Mechanistic Studies and Expansion of the Substrate Scope of Direct Enantioselective Alkynylation of α-Ketiminoesters Catalyzed by Adaptable (Phebox)Rhodium(III) Complexes

Kazuhiro Morisaki, Masanao Sawa, Ryohei Yonesaki, Hiroyuki Morimoto, Kazushi Mashima, Takashi Ohshima

研究成果: Contribution to journalArticle査読

54 被引用数 (Scopus)

抄録

Mechanistic studies and expansion of the substrate scope of direct enantioselective alkynylation of α-ketiminoesters catalyzed by adaptable (phebox)rhodium(III) complexes are described. The mechanistic studies revealed that less acidic alkyne rather than more acidic acetic acid acted as a proton source in the catalytic cycle, and the generation of more active (acetato-κ2O,O′)(alkynyl)(phebox)rhodium(III) complexes from the starting (diacetato)rhodium(III) complexes limited the overall reactivity of the reaction. These findings, as well as facile exchange of the alkynyl ligand on the (alkynyl)rhodium(III) complexes led us to use (acetato-κ2O,O′)(trimethylsilylethynyl)(phebox)rhodium(III) complexes as a general precatalyst for various (alkynyl)rhodium(III) complexes. Use of the (trimethylsilylethynyl)rhodium(III) complexes as precatalysts enhanced the catalytic performance of the reactions with an α-ketiminoester derived from ethyl trifluoropyruvate at a catalyst loading as low as 0.5 mol % and expanded the substrate scope to unprecedented α-ketiminophosphonate and cyclic N-sulfonyl α-ketiminoesters.

本文言語英語
ページ(範囲)6194-6203
ページ数10
ジャーナルJournal of the American Chemical Society
138
19
DOI
出版ステータス出版済み - 5 18 2016

All Science Journal Classification (ASJC) codes

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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