Copper‐Catalyzed Boroaminomethylation of Olefins to γ‐Boryl Amines with CO as C1 Source. (17th October 2022)

• Record Type: Journal Article
• Authors: Wu, Fu‐Peng; Geng, Hui‐Qing; Wu, Xiao‐Feng
• Is Part Of: Angewandte Chemie. Volume 134:Number 46(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-10-17
• Subjects: Amine -- Boroaminomethylation -- Carbonylation -- Copper Catalyst -- Multi-Component Reaction; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202211455
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Boroaminomethylation of olefins is an efficient process to convert hydrocarbons directly into boron‐, nitrogen‐containing molecules. Such chemicals are a good handle for obtaining more complexed amine derivatives through the various transformations of organoboron. However, using simple and easily available CO as the C1 feedstock to achieve boroaminomethylation is still elusive. Here we report a copper‐catalyzed boroaminomethylation of olefins with CO as the C1 source via the mechanism of a carbene insertion into the N−H bond. This method affords valuable γ ‐boryl amines from four inexpensive readily chemicals. The wide synthetic transformations of the γ ‐boryl amines demonstrates their utility. Notably, 13 C labeling studies revealed that the −CH2 ‐building block was derived from one molecule of CO. Abstract : Boroaminomethylation of olefins with CO as −CH2 ‐source via the mechanism of a carbene insertion into the N−H bond was described. In the present of CuCl and Xantphos as the catalyst, a variety of γ ‐boryl amines were obtained with broad functional groups tolerance. The new aromatization and other transformations of the γ ‐boryl amines demonstrate their utility. Notably, 13 C labeled product was produced with isotope‐labeled 13 CO.