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

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Amatov,  Tynchtyk
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Maji,  Rajat
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Schreyer,  Lucas
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Zhou,  Hui
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Leutzsch,  Markus
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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List,  Benjamin
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Japan;

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Citation

Amatov, T., Tsuji, N., Maji, R., Schreyer, L., Zhou, H., Leutzsch, M., et al. (2021). Confinement-Controlled, Either syn- or anti-Selective Catalytic Asymmetric Mukaiyama Aldolizations of Propionaldehyde Enolsilanes. Journal of the American Chemical Society, 143(36), 14475-14481. doi:10.1021/jacs.1c07447.


Cite as: http://hdl.handle.net/21.11116/0000-0009-16C5-0
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.