ether); IR
f
3
2
1
(KBr) 3020, 2950, 1735, 1710, 1210, 830, 750 cm ; H
1
5.95 (s, 1H), 7.33±7.46 (m, 5H). Anal. calcd for
C H O : C, 68.18; H, 7.57. Found: C, 68.66; H, 7.42.
NMR (CDCl , 400 MHz) d 1.62 (s, 6H), 6.31 (s, 2H),
3
1
5
20
4
7
.12±7.34 (m, 16H), 7.59 (d, J8 Hz, 4H). Anal. calcd
1
.1.4. tert-Butyl (S)-3-acetoxy-3-phenyl propanoate
entry 17). Yield 92% as a colorless liquid; R 0.50 (10%
for C H O : C, 75.29; H, 5.88. Found: C, 75.46; H, 5.90.
3
2
30
6
(
EtOAc in petroleum ether); IR (neat) 1720, 1640, 1250,
7
2
f
1.1.12. 2-Hydroxy-1,2,2-triphenylethylacetate (entry 26).
Yield 88%; white solid, mp 70±728C; R 0.70 (20% EtOAc
2
1
60 cm ; H NMR (CDCl , 400 MHz) d 1.39 (s, 9H),
1
3
f
1
2
in petroleum ether); IR (KBr) 1730 cm ; H NMR (CDCl ,
1
.03(s, 3H ), 2.65±2.70 (dd, J15, 6 Hz, 1H), 2.84±2.90
3
(
dd, J15, 8 Hz, 1H), 6.11±6.15 (dd, J9, 5 Hz, 1H), 7.27±
400 MHz) d 1.97 (s, 3H), 7.06 (m, 1H), 7.12±7.4 (m, 15H).
MS (EI, m/z): 308 (M ). Anal. calcd for C H O : C, 79.51;
H, 6.02. Found: C, 79.66; H, 6.12.
1
7
Found: C, 68.26; H, 7.62.
.37 (m, 5H). Anal. calcd for C H O : C, 68.18; H, 7.57.
1
5
20
4
22 20
3
1.1.5. 1-Cyano heptanyl-1-acetate (entry 18). Yield 99%
as a viscous liquid; R 0.40 (5% EtOAc in petroleum ether);
1.1.13. 1,4 Bis (S,S)-(t-butyl 1-propanoyl-1-acetoxy)-
xylene (entry 28). Yield 88% as a white solid; mp 133±
1358C; R 0.50 (20% EtOAc in petroleum ether);
f
2
1
1
IR (neat) 2250, 1730, 760 cm ; H NMR (CDCl3,
f
2
5
4
(
1
00 MHz) d 0.89 (t, J6.5 Hz, 3H), 1.30 (m, 6H), 1.49
m, 2H), 1.88 (m, 2H), 2.13(s, 3H ), 5. 31 (t,
J7.5 Hz,
H); MS (EI, m/z): 182 (M ). Anal. calcd for C H NO :
[a]D 117.9 (c 1.0, CHCl ); IR (KBr) 3010, 2980,
3
2
1
1
1735, 1710, 1670, 830, 760 cm ; H NMR (CDCl ,
3
1
400 MHz) d 1.39 (s, 18H), 2.17 (s, 6H), 2.62±2.67 (dd,
J15, 6 Hz, 2H), 2.81±2.87 (dd, J15, 9 Hz, 2H), 6.09±
1
0
17
2
C, 65.57; H, 9.28; N, 7.65. Found: C, 65.38; H, 9.32; N,
.74.
1
3
7
6.12 (m, 2H), 7.34 (s, 4H, aromatics); C NMR (CDCl ,
3