1284
U. M. Dzhemilev et al. / Tetrahedron 60 (2004) 1281–1286
144(100), 143(53), 118(26), 104(54), 90(2), 77(30), 29(18).
Anal. Calcd for C11H14O: C, 81.44; H, 8.70; Found: C,
81.23; H, 8.52. Yield 64%.
4.4. Reaction of trans-3-alkylaluminacyclopentanes with
thionyl chloride
A 50 mL glass reactor was charged with Cp2ZrCl2
(0.5 mmol) in dry hexane (3 mL), olefin (10 mmol), and
AlEt3 (12 mmol) under a dried argon atmosphere at 0 8C.
The resulting solution was raised to ambient temperature
and stirred for 12 h, then cooled to 240 8C, and thionyl
chloride (30 mmol) was added dropwise, stirred for 8 h and
treated with 8–10% (aq.) solution of HCl. The crude
products were extracted with diethyl ether or hexane and
purified by distillation in vacuo.
4.2.7. cis/trans-3-Benzylcyclopentanol ,(2:1) (2j). IR
(thin film) 3380, 2990, 3015, 2995, 2950, 1715, 1600,
1490, 1450, 1400, 1180, 750, 700 cm-1; 1H NMR (CDCl3) d
1.58–2.25 (m, 7H, CH, CH2), 2.62 (d, J¼5.6 Hz, 2H, CH2–
Ph), 4.28 (m, H, CH–OH), 7.00–7.48 (m, 5H, Ph); 13C
NMR (CDCl3) d 30.34(30.54), 32.09(32.39), 38.78(39.36),
39.72(40.33), 42.06(41.60), 76.38(76.57), 126.00, 128.24,
128.42, 141.38; MS (m/z, %): 176(19, Mþ), 158(7), 132(2),
118(7), 104(5), 91(100), 77(7), 29(27). Anal. Calcd for
C12H16O: C, 81.77; H, 9.15; Found: C, 81.59; H, 9.01. Yield
69%.
4.4.1. 3-(n-Butyl)tetrahydrothiophene (6a). IR (thin film)
1
2970, 2940, 2870, 1470, 1385, 1265, 1220, 750 cm21; H
NMR (CDCl3) d 0.87–0.95 (m, 3H, CH3), 1.35 (m, 6H,
CH2), 1.87–2.48 (m, 3H, CH and CH2 ring), 2.65–3.01 (m,
4H, CH2–S); 13C NMR (CDCl3) d 14.10, 22.90, 30.80,
31.00, 33.30, 36.81, 44.80; MS m/z: 144 Mþ. Yield 85%.
4.3. Reaction of trans-3,4-dialkylaluminacyclopentanes
with carboxylic esters catalyzed by CuCl
To the solution of tri(n-hexyl)aluminium (10 mmol),
prepared in situ according to the literature method37 at
215 8C under a dried argon atmosphere was added CuCl
(1 mmol) and dropwise the corresponding ester (30 mmol).
The reaction temperature was raised to rt (ca. 20 8C), and the
mixture was stirred for 8 h. The reaction was quenched with
8–10% (aq.) solution of HCl. The layers were separated and
the aqueous phase was extracted with Et2O or hexane. The
combined organic extracts were washed with water,
saturated aqueous NaHCO3, dried (CaCl2), filtered and
concentrated in vacuo. The products were isolated by
column chromatography on silica gel (40–100 mesh grade)
with hexane/Et2O¼10:1 for elution.
4.4.2. 3-(n-Nonyl)tetrahydrothiophene (6b). IR (thin film)
1
2960, 2925, 2855, 1460, 1375, 1260, 1210, 720 cm21; H
NMR (CDCl3) d 0.83–0.92 (m, 3H, CH3), 1.21 (m, 16H,
CH2), 1.93–2.47 (m, 3H, CH, CH2 ring), 2.58–2.83 (m, 4H,
CH2–S); 13C NMR (CDCl3) d 14.10, 22.70, 28.80, 29.40,
29.70, 29.90, 30.80, 31.90, 33.60, 36.80, 44.80; MS m/z: 214
Mþ. Yield 83%.
4.5. Reaction of trans-3,4-dialkylaluminacyclopentanes
with thionyl chloride
A 50 mL glass reactor was charged with Cp2ZrCl2
(0.5 mmol), Mg (powder) (12 mmol), dry THF (10 mL),
olefin (20 mmol), and EtAlCl2 (12 mmol) under a dried
argon atmosphere at 0 8C. The resulting solution was
allowed to warm to ambient temperature and stirred for
12 h, then cooled up to 240 8C and thionyl chloride
(30 mmol) was added dropwise, stirred for 8 h and treated
with 8–10% (aq.) solution of HCl. The crude products were
extracted with diethyl ether or hexane and purified by
1
4.3.1. trans-3,4-Di(n-butyl)cyclopentanol (4a). H NMR
(CDCl3) d 0.86–0.90 (m, 6H, CH3), 1.15–1.30 (m, 12H,
CH2), 1.65–2.35 (m, 6H, CH and CH2 ring), 5.30 (m, H,
CH–OH); 13C NMR (CDCl3) d 14.12, 22.66, 29.85, 34.35,
39.10, 42.02, 73.25. Anal. Calcd for C13H26O: C, 78.72; H,
13.21; Found: C, 76.68; H, 13.01. Yield 75%.
1
4.3.2. trans-3,4-Di(n-hexyl)cyclopentanol (4b). H NMR
distillation in vacuo. Compounds 8a–c were identified by
31
(CDCl3) d 0.88–0.91 (m, 6H, CH3), 1.15–1.30 (m, 20H,
CH2), 1.65–2.35 (m, 6H, CH and CH2 ring), 5.30 (m, H,
CH–OH); 13C NMR (CDCl3) d 14.15, 22.54, 26.15, 29.42,
31.72, 34.31, 39.02, 41.45, 72.18. Anal. Calcd for C17H34O:
C, 80.24; H, 13.47; Found: C, 80.03; H, 13.29. Yield
74%.
comparison with the known samples
.
4.6. Reaction of trans-3,4-di(alkyl)aluminacyclopentanes
with dichlorophenylphosphine
A 50 mL glass reactor was charged with Cp2ZrCl2
(0.5 mmol), Mg (powder) (12 mmol), dry THF (10 mL),
olefin (20 mmol), and EtAlCl2 (12 mmol) under a dried
argon atmosphere at 0 8C. The solution was raised to
ambient temperature and stirred for 12 h, then cooled to
215 8C and dichlorophenylphosphine (12 mmol) was
slowly added dropwise. The reaction mixture was allowed
to warm to rt (ca. 20 8C), stirred for 8 h and treated with
8–10% (aq.) solution of HCl. The crude products were
extracted with diethyl ether or hexane and purified by
distillation in vacuo.
4.3.3. 1-Methyl-trans-3,4-di(n-butyl)cyclopentanol (4c).
1H NMR (CDCl3) d 0.83–0.95 (m, 6H, CH3), 1.14–1.29
(m, 12H, CH2), 1.32 (s, 3H, CH3), 1.65–2.35 (m, 6H, CH
and CH2 ring); 13C NMR (CDCl3) d 14.12, 22.69, 26.92,
31.93, 34.53, 38.15, 41.94, 72.83. Anal. Calcd for C14H28O:
C, 79.18; H, 13.29; Found: C, 78.98; H, 13.11. Yield
73%.
4.3.4. 1-Ethyl-trans-3,4-di-(n-butyl)cyclopentanol (4d).
1H NMR (CDCl3) d 0.86–0.92 (m, 9H, CH3), 1.24–1.62
(m, 14H, CH2), 1.67–2.54 (m, 6H, CH and CH2 ring);
13C NMR (CDCl3) d 8.80, 14.11, 22.69, 29.95, 33.90,
32.42, 37.41, 38.44, 76.65. Anal. Calcd for C15H30O:
C, 79.58; H, 13.36; Found: C, 79.41; H, 13.20. Yield
69%.
4.6.1. 1-Phenyl-trans-3,4-di(n-butyl)phospholane (9a).
1H NMR (CDCl3) d 0.89 (t, J¼6.5 Hz, 6H, CH3), 1.26–
1.75 (m, 14H, CH2 and CH), 3.40–3.51 (m, 4H, CH2P),
7.17–7.87 (m, 5H, Ph). Anal. Calcd for C18H29P: C, 78.22;
H, 10.58; Found: C, 77.99; H, 10.42. Yield 60%.