Escudero-Casao Margarita, Licini Giulia, Orlandi Manuel
Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy.
CIRCC-Consorzio Interuniversitario per le Reattività Chimiche e la Catalisi, University of Padova, via Marzolo 1, 35131 Padova, Italy.
J Am Chem Soc. 2021 Mar 10;143(9):3289-3294. doi: 10.1021/jacs.0c13236. Epub 2021 Feb 26.
A novel catalytic system based on copper(I) and chiral bis(phosphine) dioxides is described. This allows the arylation of silyl enol ethers to access enolizable α-arylated ketones in good yields and enantiomeric excess up to 95%. Noncyclic ketones are amenable substrates with this method, which complements other approaches based on palladium catalysis. Optimization of the ligand structure is accomplished via rational design driven by correlation analysis. Preliminary mechanistic hypotheses are also evaluated in order to identify the role of chiral bis(phosphine) dioxides.
描述了一种基于铜（I）和手性双（膦）二氧化物的新型催化体系。这使得硅烯醇醚的芳基化能够以良好的产率和高达95%的对映体过量获得可烯醇化的α-芳基化酮。非环状酮是该方法适用的底物，它补充了基于钯催化的其他方法。通过相关性分析驱动的合理设计实现了配体结构的优化。还评估了初步的机理假设，以确定手性双（膦）二氧化物的作用。
