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Incremental substituent effects leading to steric blockade of the boat-like six-center Cope rearrangement of cis-1,2-dialkenylcyclobutanes

Berson, Jerome A. and Dervan, Peter B. (1972) Incremental substituent effects leading to steric blockade of the boat-like six-center Cope rearrangement of cis-1,2-dialkenylcyclobutanes. Journal of the American Chemical Society, 94 (21). pp. 7597-7598. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20160516-100949422

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Abstract

Although the rate of the chair-like, four-center Cope rearrangement of acyclic biallyls is faster than that of the boat-like, six-center one by a factor greater than exp((6000 cal/mol)/RT), there are several cases in the literature in which the order of preference is qualitatively reversed. Among the earliest examples so interpreted are the thermal transformations of cis-1,2-dialkenylcyclobutanes to cis,cis-cycloocta-1,5-dienes. The normal preference for the chair-like pathway in these systems should be diminished because of the high strain energy of the product, a cis,trans-cycloocta-1,5-diene. Although the transient intermediacy of that substance cannot be excluded on purely energetic grounds, the present results strongly support the formulation of the rearrangement of cis-1,2-divinylcyclobutane to cis,cis-cycloocta-1,5-diene as a direct process via a boat-like transition state. Moreover, they show how cis-1,2-dialkenylcyclobutanes, already deprived of the normal chair-like pathway by product strain, can be subjected to incremental steric effects that gradually deny access even to the "second-best" boat-like reaction.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja00776a064DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00776a064PublisherArticle
ORCID:
AuthorORCID
Dervan, Peter B.0000-0001-8852-7306
Additional Information:© 1972 ACS. Received August 5, 1972. We thank the National Science Foundation (Grant No. GP11017X) and the Hoffmann-La Roche Foundation for partial support of this work.
Funders:
Funding AgencyGrant Number
NSFGP11017X
Hoffmann-La Roche FoundationUNSPECIFIED
Record Number:CaltechAUTHORS:20160516-100949422
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160516-100949422
Official Citation:Incremental substituent effects leading to steric blockade of the boat-like six-center Cope rearrangement of cis-1,2-dialkenylcyclobutanes Jerome A. Berson and Peter B. Dervan Journal of the American Chemical Society 1972 94 (21), 7597-7598 DOI: 10.1021/ja00776a064
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67124
Collection:CaltechAUTHORS
Deposited By: Victoria Brennan
Deposited On:17 May 2016 15:05
Last Modified:09 Nov 2017 00:05

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