P.F. Hudrlik et al. / Tetrahedron 67 (2011) 10089e10096
10095
139.9 (C). GC analysis37b showed a major peak at 12.7 min (96%);
C24H50 at 21.3 min.
(11),44 with a few additional smaller peaks in the NMR spectra.
The IR spectrum had only a very small shoulder at 963 cmꢁ1 (pos-
sibly E isomer) suggesting the major isomer was Z. (For the IR spectra
of the E and Z isomers of 11, see ref 45.) GC analysis37b gave major
peaks at 8.1, 8.2 min (14%, 81%, not well resolved, 11 (E and Z)).
4.13. o-((Z)-Crotyldimethylsilyl)benzyl alcohol (2d)
To a solution of 3.000 g (10.025 mmol) of crotylsilyl ether 1d in
50 mL of anhydrous ether was added 0.70 g (101 mmol) of lithium
wire. The reaction mixture was stirred at rt for 2 h, and then added
to 100 mL of saturated NaHCO3. The aqueous layer was extracted
with ether (2ꢂ20 mL), and the combined organic layers were dried
(MgSO4), concentrated, and chromatographed (40 g of silica gel,
19.0ꢂ2.5 cm, petroleum ether/ether 9:1) giving 1.274 g (58% yield)
of crotylsilyl alcohol 2d as a clear and colorless oil: IR (film): 3318
(br), 3057, 3014, 2957, 1650, 1436, 1397, 1250, 1150, 1079, 837,
References and notes
1. (a) Stork, G.; Hudrlik, P. F. J. Am. Chem. Soc. 1968, 90, 4462e4464; (b) Stork, G.;
Hudrlik, P. F. J. Am. Chem. Soc. 1968, 90, 4464e4465.
2. (a) Stork, G.; Colvin, E. J. Am. Chem. Soc. 1971, 93, 2080e2081; (b) Stork, G.; Jung,
M. E. J. Am. Chem. Soc. 1974, 96, 3682e3684; (c) Stork, G.; Jung, M. E.; Colvin, E.;
Noel, Y. J. Am. Chem. Soc. 1974, 96, 3684e3686.
3. (a) Stork, G.; Ganem, B. J. Am. Chem. Soc. 1973, 95, 6152e6153; (b) Stork, G.;
Singh, J. J. Am. Chem. Soc. 1974, 96, 6181e6182; (c) See also: Boeckman, R. K., Jr. J.
Am. Chem. Soc. 1974, 96, 6179e6181.
4. Fleming views 1968 as ‘a date, which marks the turning point in the applica-
tions of organosilicon chemistry to organic synthesis.’ Fleming, I. Chem. Soc. Rev.
1981, 10, 83e111.
750 cmꢁ1 1H NMR (400 MHz, 1,4-dioxane as standard at
; d 3.71):
d
0.40 (s, 6H), 1.58 (d, J¼5.1 Hz, 3H), 1.84 (d, J¼7.4 Hz, 2H), 2.01 (s,
1H), 4.80 (s, 2H), 5.51e5.39 (m, 2H), 7.33 (td, J¼7.4, 1.0 Hz, 1H) 7.44
(td, J¼7.5, 1.2 Hz, 1H), 7.51 (d, J¼7.6 Hz, 1H), 7.58 (dd, J¼7.2, 0.7 Hz,
5. For reviews, see: (a) Lalonde, M.; Chan, T. H. Synthesis 1985, 817e845; (b)
€
Rucker, C. Chem. Rev. 1995, 95, 1009e1064; (c) Nelson, T. D.; Crouch, R. D.
1H); 13C NMR (100 MHz):
d
ꢁ1.6 (CH3), 12.6 (CH3), 17.7 (CH2), 65.4
Synthesis 1996, 1031e1069; (d) van Look, G.; Heberle, J.; Simchen, G. Silylating
Agents, 2nd ed.; Fluka Chemie: Buchs, Switzerland, 1995.
(CH2), 122.3 (CH), 125.9 (CH), 127.0 (CH), 127.9 (CH), 129.6 (CH),
135.0 (CH), 136.8 (C), 146.2 (C); GC/MS m/z (relative intensity, ten-
tative assignment): 220 (not visible, Mþ), 165 (63, Mꢁcrotyl), 147
(100), 145 (58). HRMS (ESI) calcd for C13H20OSiNa (MþNa),
243.1181. Found, 243.1183. (For examples of mass spectra of similar
compounds, see Ref. 13.) GC analysis37a showed a major peak at
12.1 min (98%); C24H50 at 21.7 min. From earlier chromatography
fractions was obtained an additional 0.604 g (27% yield) of 2d as
a clear and colorless oil, which was 85% pure by GC.
6. Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.;
Wiley: New York, NY, 1999; 113e148.
7. (a) Stork, G.; Kahn, M. J. Am. Chem. Soc. 1985, 107, 500e501; (b) Stork, G.; Sofia,
M. J. J. Am. Chem. Soc. 1986, 108, 6826e6828; (c) Stork, G. Bull. Chem. Soc. Jpn.
1988, 61, 149e154; (d) Stork, G.; Mah, R. Tetrahedron Lett. 1989, 30, 3609e3612;
(e) Stork, G.; Suh, H. S.; Kim, G. J. Am. Chem. Soc. 1991, 113, 7054e7056.
8. (a) Stork, G.; Chan, T. Y.; Breault, G. A. J. Am. Chem. Soc. 1992, 114, 7578e7579;
(b) See also: Stork, G.; Chan, T. Y. J. Am. Chem. Soc. 1995, 117, 6595e6596.
9. (a) Stork, G.; Kim, G. J. Am. Chem. Soc. 1992, 114, 1087e1088; (b) Stork, G.; La
Clair, J. J. J. Am. Chem. Soc. 1996, 118, 247e248.
10. For reviews, see (a) Bols, M.; Skrydstrup, T. Chem. Rev. 1995, 95, 1253e1277; (b)
Bracegirdle, S.; Anderson, E. A. Chem. Soc. Rev. 2010, 39, 4114e4129.
11. Hudrlik, P. F.; Abdallah, Y. M.; Hudrlik, A. M. Tetrahedron Lett. 1992, 33,
6743e6746.
4.14. Reaction of o-((Z)-crotyldimethylsilyl)benzyl alcohol
(2d) with benzaldehyde: 1-phenyl-3-penten-1-ol (11) and
2-methyl-1-phenyl-3-buten-1-ol (12s and 12a)
12. Hudrlik, P. F.; Abdallah, Y. M.; Hudrlik, A. M. Tetrahedron Lett. 1992, 33,
6747e6750.
13. Hijji, Y. M.; Hudrlik, P. F.; Okoro, C. O.; Hudrlik, A. M. Synth. Commun. 1997, 27,
4297e4308.
To an ice-cooled solution of 0.317 g (1.437 mmol) of the cro-
tylsilyl alcohol 2d in 9 mL of anhydrous ether was added 0.60 mL
(1.5 mmol) of n-butyllithium (2.5 M in hexanes) dropwise. The
resulting mixture was stirred for 0.5 h at 0 ꢀC. Benzaldehyde
(0.12 mL, 1.18 mmol) was added followed by 9 mL of THF. The ice
bath was removed and the reaction mixture was stirred at rt for
18.5 h, then added to 40 mL of saturated NaHCO3. The aqueous layer
was extracted with ether (2ꢂ10 mL), and the combined organic
layers were dried (MgSO4). GC analysis37b showed major peaks at
5.5 min (50%, oxasilacyclopentane 5), 7.3 min (25%, syn and anti
isomers of 12: 12s, 12a), and 8.05, 8.14 min (4%, 15%, not well re-
solved, 11 (E and Z)). The product was quickly chromatographed on
silica gel to remove oxasilacyclopentane 5, and then purified by
bulb-to-bulb distillation (90 ꢀC, 0.25 mm) to give 0.169 g (88% yield)
of a clear and colorless oil as a mixture of 11 (E and Z) and 12 (syn
and anti). GC analysis37b showed major peaks at 7.1 min (55%, 12s,
12a) and 7.8, 7.9 min (7%, 28%, not well resolved, 11 (E and Z)). The
proton NMR spectrum of the oil showed peaks that are consistent
with the purified isomers of 11 and 12 (below). The oil was chro-
matographed (8 g of silica gel, petroleum ether/ether 9:1) to give
(a) 0.053 g (28% yield) of 12, (b) 0.060 g of a mixture of 11 and 12,
and (c) 0.026 g (14% yield) of 11, all as clear and colorless oils.
The first portion (a) had IR, 1H NMR, and 13C NMR spectra
consistent with a mixture of 12s and 12a. In particular, the peaks in
the 1H NMR were those of the reported43 spectra of the syn and anti
14. Hijji, Y. M.; Hudrlik, P. F.; Hudrlik, A. M. Chem. Commun. 1998, 1213e1214.
15. Hudrlik, P. F.; Arango, J. O.; Hijji, Y. M.; Okoro, C. O.; Hudrlik, A. M. Can. J. Chem.
2000, 78, 1421e1427.
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for example) where cleavage of the endocyclic bond is observed: (a) Taguchi,
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isomers of 12; the integration (especially the peaks at
d 0.87, 1.01,
4.35, 4.61) indicated a syn/anti ratio of 1.5e1.7/1. GC analysis37b
gave major peaks at 7.3 min (96%, 12s, 12a) and 8.1 min (2%).
The second portion (b) in the GC analysis37b showed major
peaks at 7.4 min (60%, 12) and 8.1, 8.2 min (14%, 25%, not well re-
solved, 11 (E and Z)).
22. (a) Wakefield, B. J. The Chemistry of Organolithium Compounds; Pergamon:
Oxford, 1974; p. 23; (b) Negishi, E. Organometallics in Organic Synthesis; Wiley:
New York, NY, 1980; p. 96.
~
23. Guijarro, D.; Mancheno, B.; Yus, M. Tetrahedron 1992, 48, 4593e4600.
The third portion (c) had 1H NMR, and 13C NMR spectra con-
taining all of the peaks reported for (Z)-1-phenyl-3-penten-1-ol
24. Cohen, T.; Kreethadumrongdat, T.; Liu, X.; Kulkarni, V. J. Am. Chem. Soc. 2001,
123, 3478e3483.