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H. Fang et al. / Tetrahedron 59 (2003) 3779–3786
24.06, 25.19, 25.54, 26.55, 26.75, 27.62, 27.90, 28.96,
29.00, 29.14, 29.17, 30.39, 30.40, 33.00, 33.24, 36.06,
38.59, 38.62, 44.59, 44.61, 50.26, 50.77, 50.96, 115.69,
139.46, 19.67, 139.69, 139.72, 141.16, 141.41, 141.47,
141.62; HRMS m/z calcd for C21H38: 290.2974, found:
290.2975.
23.03, 23.74, 24.00, 24.68, 25.01, 26.11, 26.16, 26.63,
26.81, 27.95, 28.00, 28.54, 29.01, 29.23, 30.69, 31.48,
31.52, 31.61, 32.65, 32.98, 33.11, 52.92, 54.49, 59.90,
125.69, 125.90, 126.16, 126.31, 126.37, 127.89, 128.16,
128.30, 128.42, 128.49, 128.65, 129.32, 129.48, 129.81,
137.69, 142.94, 143.08; HRMS m/z calcd for C28H36:
372.2817, found: 372.2803.
4.2.7. 1-Phenyl-2,3,4,5-tetrabutyl-1,3-cyclopentadiene
(8a). Pale yellow liquid, isolated yield 60% (219 mg), GC
yield 85%. Three isomers (3:1:1). IR (neat): 2957, 1704,
4.2.11. 1,3-Dibutyl-2-phenyl-4,5,6,7-tetrahydroindene
(10a). Pale yellow liquid, isolated yield 91% (280 mg),
GC yield 96%. Five isomers (4:2:2:1:1). IR (neat): 2956,
1
1600, 1492, 1458, 1378, 1071, 756, 700 cm21; H NMR
1
(CDCl3, Me4Si) for the mixture: d 0.66–1.07 (m, 16H),
1.22–1.55 (m, 14H), 2.16–2.42 (m, 8H), 3.06 (t, J¼4.2 Hz,
0.2H), 3.43 (t, J¼3.6 Hz, 0.6H), 3.82 (s, 0.2H), 7.13–7.36
(m, 5H); 13C NMR (CDCl3, Me4Si) for the major: d 13.92,
14.02, 14.10 (2 CH3), 22.79, 22.91, 23.07 (2 CH2), 24.80,
25.43, 26.30, 26.64, 27.76, 32.67, 33.07, 33.21, 52.42,
125.33, 128.00, 128.45, 137.86, 140.63, 141.44, 142.60,
144.28; HRMS m/z calcd for C27H42: 366.3287, found:
366.3283.
2925, 2861, 1701, 1646, 1456, 1377, 1089, 745 cm21; H
NMR (CDCl3, Me4Si) for the mixture: d 0.67–0.91 (m, 8H),
1.05–1.48 (m, 4H), 1.63–1.74 (m,.8H), 2.14–2.16 (m, 6H),
3.31 (s, 0.2H), 3.42 (s, 0.2H), 3.56 (t, J¼5.2 Hz, 0.4H), 5.12
(t, J¼7.8 Hz, 0.1H), 5.41 (t, J¼7.8 Hz, 0.1H), 7.11–7.32
(m, 5H); 13C NMR(CDCl3, Me4Si) for the mixture: d 13.63,
13.76, 13.95, 14.07, 14.09, 22.09, 22.41, 22.72, 22.87,
22.91, 22.96, 23.03, 23.08, 23.22, 23.27, 23.65, 24.38,
25.12, 25.38, 25.72, 26.11, 26.41, 27.90, 28.85, 29.05,
29.77, 30.77, 32.34, 33.59, 36.11, 50.58, 52.03, 54.00,
57.89, 58.82, 114.13, 116.66, 125.37, 125.41, 125.83,
127.16, 127.70, 128.05, 128.10, 128.23, 128.26, 128.49,
129.09, 138.99, 142.04, 142.36; HRMS m/z calcd for
C23H32: 308.2504, found: 308.2497.
4.2.8. 1-Propyl-2,3,4,5-tetrabutyl-1,3-cyclopentadiene
(8b). Pale yellow liquid, isolated yield 54% (179 mg), GC
yield 77%. Four isomers (5:2:2:1). IR (neat): 2959, 2873,
1702, 1460, 1379, 1103 cm21; 1H NMR (CDCl3, Me4Si) for
the mixture: d 0.78–0.97 (m, 19H), 1.18–1.1.62 (m, 14H),
2.05–2.40 (m, 8H), 2.60 (t, J¼7.5 Hz, 0.5H); 2.84 (t,
J¼7.2 Hz, 0.2H), 5.09 (dt, J¼7.2 Hz, J¼1.8 Hz, 0.2H), 5.33
(t, J¼7.2 Hz, 0.1H); 13C NMR (CDCl3, Me4Si) for the
mixture: d 13.95, 13.98, 14.06, 14.09, 14.14, 14.47, 14.58,
14.71, 16.40, 19.89, 20.29, 22.49, 22.67, 22.81, 22.89,
22.93, 23.01, 23.04, 23.08, 23.17, 23.24, 23.63, 24.07,
24.47, 5.20, 25.55, 26.52, 26.77, 27.06, 27.62, 27.93, 28.99,
29.10, 29.41, 30.35, 30.40, 31.00, 31.33, 32.34, 32.97,
33.23, 33.35, 34.13, 35.80, 36.10, 38.55, 44.62, 44.77,
50.31, 50.44, 50.85, 51.03, 115.60, 125.96, 135.30, 136.73,
136.89, 19.70, 139.73, 139.94, 146.04, 141.34, 141.37,
150.75; HRMS m/z calcd for C24H44: 332.3443, found:
332.3442.
4.2.12. 1,3-Dibutyl-2-propyl-4,5,6,7-tetrahydroindene
(10b). Pale yellow liquid, isolated yield 63% (173 mg),
GC yield 85%. Two isomers (2:1). IR (neat): 2957, 2870,
1
1702, 1599, 1492, 1458, 1378, 1032, 762, 701 cm21; H
NMR (CDCl3, Me4Si) for the mixture: d 0.81–0.95 (m,
13H), 1.17–1.66 (m, 14H), 2.02–2.17 (m, 6H), 5.00 (t,
J¼7.2 Hz, 0.7H); 5.27 (t, J¼3.0 Hz, 0.3H); 13C NMR
(CDCl3, Me4Si) for the major isomer: d 14.07, 14.14, 14.49,
19.97, 21.90, 22.75, 23.15, 23.20, 23.28, 23.65, 25.12,
29.36, 30.93, 33.51, 38.52, 45.37 (CH), 114.57, 134.64,
144.99, 150.78; HRMS m/z calcd for C20H34: 274.2661,
found: 274.2659.
4.2.13. Alcohol (12). Colorless crystals (mp: 838C), isolated
yield 67% (216 mg), GC yield 78%. 1H NMR (CDCl3,
Me4Si) 0.80–0.97 (m, 6H), 1.17–1.34 (m, 10H), 1.59 (br,
1H), 1.95–2.40 (m, 2H), 5.34 (s, 1H), 7.17–7.36 (m, 10H);
13C NMR (CDCl3, Me4Si) d 13.78, 13.98, 22.86, 23.41,
27.16, 30.15, 33.21, 34.24, 73.85, 125.73, 126.45, 126.66,
127.94, 128.21, 128.73, 137.17, 141.20, 142.59, 143.10;
HRMS m/z calcd for C23H30O: 322.2297, found: 322.2289.
4.2.9. 1,3,5-Triphenyl-2,4-dibutyl-1,3-cyclopentadiene
(9a). Pale yellow liquid, isolated yield 61% (247 mg), GC
yield 86%. Two isomers (2:1). IR (neat): 2958, 2871, 1703,
1
1598, 1492, 1445, 1378, 1071, 910, 699 cm21; H NMR
(CDCl3, Me4Si) for the mixture: d 0.51–1.53 (m, 14H),
2.14–2.55 (m, 4H), 4.17 (t, J¼4.8 Hz, 0.7H), 4.51 (t,
J¼3.3 Hz, 0.3H), 7.02–7.41 (m, 15H); 13C NMR (CDCl3,
Me4Si) for the major: d 22.54 (2 CH3), 22.58, 24.56, 25.90,
28.35, 31.33 (2 CH2), 54.14, 126.12, 126.65, 127.84,
127.89, 127.98, 128.15, 128.20, 128.25, 128.40, 128.47,
128.57, 128.60, 128.83, 128.88, 129.39, 129.68; HRMS m/z
calcd for C31H34: 406.2661, found: 406.2664.
4.3. Typical procedure for the preparation of benzene
derivatives from reactions of aluminacyclopentadienes
with dimethylacetylene dicarboxylate (DMAD)
To a diethyl ether (5 mL) solution of 1,4-dilithio-1,3-
butadiene (1 mmol) at 2788C was added AlCl3 (1.2 mmol).
The reaction mixture was warmed to room temperature and
stirred for 1 h. The reaction mixture was then again cooled
down to 2788C and was added dimethylacetylene dicar-
boxylate (DMAD) (2 mmol). The reaction mixture was then
warmed to room temperature and stirred for 2 h. The
reaction mixture was quenched with 3N HCl and extracted
with ether. The extract was washed with aqueous NaHCO3,
water, and brine and dried over MgSO4. The solvent was
then evaporated in vacuo to give a residue, which was
4.2.10. 1,3-Diphenyl-2,5-dibutyl-4-propyl-1,3-cyclo-
pentadiene (9b). Pale yellow liquid, isolated yield 52%
(193 mg), GC yield 78%. Three isomers (2:1:1). IR (neat):
2961, 2361, 1717, 1598, 1492, 1449, 1071, 753, 701 cm21
;
1H NMR (CDCl3, Me4Si) for the mixture: d 0.52–1.43 (m,
19H), 2.15–2.33 (m, 6H), 3.60 (t, J¼3.9 Hz, 0.6H), 3.93 (t,
J¼3.9 Hz, 0.2H), 3.98 (t, J¼3.9 Hz, 0.2H), 7.21–7.40 (m,
10H); 13C NMR (CDCl3, Me4Si) for the mixture: d 13.61,
13.74, 13.81, 13.86, 13.95, 13.99, 14.11, 14.24, 14.29,
14.46, 14.51, 16.33, 22.55, 22.62, 22.66, 22.75, 22.95,