Palladium(0)-Catalyzed Anti-Selective Addition-Cyclizations of Alkynyl Electrophiles

Hirokazu Tsukamoto, Kazuya Ito, Tatsuhiko Ueno, Mitsugu Shiraishi, Yoshinori Kondo, Takayuki Doi

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1 Citation (Scopus)


Palladium(0)/monophosphine complexes catalyze anti-selective alkylative, arylative, and alkynylative cyclizations of alkynyl electrophiles with organometallic reagents. The remarkable anti-selectivity results from novel oxidative addition, that is, the nucleophilic attack of electron-rich palladium(0) on the electrophile across the alkyne followed by transmetalation and reductive elimination (“anti-Wacker”-type cyclization). With regard to 5-alkynals, triphenylphosphine (PPh3)-ligated palladium(0) catalyzes the cyclization of terminal alkynes and conjugated alkenyl- or alkynyl-substituted ones to afford 2-cyclohexen-1-ol and 2-alkylidene-cyclopentanol derivatives, respectively. For 6-alkyl- or 6-aryl-5-alkynals, the cyclization does not proceed with the palladium/PPh3 catalyst; however, it does proceed with palladium/tricyclohexylphosphine (PCy3), to yield the former products predominantly. Remarkably, the latter catalyst completely switches the regioselectivity in the cyclization of the conjugated diyne-aldehydes. Notably, palladium/PPh3-catalyzed cyclizations also proceed with other organometallics or even without them.

Original languageEnglish
Article numbere202203068
JournalChemistry - A European Journal
Issue number6
Publication statusPublished - 2023 Jan 27


  • anti-selective cyclization
  • conjugated alkyne
  • oxidative addition
  • palladium
  • phosphine

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry


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