Catalytic enantioselective functionalization of cyclobutenes constitutes a general and modular strategy for construction of enantioenriched complex cyclobutanes bearing multiple stereogenic centers, as chiral four-membered rings are common motifs in biologically active molecules and versatile intermediates in organic synthesis. However, enantioselective synthesis of cyclobutanes through such a strategy remained significantly limited. Herein, we report a series of unprecedented cobalt-catalyzed carbon–carbon bond forming reactions of cyclobutenes that are initiated through enantioselective carbometalation. The protocols feature diastereo- and enantioselective introduction of allyl, alkynyl, and functionalized alkyl groups. Mechanistic studies indicated an unusual 1,3-cobalt migration and subsequent β-carbon elimination cascade process occurred in the allyl addition. These new discoveries established a new elementary process for cobalt catalysis and an extension of diversity of nucleophiles for enantioselective transformations of cyclobutenes.

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