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

Herein, we report a Mo-catalyzed allylic alkylation that couples malonate nucleophiles with linear, trisubstituted allylic electrophiles, followed by a rapid ozonolysis. The process delivers 1,4-dicarbonyl compounds containing an α-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 reactivity and stereoselectivity of the process was enabled by the invention of <i>ShabyDACH</i>, a novel <i>C</i>₁-symmetric diaminocyclohexane (DACH) pyridyl ligand. The utility of this method was demonstrated through a series of diverse synthetic transformations.