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Gosteli-Claisen Rearrangement: DFT Study of Substituent-Rate Effects

Rehbein, Julia and Hiersemann, M. 2009. Gosteli-Claisen Rearrangement: DFT Study of Substituent-Rate Effects. Journal of Organic Chemistry 74 (11) , pp. 4336-4342. 10.1021/jo900635k

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The uncatalyzed Gosteli−Claisen rearrangement of four double bond isomeric allyl vinyl ethers has been studied at the B3LYP/6-31G* and B3LYP/6-31G*+PCM levels of theory. The experimentally determined structure−reactivity relationship was successfully reproduced; the relative reactivity of the (E,E)-, (E,Z)-, (Z,E)-, and (Z,Z)-configured allyl vinyl ethers can be attributed to unfavorable interactions caused by pseudoaxial substituents within the chairlike transition-state structures. As expected, the isolated assessment of the calculated ground-state or transition-state stabilities is not suitable to explain the experimentally observed structure−reactivity relationship.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: ACS
ISSN: 0022-3263
Last Modified: 19 Mar 2016 22:21

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