4.5 Article

Explorations into the Potential of Chiral Sulfonium Reagents to Effect Asymmetric Halonium Additions to Isolated Alkenes

Journal

SYNTHESIS-STUTTGART
Volume 45, Issue 13, Pages 1886-1898

Publisher

GEORG THIEME VERLAG KG
DOI: 10.1055/s-0033-1338865

Keywords

chirality; halogenations; alkenes; enantioselectivity; hydroxylations

Funding

  1. Columbia University
  2. NSF [CHE-0844593]
  3. Ludwig-Maximilians-University-Munich
  4. ACS Petroleum Research Fund [47481-G]
  5. Camille and Henry Dreyfus Foundation

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While methods for the racemic dihalogenation and halohydroxylation of alkenes have been known for decades, enantioselective variants of these processes remain elusive. Initial attempts were made to overcome this long-standing challenge by exploring the potential of chiral, crystalline, sulfur-derived halonium reagents to accomplish the asymmetric dichlorination and iodohydroxylation of 1,2-dihydronaphthalene. Asymmetric dichlorination of this substrate was achieved in 57% yield and 14% enantiomeric excess (ee), but asymmetric iodohydroxylation was much more successful, giving 67% yield and 63% ee. Thorough studies were made of these processes, including investigation of various chiral sulfide derivatives, their substrate scopes, and the reaction conditions.

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