N‐Heterocycle‐Editing to Access Fused‐BN‐Heterocycles via Ring‐Opening/C−H Borylation/Reductive C−B Bond Formation

• Published in: Angewandte Chemie International Edition Vol. 63; no. 10; pp. e202318613 - n/a
• Main Authors: Zhang, Xu, Su, Wanlan, Guo, Huosheng, Fang, Pengyuan, Yang, Kai, Song, Qiuling
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 04.03.2024; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Azaborine; Boron; Chemistry; Chemistry, Multidisciplinary; C−H Borylation; Editing; Insertion; N-Heterocycles; Nickel; Physical Sciences; Reductive Coupling; Science & Technology; Substrates; Reductive Coupling; TANDEM REACTIONS; N-Heterocycles; PALLADIUM-CATALYZED CARBOBORATION; NITROGEN-HETEROCYCLES; ALKYNES; FUNCTIONALIZATION; CHLOROBORANE; C-H Borylation; EXPANSION; SYNTHETIC METHODS; Nickel; Azaborine; PHOTOOXYGENATION; QUINAZOLINES; C−H Borylation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202318613

Skeletal editing of N‐heterocycles has recently received considerable attention, and the introduction of boron atom into heterocycles often results in positive property changes. However, direct enlargement of N‐heterocycles through boron atom insertion is rarely reported in the literature. Here, we report a N‐heterocyclic editing reaction through the combination boron atom insertion and C−H borylation, accessing the fused‐BN‐heterocycles. The synthetic potential of this chemistry was demonstrated by substrate scope and late‐stage diversification of products. An N‐heterocyclic editing reaction through the tandem BBr3‐induced ring‐opening of tertiary cyclic amine, intramolecular C−H borylation, and Ni‐catalyzed intramolecular B−Br/C−Br reductive coupling was developed. This method represents a simple route to construct the fused‐BN‐heterocycles.