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A mechanistic rationale for the high diastereo\u2010 and enantioselectivity achieved experimentally at high reaction temperature was uncovered through modeling the reaction with a chiral ligand and the predicted stereochemical outcome corroborates with experimental results. An unprecedented mechanism for the base\u2010free organoboron transmetalation was revealed and the regioselectivity of migratory insertion of tethered allene\u2010ketones as well as the stability of the possible allylnickel isomers (\u03c3\u2010allyl vs \u03c0\u2010allyl) were clarified. 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