A Catalyst Designed for the Enantioselective Construction of Methyl- and Alkyl-Substituted Tertiary Stereocenters

Aurélie Claraz, Gokarneswar Sahoo, Dénes Berta, Ádám Madarász, I. Pápai, Petri M. Pihko

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Tertiary methyl-substituted stereocenters are present in numerous biologically active natural products. Reported herein is a catalytic enantioselective method for accessing these chiral building blocks using the Mukaiyama-Michael reaction between silyl ketene thioacetals and acrolein. To enable remote enantioface control on the nucleophile, a new iminium catalyst, optimized by three-parameter tuning and by identifying substituent effects on enantioselectivity, was designed. The catalytic process allows rapid access to chiral thioesters, amides, aldehydes, and ketones bearing an α-methyl stereocenter with excellent enantioselectivities, and allowed rapid access to the C4-C13 segment of (-)-bistramide A. DFT calculations rationalized the observed sense and level of enantioselectivity.

Original languageEnglish
Pages (from-to)669-673
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number2
DOIs
Publication statusPublished - Jan 11 2016

Fingerprint

Enantioselectivity
Catalysts
Bearings (structural)
Acrolein
Nucleophiles
Remote control
Biological Products
Ketones
Aldehydes
Amides
Discrete Fourier transforms
Tuning

Keywords

  • asymmetric catalysis
  • density functional calculations
  • diastereoselectivity
  • natural products
  • organocatalysis

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

A Catalyst Designed for the Enantioselective Construction of Methyl- and Alkyl-Substituted Tertiary Stereocenters. / Claraz, Aurélie; Sahoo, Gokarneswar; Berta, Dénes; Madarász, Ádám; Pápai, I.; Pihko, Petri M.

In: Angewandte Chemie - International Edition, Vol. 55, No. 2, 11.01.2016, p. 669-673.

Research output: Contribution to journalArticle

Claraz, Aurélie ; Sahoo, Gokarneswar ; Berta, Dénes ; Madarász, Ádám ; Pápai, I. ; Pihko, Petri M. / A Catalyst Designed for the Enantioselective Construction of Methyl- and Alkyl-Substituted Tertiary Stereocenters. In: Angewandte Chemie - International Edition. 2016 ; Vol. 55, No. 2. pp. 669-673.
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