Stereoselective olefination of unfunctionalized ketones via ynolates

Mitsuru Shindo, Yusuke Sato, Takashi Yoshikawa, Ryoko Koretsune, Kozo Shishido

Research output: Contribution to journalArticlepeer-review

54 Citations (Scopus)


Ynolates react with ketones at room temperature to afford α,β,β,-trisubstituted acrylates (tetra-substituted olefins) with 2:1-8:1 geometrical selectivities. This can be regarded as a new olefination reaction of ketones giving tetrasubstituted olefins in good yield, even in the case of sterically hindered substrates. The reaction mechanism involves cycloaddition of ynolates with a carbonyl group and subsequent thermal electrocyclic ring-opening of the resulting β-lactone enolates. The stereoselectivity is determined in the ring-opening, which is regulated by torquoselectivity. In this paper, we describe the scope and limitations of olefination of ketones via ynolates and discuss the stereocontrol mechanism.

Original languageEnglish
Pages (from-to)3912-3916
Number of pages5
JournalJournal of Organic Chemistry
Issue number11
Publication statusPublished - May 28 2004
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Organic Chemistry


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