Asymmetric Catalysis of Epoxide Ring-Opening Reactions
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- 16 May 2000
- journal article
- review article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 33 (6) , 421-431
- https://doi.org/10.1021/ar960061v
Abstract
The discovery of the metal salen-catalyzed asymmetric ring-opening (ARO) of epoxides is chronicled. A screening approach was adopted for the identification of catalysts for the addition of TMSN3 to meso-epoxides, and the chiral (salen)CrN3 complex was identified as optimal. Kinetic and structural studies served to elucidate the mechanism of catalysis, which involves cooperative activation of both epoxide and azide by two different metal centers. Covalently linked bimetallic complexes were constructed on the basis of this insight, and shown to catalyze the ARO with identical enantioselectivity but 1−2 orders of magnitude greater reactivity than the monomeric analogues. Extraordinarily high selectivity is observed in the kinetic resolution of terminal epoxides using the (salen)CrN3/TMSN3 system. A search for a practical method for the kinetic resolution reaction led to the discovery of highly enantiomer-selective hydrolytic ring-opening using the corresponding (salen)CoIII catalyst. This system displays extraordinary substrate generality, and allows practical access to enantiopure terminal epoxides on both laboratory and industrial scales.Keywords
This publication has 21 references indexed in Scilit:
- Asymmetric Catalytic Synthesis of α-Aryloxy Alcohols: Kinetic Resolution of Terminal Epoxides via Highly Enantioselective Ring-Opening with PhenolsJournal of the American Chemical Society, 1999
- Polymer-Supported Chiral Co(Salen) Complexes: Synthetic Applications and Mechanistic Investigations in the Hydrolytic Kinetic Resolution of Terminal EpoxidesJournal of the American Chemical Society, 1999
- An Enantioselective Synthesis of (−)-Allosamidin by Asymmetric Desymmetrization of a Highly Functionalized meso-EpoxideThe Journal of Organic Chemistry, 1999
- Cooperative Asymmetric Catalysis with Dimeric Salen ComplexesJournal of the American Chemical Society, 1998
- Mechanistic Studies of the Zirconium−Triisopropanolamine-Catalyzed Enantioselective Addition of Azide to Cyclohexene OxideThe Journal of Organic Chemistry, 1998
- Practical Synthesis of Enantiopure Cyclic 1,2-Amino Alcohols via Catalytic Asymmetric Ring Opening of Meso EpoxidesThe Journal of Organic Chemistry, 1997
- Efficient Synthesis of (R)-4-((Trimethylsilyl)oxy)-2-cyclopentenone by Enantioselective Catalytic Epoxide Ring OpeningThe Journal of Organic Chemistry, 1996
- Highly Enantioselective Ring Opening of Epoxides Catalyzed by (salen)Cr(III) ComplexesJournal of the American Chemical Society, 1995
- Enzymatic Ring-Opening Polymerization of Lactones to Polyesters by Lipase Catalyst: Unusually High Reactivity of MacrolidesBulletin of the Chemical Society of Japan, 1995
- Chiral Lewis acid catalysis. Enantioselective addition of azide to meso epoxidesJournal of the American Chemical Society, 1992