Qui-Hien NguyenGuo, Shu-MinRoyal, TitouanBaudoin, OlivierCramer, Nicolai2020-03-032020-03-032020-03-032020-02-0510.1021/jacs.9b12299https://infoscience.epfl.ch/handle/20.500.14299/166677WOS:000512222700015Atropisomeric (hetero)biaryls are motifs with increasing significance in ligands, natural products, and biologically active molecules. The straightforward construction of the stereogenic axis by efficient C-H functionalization methods is extremely rare and challenging. An intermolecular and highly enantioselective C-H arylation of relevant heteroarenes providing an efficient access to atropisomeric (hetero)biaryls is reported. The use of a Pd(0) complex equipped with H-8-BINAPO as a chiral ligand enables the direct functionalization of a broad range of 1,2,3-triazoles and pyrazoles in excellent yields and selectivities of up to 97.5:2.5 er. The method also allows for an atroposelective double C-H arylation for the construction of two stereogenic axes with >99.5:0.5 er.Chemistry, MultidisciplinaryChemistrycatalyzed direct arylationphosphine oxide ligandsaxially chiral biarylsatroposelective synthesisbond functionalizations2+2+2 cycloadditionnatural-products1,2,3-triazolesatropisomerismchemistrytext::journal::journal article::research article