Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction) represents a prototypical example of enantioselective C–C bond-forming reactions of alkenes, which has been used to significantly modernize and improve the syntheses of chiral natural products including deoxypolypropionates, isoprenoids, and other compounds of biological and medicinal interest. Recent advances of ZACA reaction will be discussed with emphasis on several methodological developments including: (i) ZACA–lipase-catalyzed acetylation–transition metal-catalyzed cross-coupling processes for preparing various enantiopure chiral alcohols; (ii) one-step homologation for the synthesis of deoxypropionates; (iii) the ZACA reaction of dienes to generate chiral cyclic compounds including those with all-carbon quaternary stereocenters.
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