Nickel-Catalyzed Alkyl–Alkyl Cross-Electrophile Coupling Reaction of 1,3-Dimesylates for the Synthesis of Alkylcyclopropanes

Cross-electrophile coupling reactions of two Csp3–X bonds remain challenging. Herein we report an intramolecular nickel-catalyzed cross-electrophile coupling reaction of 1,3-diol derivatives. Notably, this transformation is utilized to synthesize a range of mono- and 1,2-disubstituted alkylcycloprop...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2020-03, Vol.142 (11), p.5017-5023
Main Authors: Sanford, Amberly B, Thane, Taylor A, McGinnis, Tristan M, Chen, Pan-Pan, Hong, Xin, Jarvo, Elizabeth R
Format: Article
Language:English
Subjects:
Catalysis
Coordination Complexes - chemistry
Cyclization
Cyclopropanes - chemical synthesis
Mesylates - chemistry
Nickel - chemistry
Oxidation-Reduction
Stereoisomerism
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Summary:Cross-electrophile coupling reactions of two Csp3–X bonds remain challenging. Herein we report an intramolecular nickel-catalyzed cross-electrophile coupling reaction of 1,3-diol derivatives. Notably, this transformation is utilized to synthesize a range of mono- and 1,2-disubstituted alkylcyclopropanes, including those derived from terpenes, steroids, and aldol products. Additionally, enantioenriched cyclopropanes are synthesized from the products of proline-catalyzed and Evans aldol reactions. A procedure for direct transformation of 1,3-diols to cyclopropanes is also described. Calculations and experimental data are consistent with a nickel-catalyzed mechanism that begins with stereoablative oxidative addition at the secondary center.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.0c01330