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

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Alkenes
Synthetic Chemistry Techniques
Biological Products
Chlorides
Kinetics

Keywords

  • Electrophilic selenium
  • Enantioselective dichlorination
  • Redox catalysis

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes. / Gilbert, Bradley B.; Eey, Stanley T.C.; Ryabchuk, Pavel; Garry, Olivia; Denmark, Scott E.

In: Tetrahedron, Vol. 75, No. 31, 02.08.2019, p. 4086-4098.

Research output: Contribution to journalArticle

Gilbert, Bradley B. ; Eey, Stanley T.C. ; Ryabchuk, Pavel ; Garry, Olivia ; Denmark, Scott E. / Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes. In: Tetrahedron. 2019 ; Vol. 75, No. 31. pp. 4086-4098.
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