Structural, Mechanistic, Spectroscopic, and Preparative Studies on the Lewis Base Catalyzed, Enantioselective Sulfenofunctionalization of Alkenes

Eduard Hartmann, Scott E Denmark

Research output: Contribution to journalArticle

Abstract

The full details of mechanistic investigation on enantioselective sulfenofunctionalization of alkenes under Lewis base catalysis are described. Solution spectroscopic identification of the catalytically active sulfenylating agent has been accomplished along with the spectroscopic identification of putative thiiranium ion intermediates generated in the enantiodetermining step. The structural insights gleaned from these studies informed the design of new catalyst architectures to improve enantioselectivity. In addition, structural modification of the sulfenylating agents had a significant and salutary effect on the enantioselectivity of sulfenofunctionalization which was demonstrated to be general for trans disubstituted alkenes. Whereas electronic modulation had little effect on the rate and selectivity, steric bulk on arylsulfenylphthalimides was very beneficial.

Original languageEnglish (US)
JournalHelvetica Chimica Acta
Volume100
Issue number9
DOIs
StatePublished - Jan 1 2017

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Lewis Bases
Lewis base
Enantioselectivity
Alkenes
alkenes
Olefins
Catalysis
catalysis
selectivity
Modulation
Ions
modulation
catalysts
Catalysts
electronics
ions

Keywords

  • Lewis base catalysis
  • Selenophosphoramides
  • Sulfenofunctionalization
  • Sulfenylating agents
  • Thiiranium ions

ASJC Scopus subject areas

  • Catalysis
  • Biochemistry
  • Drug Discovery
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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abstract = "The full details of mechanistic investigation on enantioselective sulfenofunctionalization of alkenes under Lewis base catalysis are described. Solution spectroscopic identification of the catalytically active sulfenylating agent has been accomplished along with the spectroscopic identification of putative thiiranium ion intermediates generated in the enantiodetermining step. The structural insights gleaned from these studies informed the design of new catalyst architectures to improve enantioselectivity. In addition, structural modification of the sulfenylating agents had a significant and salutary effect on the enantioselectivity of sulfenofunctionalization which was demonstrated to be general for trans disubstituted alkenes. Whereas electronic modulation had little effect on the rate and selectivity, steric bulk on arylsulfenylphthalimides was very beneficial.",
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AU - Denmark, Scott E

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N2 - The full details of mechanistic investigation on enantioselective sulfenofunctionalization of alkenes under Lewis base catalysis are described. Solution spectroscopic identification of the catalytically active sulfenylating agent has been accomplished along with the spectroscopic identification of putative thiiranium ion intermediates generated in the enantiodetermining step. The structural insights gleaned from these studies informed the design of new catalyst architectures to improve enantioselectivity. In addition, structural modification of the sulfenylating agents had a significant and salutary effect on the enantioselectivity of sulfenofunctionalization which was demonstrated to be general for trans disubstituted alkenes. Whereas electronic modulation had little effect on the rate and selectivity, steric bulk on arylsulfenylphthalimides was very beneficial.

AB - The full details of mechanistic investigation on enantioselective sulfenofunctionalization of alkenes under Lewis base catalysis are described. Solution spectroscopic identification of the catalytically active sulfenylating agent has been accomplished along with the spectroscopic identification of putative thiiranium ion intermediates generated in the enantiodetermining step. The structural insights gleaned from these studies informed the design of new catalyst architectures to improve enantioselectivity. In addition, structural modification of the sulfenylating agents had a significant and salutary effect on the enantioselectivity of sulfenofunctionalization which was demonstrated to be general for trans disubstituted alkenes. Whereas electronic modulation had little effect on the rate and selectivity, steric bulk on arylsulfenylphthalimides was very beneficial.

KW - Lewis base catalysis

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KW - Thiiranium ions

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