Photochemistry of α,β-Unsaturated Thiones: Cycloaddition to Electron-Deficient Olefins from Higher Excited States

V. Pushkara Rao, V. Ramamurthy

Research output: Contribution to journalArticle

7 Scopus citations

Abstract

Electron-deficient olefins add to thioenone 1 upon ππ* excitation. Cycloaddition occurs to the thiocarbonyl chromophore preferentially from the less-hindered side to yield thietanes. Thietane formation is stereospecific and regioselective. This addition has been inferred to originate from the second excited singlet, S2(ππ*), state. The exciplex intermediacy has been inferred from the dependence of the fluorescence quenching rate constant on the electron-acceptor properties of the olefin. The observed site specificity and regioselectivity are rationalized on the basis of PMO theory. The observed photochemical behavior of thioenone is different from that of enones.

Original languageEnglish (US)
Pages (from-to)332-339
Number of pages8
JournalJournal of Organic Chemistry
Volume53
Issue number2
DOIs
StatePublished - Jan 1 1988
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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