Palladium(0)-Lithium Iodide Cocatalyzed Asymmetric Hydroalkylation of Conjugated Enynes with Pronucleophiles Leading to 1,3-Disubstituted Allenes

Hirokazu Tsukamoto, Tatsuya Konno, Kazuya Ito, Takayuki Doi

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Axially chiral 1,3-disubstituted allenes were synthesized via hydroalkylation of alkyl- or aryl-substituted conjugated enynes (readily prepared via a Sonogashira reaction) with pronucleophiles such as dimethyl malonate under the cocatalysis of DTBM-SEGPHOS-ligated palladium and lithium iodide. Although the palladium catalyst ligated with (S)-DTBM-SEGPHOS prefers the formation of (R)-1,3-disubstituted allenes, lithium iodide recovers and increases the intrinsic selectivity producing (S)-allenes by promoting the isomerization of the exo-alkylidene-π-allylpalladium intermediate prior to the nucleophilic substitution step.

Original languageEnglish
Pages (from-to)6811-6814
Number of pages4
JournalOrganic letters
Volume21
Issue number17
DOIs
Publication statusPublished - 2019 Jul 14

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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