Oxygen‐Linked Cyclopentadienyl Rhodium(III) Complexes‐Catalyzed Asymmetric C−H Arylation of Benzo[h]quinolines with 1‐Diazonaphthoquinones

• Published in: Angewandte Chemie International Edition Vol. 60; no. 28; pp. 15510 - 15516
• Main Authors: Pan, Chongqing, Yin, Si‐Yong, Wang, Shao‐Bo, Gu, Qing, You, Shu‐Li
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 05.07.2021
• Subjects: axial chirality; Chemistry; Chemistry, Multidisciplinary; chiral cyclopentadienyl; heterobiaryl; Physical Sciences; rhodium; Science & Technology; heterobiaryl; ACTIVATION; ENANTIOSELECTIVE SYNTHESIS; CHIRAL (CPRH)-RH-X; ALKYLATION; BIARYL COMPOUNDS; axial chirality; FUNCTIONALIZATION; OLEFINATION; LIGANDS; CONSTRUCTION; chiral cyclopentadienyl; BOND; rhodium
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202103638

Chiral cyclopentadienyl rhodium (CpRh) complex‐catalyzed asymmetric C−H functionalization reactions have witnessed a significant progress in organic synthesis. In sharp contrast, the reported chiral Cp ligands are limited to C‐linked Cp and are often synthetically challenging. To address these issues, we have developed a novel class of tunable chiral cyclopentadienyl ligands bearing oxygen linkers, which were efficient catalysts for C−H arylation of benzo[h]quinolines with 1‐diazonaphthoquinones, affording axially chiral heterobiaryls in excellent yields and enantioselectivity (up to 99 % yield, 98.5:1.5 er). Mechanistic studies suggest that the reaction is likely to proceed by electrophilic C−H activation, and followed by coupling of the cyclometalated rhodium(III) complex with 1‐diazonaphthoquinones. A class of chiral cyclopentadienyl ligands (BOCps) bearing an oxygen linker was developed. The BOCpRh complexes are powerful catalysts in an asymmetric C−H arylation of benzo[h]quinolines with 1‐diazonaphthoquinones to construct axially chiral heterobiaryls. Preliminary mechanistic studies suggest that this reaction is likely to proceed via an electrophilic C−H rhodation and subsequent coupling with 1‐diazonaphthoquinones.