Homolytic rearrangements of bicyclo[2.2.0]hexane and bicyclo[3.2.0]heptane

John C. Walton*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)

Abstract

Free radicals abstract hydrogen from both the bridge and bridgehead sites in bicyclo[2.2.0]hexane (4). The bicyclo[2.2.0]hexan-1-yl radical was observed by e.p.r. spectroscopy. The bicyclo[2.2.0]hexan2-yl radical rearranges by stereoelectronically forbidden β-scission to give cyclohex-3-enyl radicals. Unlike other cyclobutanes, compound (4) undergoes an SH2 reaction with bromine atoms. Free radicals abstract hydrogen only from the methylene groups of the C5 ring in bicyclo[3.2.0]heptane (15a). The bicyclo[3.2.0] heptan-2-yl radicals were observed by e.p.r. spectroscopy, as was their rearrangement, by stereoelectronically allowed β-scission, to 2-(cyclopent-2-enyl)ethyl radicals. Bromine atoms abstract hydrogen from (15a) and no SH2 reaction was detected. The radicals and their rearrangements were studied by semi-empirical MlNDO/3 and MNDO methods.

Original languageEnglish
Pages (from-to)1371-1376
Number of pages6
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number7
DOIs
Publication statusPublished - 1 Jan 1988

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