Rhenium-catalyzed synthesis of 2 H -1,2-oxaphosphorin 2-oxides via the regio- and stereoselective addition reaction of β-keto phosphonates with alkynes

Masahito Murai, Masahiro Nakamura, Kazuhiko Takai

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Treatment of β-keto phosphonates (Horner-Wadsworth-Emmons reagents) with terminal alkynes in the presence of a rhenium catalyst gave 2H-1,2-oxaphosphorin 2-oxides with various substitution patterns. The reaction proceeds via two consecutive processes: cleavage of a carbon-carbon σ-bond of the β-keto phosphonate with insertion of the alkyne in a regio- and stereoselective manner, followed by cyclization of the resulting δ-phosphonyl α,β-unsaturated ketone yielding the 2H-1,2-oxaphosphorin 2-oxide. Horner-Wadsworth-Emmons reagents were found to add to nonpolar unsaturated compounds under neutral conditions.

Original languageEnglish
Pages (from-to)5784-5787
Number of pages4
JournalOrganic Letters
Volume16
Issue number21
DOIs
Publication statusPublished - Nov 7 2014

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Rhenium
Organophosphonates
Addition reactions
Alkynes
rhenium
alkynes
Oxides
reagents
Carbon
Unsaturated compounds
oxides
carbon
Cyclization
synthesis
Ketones
ketones
insertion
cleavage
Substitution reactions
substitutes

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Biochemistry

Cite this

Rhenium-catalyzed synthesis of 2 H -1,2-oxaphosphorin 2-oxides via the regio- and stereoselective addition reaction of β-keto phosphonates with alkynes. / Murai, Masahito; Nakamura, Masahiro; Takai, Kazuhiko.

In: Organic Letters, Vol. 16, No. 21, 07.11.2014, p. 5784-5787.

Research output: Contribution to journalArticle

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