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.
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| 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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| 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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