Photoinduced electron-transfer, pyrolyses, and direct irradiation reactions of 2-methylenecyclobutanones: Regioselective bond cleavage depends on the substituents and the method of activation

Hiroshi Ikeda, Futoshi Tanaka, Tsutomu Miyashi, Kimio Akiyama, Shozo Tero-Kubota

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The regioselectivity of bond cleavage and the subsequent reactivity of 4-methylene-3,3-dimethyl-2,2-diphenylcyclobutan-1-one (5) and 4-isopropylidene-2,2-diphenylcyclobutan-1-one (6) in photoinduced electron transfer, pyrolysis, and direct irradiation reactions were investigated. Novel photoinduced electron-transfer rearrangements of 5 and 6 were found to occur through 1,4-diyl radical cations formed by C1-C2 cleavage of 5.+ and 6.+; that is, similarly to radical-cation Norrish type I cleavage, but in contrast to the diansyl derivative 1.+ corresponding to 5 .+, which gives an oxatetramethyleneethane (OTME)-type radical cation through C2-C3 cleavage. In contrast, solvent effects on the thermal rearrangement of 5 to 6 and theoretical calculations suggested the intervention of an OTME-type diradical intermediate 16.. formed by homolytic C2-C3 cleavage of 5. In direct photoreactions, 5 and 6 undergo [2+2] cycloreversion to give 1,1-diphenylethylenes and methyleneallenes, which are explained by both C1-C2 and C3-C4 cleavage. Consequently, the regioselectivity of 5 and 6 in bond cleavage and their reactivity strongly depend on the substituents and the method of activation.

Original languageEnglish
Pages (from-to)1500-1508
Number of pages9
JournalEuropean Journal of Organic Chemistry
Issue number7
DOIs
Publication statusPublished - 2004 Mar 26

Keywords

  • Bond cleavage
  • Electron transfer
  • Methylenecyclobutanone
  • Photochemistry
  • Regioselectivity

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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