Confinement-Controlled, Either syn- or anti-Selective Catalytic Asymmetric Mukaiyama Aldolizations of Propionaldehyde Enolsilanes

Amatov, Tynchtyk; Tsuji, Nobuya; Maji, Rajat; Schreyer, Lucas; Zhou, Hui; Leutzsch, Markus; List, Benjamin

Confinement-Controlled, Either syn- or anti-Selective Catalytic Asymmetric Mukaiyama Aldolizations of Propionaldehyde Enolsilanes

Amatov, Tynchtyk; Tsuji, Nobuya; Maji, Rajat et al.

Journal of the American Chemical Society, 2021, 143(36), 14475-14481

Permalink : https://hdl.handle.net/2115/83043

このアイテムのアクセス数:523件（2026-08-15 10:06 集計）

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ファイル	フォーマット	サイズ	閲覧回数	説明
https://doi.org/10.1021/jacs.1c07447			21

論文情報

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アクセス権	open access
URI	https://hdl.handle.net/2115/83043
タイトル	Confinement-Controlled, Either syn- or anti-Selective Catalytic Asymmetric Mukaiyama Aldolizations of Propionaldehyde Enolsilanes
著者	Amatov, Tynchtyk ; Tsuji, Nobuya ; Maji, Rajat ; Schreyer, Lucas ; Zhou, Hui ; Leutzsch, Markus ; List, Benjamin
著者名 Amatov, Tynchtyk
e-Rad_Researcher 30873575 著者名 Tsuji, Nobuya
著者名 Maji, Rajat
著者名 Schreyer, Lucas
著者名 Zhou, Hui
著者名 Leutzsch, Markus
e-Rad_Researcher 80899253 著者名 List, Benjamin
言語	英語
キーワード	Catalysts
	Aldehydes
	Metabolism
	Aldol reactions
	Stereoselectivity
発行日	2021-09-15
出版者	American Chemical Society
収録物名	Journal of the American Chemical Society
巻(号)	143(36)
ページ	14475-14481
抄録	Protected aldols (i.e., true aldols derived from aldehydes) with either syn- or anti- stereochemistry are versatile intermediates in many oligopropionate syntheses. Traditional stereoselective approaches to such aldols typically require several nonstrategic operations. Here we report two highly enantioselective and diastereoselective catalytic Mukaiyama aldol reactions of the TBS- or TES- enolsilanes of propionaldehyde with aromatic aldehydes. Our reactions directly deliver valuable silyl protected propionaldehyde aldols in a catalyst controlled manner, either as syn- or anti- isomer. We have identified a privileged IDPi catalyst motif that is tailored for controlling these aldolizations with exceptional selectivities. We demonstrate how a single atom modification in the inner core of the IDPi catalyst, replacing a CF3-group with a CF2H-group, leads to a dramatic switch in enantiofacial differentiation of the aldehyde. The origin of this remarkable effect was attributed to tightening of the catalytic cavity via unconventional C-H hydrogen bonding of the CF2H group.
資源タイプ	学術雑誌論文
出版タイプ	Version of Record
PISSN	0002-7863
関連情報 (isIdenticalTo)	出版社版DOI https://doi.org/10.1021/jacs.1c07447