An Efficient Method for the Direct Peroxygenation of Various Olefinic Compounds with Molecular Oxygen and Triethylsilane Catalyzed by a Cobalt(II) Complex
Author:
- 1 May 1990
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 63 (5) , 1305-1310
Abstract
An efficient method for the direct peroxygenation of various olefinic compounds with molecular oxygen and triethylsilane (Et3SiH) was developed by the use of a catalytic amount of a bis(1,3-diketonato)cobalt(II) complex. According to the above method, 1-phenyl-3-triethylsilydioxybutane (2) was directly produced from 4-phenyl-1-butene (1) by means of a reaction with O2 and Et3SiH at room temperature. Styrene (3) and ethyl acrylate (5a) were also smoothly peroxygenated to give 1-phenyl-1-triethylsilyldioxyethane (4) and ethyl 2-triethylsilyldioxypropionate (6a) by using a small amount of t-BuOOH as an initiator. The successive desilylation of 6a and reduction of the resulting ethyl 2-hydroperoxypropionate (8a) afforded the corresponding alcohol, ethyl lactate (10a), in a high yield. The synthetic utility of the present peroxygenation reaction was demonstrated in the preparation of α-hydroxy esters 10a–e from several α,β-unsaturated esters 5a–e via the corresponding triethylsilyldioxy derivatives.Keywords
This publication has 12 references indexed in Scilit:
- Catalysis of cobalt-Schiff base complexes in oxygenation of alkenes: on the mechanism of ketonizationJournal of Molecular Catalysis, 1988
- Asymmetric induction in oxygenation of styrene catalyzed by cobalt schiff base complexTetrahedron Letters, 1988
- Mechanistic studies on the cobalt(II) Schiff base catalyzed oxidation of olefins by O2Journal of the American Chemical Society, 1987
- Kinetics and mechanism of reductive dioxygen activation catalyzed by P-450 model system. Iron picket fence as a catalytic centerJournal of the American Chemical Society, 1985
- Steric and electronic effects of ligand variation on cobalt dioxygen catalystsJournal of the American Chemical Society, 1985
- Oxygenation of olefins under reductive conditions. Cobalt-catalyzed selective conversion of aromatic olefins to benzylic alcohols by molecular oxygen and tetrahydroborateThe Journal of Organic Chemistry, 1984
- Novel catalytic oxidations of terminal olefins by cobalt(II)-Schiff base complexesJournal of the American Chemical Society, 1982
- P-450 type oxygen activation by porphyrin-manganese complexJournal of the American Chemical Society, 1979
- Organoelementperoxide von elementen der 4. HauptgruppeJournal of Organometallic Chemistry, 1974
- The Synthesis of Silyl Hydroperoxides and Bissilyl Peroxides1The Journal of Organic Chemistry, 1965