Nickel-Catalyzed Cross-Electrophile Coupling of Alkyl Fluorides: Stereospecific Synthesis of Vinylcyclopropanes

The stereospecific reductive cross-electrophile coupling reaction of 2-vinyl-4-halotetra­hydropyrans for vinylcyclopropane synthesis is reported. The nickel-catalyzed reaction occurs with both alkyl fluorides and alkyl chlorides. To the best of our knowledge, this is the first reported cross-electro...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2016-10, Vol.138 (42), p.14006-14011
Main Authors: Erickson, Lucas W, Lucas, Erika L, Tollefson, Emily J, Jarvo, Elizabeth R
Format: Article
Language:English
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Summary:The stereospecific reductive cross-electrophile coupling reaction of 2-vinyl-4-halotetra­hydropyrans for vinylcyclopropane synthesis is reported. The nickel-catalyzed reaction occurs with both alkyl fluorides and alkyl chlorides. To the best of our knowledge, this is the first reported cross-electrophile coupling reaction of an alkyl fluoride. Ring contraction proceeds with high stereospecificity, providing selective synthesis of either diastereomer of di- and trisubstituted cyclopropanes. The utility of this methodology is demonstrated by several synthetic applications including the synthesis of the natural product dictyopterene A. 2-Vinyl-4-fluorotetra­hydro­furans also undergo stereospecific ring contractions, providing access to synthetically useful hydroxymethyl cyclopropanes.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b07567