Work

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

Year: 2025

Type: article

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.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.5c09250

Authors: Chloe S. Cerione, Farbod A. Moghadam, Brian M. Stoltz

Institution: California Institute of Technology

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: California Institute of Technology, National Institute of General Medical Sciences