Ruthenium-catalyzed stereospecific benzylic alkylation of optically active benzyl esters with malonate nucleophiles

The transition metal-catalyzed stereospecific benzylic alkylation of optically active benzyl esters with active methylene compounds remains extremely rare. Herein, we describe the study for the ruthenium-catalyzed benzylic alkylation of chiral benzyl esters with malonates as a carbon nucleophile. A combination of [Cp*RuCl2](2) and picolinic acid found to be effective for the title reaction, providing the chiral benzylic alkylation products with retention of stereochemistry of the starting material. We proposed that the ruthenium catalysis would proceed via a double inversion mechanism. (C) 2021 Elsevier Ltd. All rights reserved.

Automated summary

In this study, the ruthenium-catalyzed benzylic alkylation of chiral benzyl esters with malonates was investigated, showing high enantioselectivity and retention of stereochemistry. The proposed mechanism for the reaction involves a double inversion process.