NUCLEOPHILIC RING-OPENING OF EPOXIDES BY ORGANOLITHIUM COMPOUNDS - AB-INITIO MECHANISMS

Journal article


Publication Details

Author(s): Harder S, van Lenthe J, van Eikema Hommes N, Schleyer P
Journal: Journal of the American Chemical Society
Publisher: American Chemical Society
Publication year: 1994
Volume: 116
Journal issue: 6
Pages range: 2508-2514
ISSN: 0002-7863


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.



FAU Authors / FAU Editors

Harder, Sjoerd Prof. Dr.
Lehrstuhl für Anorganische und Metallorganische Chemie
Schleyer, Paul Prof. Dr.
Naturwissenschaftliche Fakultät
van Eikema Hommes, Nico Dr.
Computer-Chemie-Centrum


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://dx.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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Last updated on 2018-19-04 at 03:17