Enantioselective Synthesis of N−N Biaryl Atropisomers through Iridium(I)‐Catalyzed C−H Alkylation with Acrylates

• Published in: Angewandte Chemie International Edition Vol. 62; no. 37; pp. e202305067 - n/a
• Main Authors: Yin, Si‐Yong, Zhou, Qiansujia, Liu, Chen‐Xu, Gu, Qing, You, Shu‐Li
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 11.09.2023; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Acrylates; Alkylation; Asymmetric Catalysis; Atom economy; Chemistry; Chemistry, Multidisciplinary; C−H Alkylation; Enantiomers; Enantioselectivity; Iridium; N−N Biaryl Atropisomer; Physical Sciences; Science & Technology; Substrates; Synthesis; N-N Biaryl Atropisomer; Enantioselectivity; C-H Alkylation; VINYL ETHERS; Asymmetric Catalysis; LIGANDS; REDUCTION; BONDS; CONSTRUCTION; BEARING; Iridium; HYDROARYLATION; ACCESS; C−H Alkylation; N−N Biaryl Atropisomer
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202305067

Enantioselective synthesis of N−N biaryl atropisomers is an emerging area but remains underexplored. The development of efficient synthesis of N−N biaryl atropisomers is in great demand. Herein, the construction of N−N biaryl atropisomers through iridium‐catalyzed asymmetric C−H alkylation is reported for the first time. In the presence of readily available Ir precursor and Xyl‐BINAP, a variety of axially chiral molecules based on indole‐pyrrole skeleton were obtained in good yields (up to 98 %) with excellent enantioselectivity (up to 99 % ee). In addition, N−N bispyrrole atropisomers could also be synthesized in excellent yields and enantioselectivity. This method features perfect atom economy, wide substrate scope, and multifunctionalized products allowing diverse transformations. A highly efficient iridium‐catalyzed asymmetric C−H alkylation reaction is described. A series of structurally diverse indole‐pyrrole and pyrrole‐pyrrole N−N atropisomers were obtained in good yields (up to 98 %) with excellent enantioselectivity (up to 99 % ee). This reaction features perfect atom economy, wide substrate scope, and multifunctionalized products allowing diverse transformations.