biostudies-literatureSanford ABMinistry of Education of the People's Republic of ChinaNational Natural Science Foundation of ChinaNational Institute of General Medical SciencesZhejiang UniversityNIGMS NIH HHS5017-5023https://www.ebi.ac.uk/biostudies/studies/S-EPMC7864534biostudies-literatureUnknown142(11)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.Journal of the American Chemical SocietyNickel-Catalyzed Alkyl-Alkyl Cross-Electrophile Coupling Reaction of 1,3-Dimesylates for the Synthesis of Alkylcyclopropanes.PMC7864534R01GM10021221702182R01 GM1002122019QNA300921873081McGinnis TMThane TAHong XJarvo ERChen PPSanford ABfalseNickel-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 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.2020-01-01T00:00:00Z2020 Mar2025-04-03T23:47:25.507Z2025-04-03T23:47:25.507ZS-EPMC78645343212960110.1021/jacs.0c01330