Intramolecular Photochemical Cycloaddition Reactions of 3-(1,5-Dimethylhex-4-enyl)cyclohex-2-enone: Regio- and Stereochemical Aspects

Thomas R Hoye, Steven J. Martin, David R. Peck

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34 Scopus citations

Abstract

The intramolecular photocycloaddition reaction of the title enone (1) and its 1-demethyl analogue (2) gives head-to-head, [2 + 2] adducts containing cyclopenta[1,4]cyclobuta[1,2]benzen-5(6H)-one skeletons and none of the head-to-tail isomers of the tricyclo[5.3.1.02,7]undecan-3-one variety. In addition, formal photoene adducts of a spiro[5,4]decan-3-one nature which are related to the acorane sesquiterpene carbon skeleton are also observed. The stereochemical consequences of the acyclic methyl-bearing chiral center in 1 are probed, and the ratio of epimeric products is found to be temperature dependent. Attempts to thermally convert the gem-dimethylcyclobutane moiety in the [2 + 2] adducts to spirocyclic precursors of the acoranes results instead in reversion to starting enone.

Original languageEnglish (US)
Pages (from-to)331-337
Number of pages7
JournalJournal of Organic Chemistry
Volume47
Issue number2
DOIs
StatePublished - Jan 1 1982

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