Palladium-Catalyzed Umpolung Type-II Cyclization of Allylic Carbonate-Aldehydes Leading to 3-Methylenecycloalkanol Derivatives

Hirokazu Tsukamoto, Ayumu Kawase, Takayuki Doi

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

Palladium-catalyzed umpolung type-II cyclization of allylic carbonate-aldehydes leading to 3-methylenecycloalkanol derivatives was developed. The formate reductant was effective for the cyclization without causing a reduction of the η3-allylpalladium intermediate. One-pot decarboxylative allylation of aldehyde-containing malonate with 2-[(acetyloxy)methyl]-2-propenyl methyl carbonate followed by the cyclization of the allyl acetate-aldehyde formed in situ was also achieved. The high diastereoselectivities observed in the cyclization of branched substrates indicates that a chair-chair transition state should be involved. Based on the presumed transition state, we could predict the enantioselectivity of the cyclization using SEGPHOS as a chiral diphosphine ligand and obtain optically active alcohols in up to 95:5 er. (Figure presented.).

Original languageEnglish
Pages (from-to)3733-3738
Number of pages6
JournalAdvanced Synthesis and Catalysis
Volume361
Issue number16
DOIs
Publication statusPublished - 2019 Aug 21

Keywords

  • allylic carbonate
  • diastereoselectivity
  • enantioselectivity
  • one-pot
  • palladium
  • umpolung cyclization

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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