Enantioselective Palladium-Catalyzed CH Functionalization of Indoles Using an Axially Chiral 2,2′-Bipyridine Ligand

• Published in: Angewandte Chemie International Edition Vol. 54; no. 41; pp. 11956 - 11960
• Main Authors: Gao, Xiang, Wu, Bo, Huang, Wen-Xue, Chen, Mu-Wang, Zhou, Yong-Gui
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 05.10.2015; WILEY‐VCH Verlag; Wiley
• Subjects: 2,2'-Dipyridyl - chemistry; Acetates - chemistry; asymmetric catalysis; Asymmetry; Carbenes; Catalysis; Chemistry; Chemistry, Multidisciplinary; chirality; Derivatives; diazo compounds; Indoles; Indoles - chemistry; Insertion; ligand design; Ligands; Methane - analogs & derivatives; Methane - chemistry; palladium; Palladium - chemistry; Phenols; Phenols - chemistry; Physical Sciences; Science & Technology; Stereoisomerism; ALPHA-DIAZOCARBONYL COMPOUNDS; chirality; asymmetric catalysis; SPIRO PHOSPHORIC-ACIDS; HIGHLY EFFICIENT; N-TOSYLHYDRAZONES; CROSS-COUPLING REACTIONS; DIPHOSPHINE LIGANDS; INSERTION REACTION; ligand design; CARBENE INSERTION; palladium; ASYMMETRIC HYDROGENATION; diazo compounds; CYCLOPROPANATION REACTIONS
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201504483

A palladium‐catalyzed enantioselective CH functionalization of indoles was achieved with an axially chiral 2,2′‐bipyridine ligand, thus providing the desired indol‐3‐acetate derivatives with up to 98 % ee. Moreover, the reaction protocol was also effective for asymmetric OH insertion reaction of phenols using α‐aryl‐α‐diazoacetates. This represents the first successful application of bipyridine ligands with axial chirality in palladium‐catalyzed carbene migratory insertion reactions. Get the axial: The title reaction involving diazo compounds was achieved with an axially chiral 2,2′‐bipyridine ligand. Moreover, insertion into OH bonds of phenols was also realized with up to 99 % ee by using this catalytic system.