Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes

Bradley B. Gilbert, Stanley T.C. Eey, Pavel Ryabchuk, Olivia Garry, Scott E. Denmark

Research output: Contribution to journalArticle

Abstract

The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective dichlorination of isolated alkenes would allow access to a wide variety of polyhalogenated natural products. Accordingly, the enantioselective suprafacial dichlorination of alkenes catalyzed by electrophilic organoselenium reagents has been developed to address these limitations. The evaluation of twenty-three diselenides as precatalysts for enantioselective dichlorination is described, with a maximum e.r. of 76:24 Additionally, mechanistic studies suggest an unexpected Dynamic Kinetic Asymmetric Transformation (DyKAT) process may be operative.

Original languageEnglish (US)
Pages (from-to)4086-4098
Number of pages13
JournalTetrahedron
Volume75
Issue number31
DOIs
StatePublished - Aug 2 2019

Keywords

  • Electrophilic selenium
  • Enantioselective dichlorination
  • Redox catalysis

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Fingerprint Dive into the research topics of 'Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes'. Together they form a unique fingerprint.

  • Cite this