Mo-Catalyzed Asymmetric Allylic Alkylation Enabling the Con-struction of Highly Enantioenriched 1,4-Dicarbonyl Scaffolds

ABSTRACT: Herein, we report a Mo-catalyzed allylic alkylation that couples malonate nucleophiles with linear, tri-substituted allylic electrophiles, followed by a rapid ozonolysis. The process delivers 1,4-dicarbonyl compounds con-taining an -quaternary aldehyde motif with excellent enantioselectivity. This constitutes the first example of a Mo-catalyzed asymmetric allylic alkylation to form an electrophile-derived all-carbon quaternary stereocenter. The reac-tivity and stereoselectivity of the process was enabled by the invention of ShabyDACH, a novel C1-symmetric diamino-cyclohexane (DACH) pyridyl ligand. The utility of this transformation was demonstrated through a series of diverse synthetic transformations.