Oxy-Allyl Cation Catalysis: An Enantioselective Electrophilic Activation Mode

Journal of the American Chemical Society
Chun LiuDavid W C MacMillan

Abstract

A generic activation mode for asymmetric LUMO-lowering catalysis has been developed using the long-established principles of oxy-allyl cation chemistry. Here, the enantioselective conversion of racemic α-tosyloxy ketones to optically enriched α-indolic carbonyls has been accomplished using a new amino alcohol catalyst in the presence of electron-rich indole nucleophiles. Kinetic studies reveal that the rate-determining step in this S(N)1 pathway is the catalyst-mediated α-tosyloxy ketone deprotonation step to form an enantiodiscriminant oxy-allyl cation prior to the stereodefining nucleophilic addition event.

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Citations

May 13, 2017·The Journal of Organic Chemistry·Marcel Schlegel, Christoph Schneider
Jul 26, 2017·Organic Letters·Michael TopinkaMichael Harmata
Aug 24, 2017·Angewandte Chemie·Tobias StopkaNuno Maulide
Sep 1, 2018·Chemical Communications : Chem Comm·Min-Hua HuangBo Jiang
Nov 6, 2018·Chemical Society Reviews·Zengsheng YinPauline Chiu
Oct 30, 2018·Chemical Communications : Chem Comm·Yi-Ru ChenWenwei Lin
Sep 8, 2018·Angewandte Chemie·Mirza A SaputraRendy Kartika
Aug 5, 2020·Chemical Communications : Chem Comm·Takumi AbeToshiki Yamashiro
Dec 12, 2020·Angewandte Chemie·Melania Gómez-MartínezOlga García Mancheño
Feb 27, 2021·Organic Letters·Bruna S MartinsNuno Maulide
Dec 7, 2018·Chemical Reviews·Shinji Yamada
Mar 27, 2018·Organic Letters·Santu Sadhukhan, Beeraiah Baire
May 6, 2019·The Journal of Organic Chemistry·Caitlin G BresnahanRendy Kartika

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