Torquoselective olefination with ynolates

Mitsuru Shindo, Seiji Mori

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

We have developed the torquoselectivity-controlled olefination of carbonyl compounds with ynolates to afford tetrasubstituted alkenes. In the olefination of acylsilanes, α-oxy and α-aminoketones, and esters, the high selectivity and yield have been achieved under mild conditions. The E/Z selectivity is determined in the step of electrocyclic ring-opening of the β-lactone enolates (oxetenes) derived from cycloaddition of ynolates with carbonyl compounds. The theoretical calculations revealed that the several secondary orbital interactions are critical for the high torquoselectivity. The E/Z selectivity can be estimated by considerations of the electronic properties of the substituents of carbonyl compounds, wherein the electron-donating substituents would be trans to the carboxylate on the olefins and the electron accepting ones cis to it. This methodology is the novel olefination constructing multisubstituted olefins.

Original languageEnglish
Pages (from-to)28-38
Number of pages11
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume66
Issue number1
DOIs
Publication statusPublished - Jan 1 2008

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Carbonyl compounds
Alkenes
Cycloaddition
Electrons
Lactones
Electronic properties
Esters

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Torquoselective olefination with ynolates. / Shindo, Mitsuru; Mori, Seiji.

In: Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, Vol. 66, No. 1, 01.01.2008, p. 28-38.

Research output: Contribution to journalArticle

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