Optically Active N,N′-Bis(3-oxobutylidene)diaminatomanganese(III) Complexes as Novel and Efficient Catalysts for Aerobic Enantioselective Epoxidation of Simple Olefins
- 1 May 1995
- journal article
- research article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 68 (5) , 1455-1465
- https://doi.org/10.1246/bcsj.68.1455
Abstract
A novel manganese(III) complex having an optically active N,N′-bis(3-oxobutylidene)diamine ligand with bulky substituents was prepared and characterized crystallographically. In the presence of a catalytic amount of the manganese(III) complex, unfunctionalized olefins were oxygenated to give optically active epoxides with molecular oxygen by the combined use of several aliphatic aldehydes. Cyclic and acyclic cis-β-substituted styrene derivatives, conjugated dienes, and enynes were converted into the corresponding epoxides with moderate-to-good enantioselectivities. The present aerobic and enantioselective epoxidation proceeded with the opposite enantioface selection from those obtained by using terminal oxidants, such as sodium hypochlorite and iodosylbenzene. The key intermediate of the aerobic asymmetric epoxidation is also discussed.Keywords
This publication has 36 references indexed in Scilit:
- Asymmetric epoxidation of olefins catalyzed by manganese complexes of chiral "strapped" porphyrins with diastereotopic faces. A novel strategy for stereochemical modeling of the active site of cytochrome P-450Journal of the American Chemical Society, 1992
- Catalytic properties of iron and manganese glycoconjugated porphyrins.Tetrahedron Letters, 1991
- Catalytic asymmetric epoxidation of unfunctionalized alkenes using the first D4-symmetric metallotetraphenylporphyrinThe Journal of Organic Chemistry, 1991
- Catalytic and asymmetric epoxidation of olefins with iron complexes of twin-coronet porphyrins. A mechanistic insight into the chiral induction of styrene derivativesJournal of the American Chemical Society, 1991
- Asymmetric olefin epoxidation with sodium hypochlorite catalyzed by easily prepared chiral manganese(III) salen complexesThe Journal of Organic Chemistry, 1991
- Enantioselective epoxidation of unfunctionalized olefins catalyzed by salen manganese complexesJournal of the American Chemical Society, 1990
- Catalytic asymmetric epoxidation of unfunctionalized olefinsTetrahedron Letters, 1990
- Synthesis and characterization of the "chiral wall" porphyrin: a chemically robust ligand for metal-catalyzed asymmetric epoxidationsJournal of the American Chemical Society, 1989
- Asymmetric epoxidation of simple olefins catalyzed by chiral diphosphine-modified platinum(II) complexesOrganometallics, 1987
- Catalytic asymmetric epoxidations with chiral iron porphyrinsJournal of the American Chemical Society, 1983