NUCLEOPHILIC RING-OPENING OF EPOXIDES BY ORGANOLITHIUM COMPOUNDS - AB-INITIO MECHANISMS
Harder S, van Lenthe J, van Eikema Hommes N, Schleyer P (1994)
Publication Status: Published
Publication Type: Journal article
Publication year: 1994
Journal
Publisher: American Chemical Society
Book Volume: 116
Pages Range: 2508-2514
Journal Issue: 6
DOI: 10.1021/ja00085a035
Abstract
Ab initio calculations (MP4/6-31+G*//6-31+G*+DELTAZPE) have been performed on the ring-opening reaction of ethylene oxide by monomeric and dimeric lithium hydride and by dimeric methyllithium, both with retention and with inversion of configuration at the carbon being attacked. Several highly ionic transition structures were located. The large preference for reaction with inversion is due to the higher degree of rupture of the C-O bond in the retention transition structure. Cationic assistance, i.e. Li+ coordination to the epoxide oxygen, significantly lowers the activation energies. An intermolecular push-pull mechanism, or an intramolecular mechanism in which the lithium aggregate is opened to form a chain, is proposed for reaction in moderately polar solvents.
Authors with CRIS profile
Sjoerd Harder
Lehrstuhl für Anorganische und Metallorganische Chemie
Nicolaas van Eikema Hommes
Computer-Chemie-Centrum (CCC)
Paul Schleyer
Naturwissenschaftliche Fakultät
Involved external institutions
Netherlands (NL)How to cite
APA:
Harder, S., van Lenthe, J., van Eikema Hommes, N., & Schleyer, P. (1994). NUCLEOPHILIC RING-OPENING OF EPOXIDES BY ORGANOLITHIUM COMPOUNDS - AB-INITIO MECHANISMS. Journal of the American Chemical Society, 116(6), 2508-2514. https://doi.org/10.1021/ja00085a035
MLA:
Harder, Sjoerd, et al. "NUCLEOPHILIC RING-OPENING OF EPOXIDES BY ORGANOLITHIUM COMPOUNDS - AB-INITIO MECHANISMS." Journal of the American Chemical Society 116.6 (1994): 2508-2514.
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