Dirhodium‐Catalyzed Enantioselective B−H Bond Insertion of gem ‐Diaryl Carbenes: Efficient Access to gem ‐Diarylmethine Boranes

Autor:	Yu-Xuan Su, Shou-Fei Zhu, Xiao-Yu Li, Liang-Liang Yang, Yu-Tao Zhao, Ming-Yao Huang
Rok vydání:	2021
Předmět:	Diazomethane Enantioselective synthesis chemistry.chemical_element Boranes General Medicine General Chemistry Borane Medicinal chemistry Catalysis Rhodium Adduct chemistry.chemical_compound Stereospecificity chemistry Carbene
Zdroj:	Angewandte Chemie International Edition. 60:24214-24219
ISSN:	1521-3773 1433-7851
Popis:	The scarcity of reliable methods for synthesizing chiral gem-diarylmethine borons limits their applications. Herein, we report a method for highly enantioselective dirhodium-catalyzed B-H bond insertion reactions with diaryl diazomethanes as carbene precursors. These reactions afforded chiral gem-diarylmethine borane compounds in high yield (up to 99 % yield), high activity (turnover numbers up to 14 300), high enantioselectivity (up to 99 % ee) and showed unprecedented broad functional group tolerance. The borane compounds synthesized by this method could be efficiently transformed into diaryl methanol, diaryl methyl amine, and triaryl methane derivatives with good stereospecificity. Mechanistic studies suggested that the borane adduct coordinated to the rhodium catalyst and thus interfered with decomposition of the diazomethane, and that insertion of a rhodium carbene (generated from the diaryl diazomethane) into the B-H bond was most likely the rate-determining step.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::ade44c76d5e692f4223b4ab9e001e5dd https://doi.org/10.1002/anie.202109447 Zobrazit plný text záznamu Plný text