Abstract
AbstractA novel enantioselective Tsuji–Trost‐type cross coupling reaction between gem‐difluorinated cyclopropanes and N‐unprotected amino acid esters enabled by synergistic Pd/Ni/chiral aldehyde catalysis is presented herein. This transformation streamlined the diversity‐oriented synthesis (DOS) of optically active α‐quaternary α‐amino acid esters bearing a linear 2‐fluoroallylic motif, which served as an appealing platform for the construction of other valuable enantioenriched compounds. The key intermediates were confirmed by HRMS detection, while DFT calculations revealed that the excellent enantioselectivity was attributed to the stabilizing non‐covalent interactions between the Pd(II)‐π‐fluoroallyl species and the Ni(II)‐Schiff base complex.
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