Mo-Catalyzed Asymmetric Allylic Alkylation Enabling the Construction of Highly Enantioenriched 1,4-Dicarbonyl
Chloe S Cerione1, Farbod A Moghadam1, Brian M Stoltz1
1The Warren and Katherine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd, MC 101-20, Pasadena, California 91125, United States.
Abstract:
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 ShabyDACH, a novel C1-symmetric diaminocyclohexane (DACH) pyridyl ligand. The utility of this method was demonstrated through a series of diverse synthetic transformations.
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