About cookies on this site Our websites require some cookies to function properly (required). In addition, other cookies may be used with your consent to analyze site usage, improve the user experience and for advertising. For more information, please review your options. By visiting our website, you agree to our processing of information as described in IBM’sprivacy statement. To provide a smooth navigation, your cookie preferences will be shared across the IBM web domains listed here.
Paper
Stereochemistry of the (2′-Vinylcyclopropyl)cyclobutane Rearrangement. Photochemical 1,3 Addition of Benzene to 3,4-Substituted Cyclobutenes
Abstract
Thermal isomerization of cis-4,5-dimethyl-endo-tetracyclo[5.3.0.02,10.03,6]decene-8 (IX) at 300° gave rise to endo, cis-8,9-dimethyltricyclo[2.2.1.04,10]deca-2,5-diene (XII) as the major isomeric product. The reaction, which is a typical (2′-vinylcyclopropyl)cyclobutane rearrangement, thus proceeds with retention of the stereochemistry at the migrating σ bond. Arguments are presented to show that this rearrangement is distinct from the homo [1,5] sigmatropic shift which in the tricyclo[3.3.0.02,8]octene-3 systems involves the migration of hydrogen atoms only. It is also distinct from, although related to, the vinylcyclopropane rearrangement. The use of the (2′-vinylcyclopropyl)cyclobutane rearrangement in synthesis is exemplified by the preparation of endo-tetracyclo[8.2.1.02,6.-077,13]trideca-3,8,11-triene (VII) from benzene and 1,3,5-cycloheptatriene in three steps. © 1972, American Chemical Society. All rights reserved.