Cationic Iridium/Chiral Bisphosphine-Catalyzed Enantioselective Hydroacylation of Ketones

Tomohiko Shirai, Tomoya Iwasaki, Kazuya Kanemoto, Yasunori Yamamoto

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)


A facile and convenient synthesis of the chiral phthalide framework catalyzed by cationic iridium was developed. The method utilized cationic iridium/bisphosphine-catalyzed asymmetric intramolecular carbonyl hydroacylation of 2-keto benzaldehydes to furnish the corresponding optically active phthalide products in good to excellent enantioselectivities (up to 98% ee). The mechanistic studies using a deuterium-labelled substrate suggested that the reaction involved an intramolecular carbonyl insertion mechanism to iridium hydride intermediate. In addition, we investigated the kinetic isotope effect (KIE) of intramolecular hydroacylation with deuterated substrate and determined that the C−H activation step is not included in the turnover-limiting step.

Original languageEnglish
Pages (from-to)1858-1862
Number of pages5
JournalChemistry - An Asian Journal
Issue number12
Publication statusPublished - 2020 Jun 17
Externally publishedYes


  • cationic iridium
  • C−H activation
  • enantioselective
  • hydroacylation
  • ketone

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry


Dive into the research topics of 'Cationic Iridium/Chiral Bisphosphine-Catalyzed Enantioselective Hydroacylation of Ketones'. Together they form a unique fingerprint.

Cite this