Reinvestigation of the reactions of camphorketene: Structural evidence for pseudopericyclic pathways1

W. W. Shumway, N. Kent Dalley, D. M. Birney

Research output: Contribution to journalArticle

66 Scopus citations

Abstract

The stereochemistry of the dimers (3 and 4) of camphorketene (2) have been determined. The crystal structures of 3, 20 and of related compounds show ground-state distortions that are interpreted as prefiguring planar, pseudopericyclic transition states for retro-cycloadditions to form α-oxoketenes. The B3LYP/6-31G optimized geometry for the transition structure (10) for the dimerization of s-Z-formylketene (8) is consistent with this mechanism. Trapping of 2 with alcohols shows selectivity comparable to other α-oxoketenes. The lack of reaction of 2 with benzaldehyde and the lack of enol tautomers in camphoric acid derivatives is attributed to angle strain in the bicyclic camphor moiety.

Original languageEnglish
Pages (from-to)5832-5839
Number of pages8
JournalJournal of Organic Chemistry
Volume66
Issue number17
DOIs
StatePublished - Aug 24 2001

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