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Mechanistic analysis of the four pathways in the 1,3-sigmatropic rearrangements of trans-1,2-trans, trans- and trans-1,2-cis,trans-dipropenylcyclobutane

Berson, Jerome A. and Dervan, Peter B. (1973) Mechanistic analysis of the four pathways in the 1,3-sigmatropic rearrangements of trans-1,2-trans, trans- and trans-1,2-cis,trans-dipropenylcyclobutane. Journal of the American Chemical Society, 95 (1). pp. 269-270. ISSN 0002-7863. doi:10.1021/ja00782a062. https://resolver.caltech.edu/CaltechAUTHORS:20160516-100433710

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Abstract

The orbital symmetry allowed and forbidden 1,3-sigmatropic rearrangements of a trans-2-substituted-ltrans-propenylcyclobutane (e.g.. tTT. Scheme I) would give, respectively a trans- and a cis-3,4-disubstituted cyclohexene (e.g., 1 and 2). Thus, an evaluation of the relative importance of the two processes would be available merely from a determination of the trans/cis product ratio. However, a more complete mechanistic analysis would require dissection of the allowed and forbidden reactions into two subreactions each. These can be categorized according to whether the migrating carbon retains or inverts its configuration (r or i) and whether the allylic receptor framework participates in a suprafacial or antarafacial way (s or a). The use of optically active reactants now permits this analysis.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/ja00782a062DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00782a062PublisherArticle
ORCID:
AuthorORCID
Dervan, Peter B.0000-0001-8852-7306
Additional Information:© 1973 American Chemical Society. Received July 28, 1972. Publication Date: January 1973. We thank the National Science Foundation (Grant No. GP-33909X) and the Hoffmann-La Roche Foundation for partial support of this work.
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Funding AgencyGrant Number
NSFGP-33909X
Hoffmann-La Roche FoundationUNSPECIFIED
Issue or Number:1
DOI:10.1021/ja00782a062
Record Number:CaltechAUTHORS:20160516-100433710
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160516-100433710
Official Citation:Mechanistic analysis of the four pathways in the 1,3-sigmatropic rearrangements of trans-1,2-trans, trans- and trans-1,2-cis,trans-dipropenylcyclobutane Jerome A. Berson and Peter B. Dervan Journal of the American Chemical Society 1973 95 (1), 269-270 DOI: 10.1021/ja00782a062
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67120
Collection:CaltechAUTHORS
Deposited By: Victoria Brennan
Deposited On:17 May 2016 22:47
Last Modified:11 Nov 2021 00:27

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