Oxy-Allyl Cation Catalysis: An Enantioselective Electrophilic Activation Mode

Chun Liu, E. Zachary Oblak, Mark N. Vander Wal, Andrew K. Dilger, Danielle K. Almstead, David W.C. MacMillan

Research output: Contribution to journalArticle

41 Scopus citations

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 SN1 pathway is the catalyst-mediated α-tosyloxy ketone deprotonation step to form an enantiodiscriminant oxy-allyl cation prior to the stereodefining nucleophilic addition event.

Original languageEnglish (US)
Pages (from-to)2134-2137
Number of pages4
JournalJournal of the American Chemical Society
Volume138
Issue number7
DOIs
StatePublished - Mar 2 2016

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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