Stereoselective synthesis of tetrasubstituted alkenes via torquoselectivity-controlled olefination of carbonyl compounds with ynolates

Mitsuru Shindo, Kenji Matsumoto

Research output: Chapter in Book/Report/Conference proceedingChapter

28 Citations (Scopus)

Abstract

The efficient synthesis of tetrasubstituted alkenes by the olefination of carbonyl compounds with ynolates is described. This reaction involves the cycloaddition of ynolates with carbonyl groups, followed by electrocyclic ring-opening of the resulting β-lactone enolates. Orbital symmetry during the electrocyclic ring opening requires conrotatory motion. The direction of this rotation (inward or outward) determines the E/Z geometry to the tetrasubstituted olefin product through torquoselectivity. Theoretical calculations revealed that several secondary orbital interactions are essential for the high torquoselectivity. This methodology is a novel olefination for constructing multisubstituted olefins.

Original languageEnglish
Title of host publicationStereoselective Alkene Synthesis
EditorsJianbo Wang
Pages1-32
Number of pages32
DOIs
Publication statusPublished - Oct 8 2012

Publication series

NameTopics in Current Chemistry
Volume327
ISSN (Print)0340-1022

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Carbonyl compounds
Alkenes
Cycloaddition
Cycloaddition Reaction
Lactones
Geometry

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Shindo, M., & Matsumoto, K. (2012). Stereoselective synthesis of tetrasubstituted alkenes via torquoselectivity-controlled olefination of carbonyl compounds with ynolates. In J. Wang (Ed.), Stereoselective Alkene Synthesis (pp. 1-32). (Topics in Current Chemistry; Vol. 327). https://doi.org/10.1007/128-2012-313

Stereoselective synthesis of tetrasubstituted alkenes via torquoselectivity-controlled olefination of carbonyl compounds with ynolates. / Shindo, Mitsuru; Matsumoto, Kenji.

Stereoselective Alkene Synthesis. ed. / Jianbo Wang. 2012. p. 1-32 (Topics in Current Chemistry; Vol. 327).

Research output: Chapter in Book/Report/Conference proceedingChapter

Shindo, M & Matsumoto, K 2012, Stereoselective synthesis of tetrasubstituted alkenes via torquoselectivity-controlled olefination of carbonyl compounds with ynolates. in J Wang (ed.), Stereoselective Alkene Synthesis. Topics in Current Chemistry, vol. 327, pp. 1-32. https://doi.org/10.1007/128-2012-313
Shindo, Mitsuru ; Matsumoto, Kenji. / Stereoselective synthesis of tetrasubstituted alkenes via torquoselectivity-controlled olefination of carbonyl compounds with ynolates. Stereoselective Alkene Synthesis. editor / Jianbo Wang. 2012. pp. 1-32 (Topics in Current Chemistry).
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