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Confinement-Controlled, Either syn- or anti-Selective Catalytic Asymmetric Mukaiyama Aldolizations of Propionaldehyde Enolsilanes
| Title: | Confinement-Controlled, Either syn- or anti-Selective Catalytic Asymmetric Mukaiyama Aldolizations of Propionaldehyde Enolsilanes |
| Authors: | Amatov, Tynchtyk Browse this author | | Tsuji, Nobuya Browse this author →KAKEN DB | | Maji, Rajat Browse this author | | Schreyer, Lucas Browse this author | | Zhou, Hui Browse this author | | Leutzsch, Markus Browse this author | | List, Benjamin Browse this author →KAKEN DB |
| Keywords: | Catalysts | | Aldehydes | | Metabolism | | Aldol reactions | | Stereoselectivity |
| Issue Date: | 15-Sep-2021 |
| Publisher: | American Chemical Society |
| Journal Title: | Journal of the American Chemical Society |
| Volume: | 143 |
| Issue: | 36 |
| Start Page: | 14475 |
| End Page: | 14481 |
| Publisher DOI: | 10.1021/jacs.1c07447 |
| Abstract: | 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. |
| Type: | article |
| URI: | http://hdl.handle.net/2115/83043 |
| Appears in Collections: | 化学反応創成研究拠点：ICReDD (Institute for Chemical Reaction Design and Discovery : ICReDD) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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