Development of direct enantioselective alkynylation of αketoester and α-ketiminoesters catalyzed by phenylbis(oxazoline)Rh(III) complexes

Kazuhiro Morisaki, Hiroyuki Morimoto, Kazushi Mashima, Takashi Ohshima

研究成果: Contribution to journalArticle査読

1 被引用数 (Scopus)

抄録

Direct catalytic enantioselective alkynylation of carbonyl compounds and imines is one of the most efficient approaches for the synthesis of propargylic alcohols and propargylamines, which are potent building blocks for synthesizing functionalized molecules. While a variety of methods for the reactions with aldehydes and aldimines have been established, the reactions with ketones and ketimines remain underdeveloped due to their reduced reactivity and difficulty in stereocontrol. In this account, we summarized our studies on direct enantioselective alkynylation reaction of α-ketoester and α-ketiminoesters catalyzed by phenylbis(oxazolinephebox)-rhodium(III) complexes, affording enantioenriched propargyl alcohols and propargylamines with a tetrasubsti-tuted carbon stereocenter under proton-transfer conditions. The catalytic system was compatible to a wide range of functional groups, including electrophilic formyl groups, and allowed for the development of an efficient method to access enantioenriched α-CF3-substituted thalidomide analogs. Mechanistic studies revealed that generation of the (alkynyl(phebox)Rh(III) complex from the (diacetatophebox)Rh(III) complex determined the overall reaction rate in the initial stages of the reaction. These results, along with the observed facile exchange of the alkynyl ligand on the (alkynylphebox)Rh(III) complexes, led us to use (trimethylsilylethynylphebox)Rh(III) complexes as a new pre-catalyst. The new catalytic system with (trimethylsilylethynylphebox)Rh (III) precatalysts exhibited enhanced catalytic performance, reduced catalyst loading to as low as 0.5 mol%, and expanded the substrate scope of the reaction with less reactive α-ketiminophos-phonate and cyclic N-sulfonyl α-ketiminoesters.

本文言語英語
ページ(範囲)226-240
ページ数15
ジャーナルYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
76
3
DOI
出版ステータス出版済み - 2018

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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