Adrien Jules Louis Madron Du Vigné

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Chiral Cyclic Alkyl Amino Carbene (CAAC) Transition-Metal Complexes: Synthesis, Structural Analysis, and Evaluation in Asymmetric Catalysis

Despite recent advances in the field of cyclic alkyl amino carbenes (CAACs) including a few complementary synthetic strategies affording CAACs with various substitution patterns, the application potential of chiral CAACs to efficiently catalyze asymmetric organometallic transformations remains largely underdeveloped. Herein, we describe a convenient and robust route that incorporates common chiral primary amine allowing access of a broad range of chiral CAACs precursors. The corresponding transition-metal complexes with Cu, Au, Ru, Rh, Ir, and Pd were obtained in a straightforward manner. The steric parameters of the complexes were comprehensively collected by X-ray single-crystal analysis to serve as a source of information for further ligand design. The preliminary application potential of the copper CAAC complexes was tested in asymmetric conjugate borylation of an alpha,beta-unsaturated ester providing 89:11 er, thus illustrating the potential of chiral CAACs in asymmetric catalysis.

AMER CHEMICAL SOC2022

Catalytic Enantioselective Functionalizations of C-H Bonds by Chiral Iridium Complexes

Nicolai Cramer, Adrien Jules Louis Madron Du Vigné, Qui-Hien Nguyen, Jin Fay Tan, Lukasz Piotr Wozniak

The development of catalytic enantioselective transformations, enabling the construction of complex molecular scaffolds from simple precursors, has been a long-standing challenge in organic synthesis. Recent achievements in transition-metal catalyzed enantioselective functionalizations of carbon-hydrogen (C-H) bonds represent a promising pathway toward this goal. Over the last two decades, iridium catalysis has evolved as a valuable tool enabling the stereocontrolled synthesis of chiral molecules via C-H activation. The development of iridium-based systems with various chiral ligand classes, as well as studies of their reaction mechanisms, has resulted in dynamic progress in this area. This review aims to present a comprehensive picture of the enantioselective functionalizations of C-H bonds by chiral iridium complexes with emphasis on the mechanisms of the C-H activation step.

2020