Nonconvergent Cycloaddition Pathways for Thermal vs. Photochemical Reaction of N-Isobutenylpyrrolidine with Dimethyl Fumarate

Frederick D Lewis*, Tong Ing Ho, Robert J. DeVoe

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Scopus citations

Abstract

The thermal reaction of the title compounds proceeds via a reversibly formed 1,4-zwitterion intermediate to yield the thermodynamically most stable [2 + 2] cycloadduct. The rate of the thermal reaction is substantially faster in moderately polar vs. nonpolar solvent. In contrast, the photochemical reaction of the title compounds occurs only in nonpolar solvent and yields a stereoisomer of the thermal adduct. Photochemical cycloaddition is not observed for several other α,β-unsaturated esters and enamines. The mechanism of the photochemical reaction and the failure to observe photochemical ionic [2 + 2] cycloaddition are discussed.

Original languageEnglish (US)
Pages (from-to)5283-5286
Number of pages4
JournalJournal of Organic Chemistry
Volume45
Issue number26
DOIs
StatePublished - Jan 1 1980

ASJC Scopus subject areas

  • Organic Chemistry

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