Selective Reductions of α,β-Unsaturated Ketones
FULL PAPER
[2]
[3]
[4]
J. March, Advanced Organic Chemistry Wiley, New York, 4th
The saturated ketones c were prepared by reaction of substrates 1–
4 with NaBH4/CoCl2 in the specified reaction medium, with optim-
ized ratios of substrate/NaBH4/CoCl2 as reported in Table 2 and
Table 4, starting form 0.3 mmol substrate. All compounds were
purified on a silica gel column.
ed., 1992, chapter 15.
A. L. Gemal, J.-L. Luche, J. Am. Chem. Soc. 1981, 103,
5454–5459.
H. Fujii, K. Oshima, K. Utimoto, Chem. Lett. 1991, 1847–
1848.
[5]
[6]
[7]
[8]
B. C. Ranu, Synlett 1993, 885–892.
1c: Solvent: water; 82% yield. – M.p. 38–40 °C (ref.[20] 39–40 °C). –
1H NMR: δ ϭ 1.10 (s, 6 H, 2CH3), 1.70 (t, J ϭ 6.81 Hz, 4 H,
2CH2), 2.40 (t, J ϭ 6.81 Hz, 4 H, 2CH2).
G. W. Gribble, Chem. Soc. Rev. 1998, 27, 395–404.
B. Ganem, J. O. Osby, Chem. Rev. 1986, 86, 763–780.
H. I. Schlesinger, H. C. Brown, A. E. Finholt, J. R. Galbreath,
H. R. Hoekstra, E. K. Hyde, J. Am. Chem. Soc. 1953, 75,
215–221.
2c: Solvent: water; 98% yield. The 1H NMR spectrum was identical
[9]
to that in the literature.[21]
H. C. Brown, K. Ichikawa, J. Am. Chem. Soc. 1961, 83,
4372–4374.
J. O. Osby, S. W. Heinzman, B. Ganem, J. Am. Chem. Soc.
1986, 108, 67–72.
[10]
1
3c: Solvent: aqueous SDS; 77% yield. The H NMR was identical
to that of a commercial sample (Aldrich).
[11] [11a]
[11b]
C. J. Li, Chem. Rev. 1993, 93, 2023–2035. –
J. Gao, J.
[11c]
4c: Solvent: methanol; 85% yield. – M.p.: 69–70 °C (ref.[22] 67–69
°C). The 1H NMR was identical to that of a commercial sample
(Lancaster).
Am. Chem. Soc. 1994, 116, 1563–1564. –
J. B. F. N.
[11d]
Engberts, Pure Appl. Chem. 1995, 67, 823–828. –
P. A.
Grieco, Organic Synthesis in Water, Blackie Academic and Pro-
fessional, London, 1998.
[12] [12a]
J. H. Fendler, Membrane Mimetic Chemistry, Wiley, New
The saturated alcohols d for substrates 1 and 4 were prepared by
reduction with the one-pot multiple-step procedures previously de-
scribed; for substrate 3 by reduction with NaBH4 ϩ CoCl2 with
the optimized ratio reported in Table 3. Products were obtained
pure, apart form 1d which was purified on a silica gel column.
York, 1982; chapter 11.[12b] C. A. Bunton, G. Savelli, Adv. Phys.
[12c]
Org. Chem. 1986, 22, 231–309. –
Interface Sci. 1994, 51, 137–174. –
ron 1996, 52, 11113–11152.
K. Holmberg, Adv. Coll.
[12d]
S. Tascioglu, Tetrahed-
[13] [13a]
J. A. Nikles, J. Sukenik, Tetrahedron Lett. 1982, 41, 4211–
[13b]
4214. –
M. Laxman, M. M. Sharma, Synth. Comm. 1990,
20, 111–117.
1d: 79% yield. – 1H NMR: δ ϭ 0.90 (s, 3 H, CH3), 0.93 (s, 3 H,
CH3), 1.28–1.80 (m, 8 H, 4CH2), 3.61 (m, 1 H, CH).
[14] [14a]
`
R. Fargues-Sakellariou, M. Riviere, A. Lattes, Nouv. J.
[14b]
Chim. 1985, 9, 95–100. –
D. A. Jaeger, M. D. Ward, C. A.
[14c]
Martin, Tetrahedron 1984, 40, 2691–2698. –
B. Jursic, D.
2d: As mentioned we could not obtain product 2d with our proced-
ures. For analysis purpose, we prepared it by reduction of the ke-
tone 2c with LiAlH4, obtaining the cis and trans saturated alcohols
as a diastereomeric mixture, with 84% yield. – 1H NMR: δ ϭ 0.72–
1.12 (m, 9 H, 3 CH3), 1.18–2.1 (m, 7 H, 3 CH2 and CH), 3.48–4.20
(m, 1 H, CH).
E. Sunko, J. Chem. Res.(S). 1988, 202–203. – [14d] C. Denis, B.
Laignel, D. Plusquellec, J.-Y. Le Marouille, A. Botrel, Tetrahed-
ron Lett. 1996, 37, 53–56.
[15]
[16]
A. Loupy, J. Seyden-Penne, Tetrahedron 1980, 36, 1937–1942.
L. Brinchi, P. Di Profio, R. Germani, G. Savelli, C. A. Bunton,
Colloids and Surfaces 1998, 132, 303–314.
L. Brinchi, P. Di Profio, R. Germani, G. Savelli, C. A. Bunton,
Langmuir 1997, 13, 4583–4587.
L. Brinchi, Ph. D. Dissertation, University of Perugia, 1998.
[17]
1
3d: 97% yield. – H NMR: δ ϭ 1.12 (d, J ϭ 6.16 Hz, 3 H, CH3),
[18]
1.68 (m, 2 H, CH2), 2.64 (m, 2 H, CH2), 3.75 (m, 1 H, CH), 7.10–
[19] [19a] C. A. Bunton, M. M. Mhala, J. R. Moffatt, L. S. Romsted,
7.21 (m, 5 H, C6H5); m.p. 70–71 °C (ref.[23] 71 °C).
[19b]
G. Savelli, J. Phys. Chem. 1981, 85, 4118–4125. –
R. Ger-
mani, P. P. Ponti, T. Romeo, G. Savelli, N. Spreti, G. Cerichelli,
L. Luchetti, G. Mancini, C. A. Bunton, J. Phys. Org. Chem.
1989, 2, 553–558.
1
4d: 92% yield. – H NMR: δ ϭ 2.08 (m, 2 H, CH2), 2.65 (m, 2 H,
CH2), 4.64 (t, J ϭ 6.62 Hz, 1 H, CH), 7.19–7.45 (m, 10 H, 2 C6H5).
[20]
[21]
[22]
[23]
F. G. Bordwell, K. M. Wellman, J. Org. Chem. 1963, 28,
1347–1352.
J. P. Battioni, A. Sevin, W. Chodkiewicz, Bull. Soc. Chim. Fr.
1970, 2713–2714.
Acknowledgments
Support of this work by Consiglio Nazionale delle Ricerche, Rome,
M. F. Semmelhack, R. D. Stauffer, A. Yamashita, J. Org.
Chem. 1977, 42, 3180–3188.
`
and by Ministero dellЈUniversita e Ricerca Scientifica, Rome.
´
´
´
`
´ ´
M. Tuot, M. Guyard, Memoires presentes a la Societe Chimique
1947, 1087–1096.
Received October 12, 1999
[O99574]
[1]
E. Keinan, N. Greenspoon, The Chemistry of Enones (Ed.: S.
Patai and Z. Rappoport) Wiley, New York, 1989, chapter 18.
Eur. J. Org. Chem. 2000, 1793Ϫ1797
1797