Photochemical Cycloaddition of Singlet and Triplet Diphenylvinylene Carbonate with Conjugated Dienes

Frederick D Lewis*, Richard H. Hirsch

*Corresponding author for this work

Research output: Contribution to journalArticle

30 Scopus citations

Abstract

The singlet and triplet excited states of diphenylvinylene carbonate (V) react with conjugated dienes to produce 2 + 2 cycloadducts. The singlet reaction occurs with retention of diene stereochemistry via a singlet exciplex intermediate. Singlet cycloaddition is only moderately regioselective and stereoselective, indicative of a loosely bound exciplex intermediate. The triplet cycloaddition occurs with substantial loss of diene stereochemistry and high regioselectivity. The high triplet regioselectivity is a consequence of selective collapse of the more substituted biradical rather than selective bonding to the less substituted diene terminus. The regioselectivity of initial bonding is the same for the singlet and triplet reactions.

Original languageEnglish (US)
Pages (from-to)5914-5924
Number of pages11
JournalJournal of the American Chemical Society
Volume98
Issue number19
DOIs
StatePublished - Sep 1 1976

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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