| Literature DB >> 26797012 |
Chun Liu1, E Zachary Oblak1, Mark N Vander Wal1, Andrew K Dilger1, Danielle K Almstead1, David W C MacMillan1.
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.Entities:
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Year: 2016 PMID： 26797012 PMCID： PMC5103282 DOI： 10.1021/jacs.5b13041
Source DB: PubMed Journal: J Am Chem Soc ISSN： 0002-7863 Impact factor: 15.419