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

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.

SUBMITTER: Cerione CS 

PROVIDER: S-EPMC12498422 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature