A Cooperative Hydrogen Bond Donor–Brønsted Acid System for the Enantioselective Synthesis of Tetrahydropyrans

Mark A. Maskeri, Matthew J. O'Connor, Ashley A. Jaworski, Anna V. Davies, Karl A. Scheidt*

*Corresponding author for this work

Research output: Contribution to journalArticle

17 Scopus citations

Abstract

Carbocations stabilized by adjacent oxygen atoms are useful reactive intermediates involved in fundamental chemical transformations. These oxocarbenium ions typically lack sufficient electron density to engage established chiral Brønsted or Lewis acid catalysts, presenting a major challenge to their widespread application in asymmetric catalysis. Leading methods for selectivity operate primarily through electrostatic pairing between the oxocarbenium ion and a chiral counterion. A general approach to new enantioselective transformations of oxocarbenium ions requires novel strategies that address the weak binding capabilities of these intermediates. We demonstrate herein a novel cooperative catalysis system for selective reactions with oxocarbenium ions. This new strategy has been applied to a highly selective and rapid oxa-Pictet–Spengler reaction and highlights a powerful combination of an achiral hydrogen bond donor with a chiral Brønsted acid.

Original languageEnglish (US)
Pages (from-to)17225-17229
Number of pages5
JournalAngewandte Chemie - International Edition
Volume57
Issue number52
DOIs
StatePublished - Dec 21 2018

Keywords

  • chiral phosphoric acid
  • cooperative catalysis
  • hydrogen bonding
  • oxocarbenium ion
  • tetrahydropyrans

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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