Boron trihalides(BX3),inexpensive bulk chemicals,serve as key feedstocks for nearly all borylation reagents used in the cross-coupling of aryl halides.However,the direct coupling of BX3 with aryl halides has yet to be...Boron trihalides(BX3),inexpensive bulk chemicals,serve as key feedstocks for nearly all borylation reagents used in the cross-coupling of aryl halides.However,the direct coupling of BX3 with aryl halides has yet to be explored.Herein,we report a nickelcatalyzed reductive C(sp^(2))-B coupling of BCl_(3)by utilizing a dual tertiary amine activation strategy.This approach provides a straightforward route to synthesize a broad range of aryl boronate esters using BCl_(3)as the borylation reagent.Mechanistic studies characterize the crucial roles of the two tertiary amines(4-pyrrolidinopyridine and diisopropylethylamine),as well as dichloromethane solvent.展开更多
基金financial support from the National Natural Science Foundation of China(grant nos.22101279 and 22173103)the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation Funded(grant no.GZC20232603)+2 种基金the China Postdoctoral Science Foundation(grant no.2024M753178)the Shandong Provincial Natural Science Foundation(grant no.ZR2024QB080)the Fundamental Research Funds for the Central Universities,the University of the Chinese Academy of Sciences,and the Beijing National Laboratory for Molecular Sciences(grant no.BNLMS2023014)。
文摘Boron trihalides(BX3),inexpensive bulk chemicals,serve as key feedstocks for nearly all borylation reagents used in the cross-coupling of aryl halides.However,the direct coupling of BX3 with aryl halides has yet to be explored.Herein,we report a nickelcatalyzed reductive C(sp^(2))-B coupling of BCl_(3)by utilizing a dual tertiary amine activation strategy.This approach provides a straightforward route to synthesize a broad range of aryl boronate esters using BCl_(3)as the borylation reagent.Mechanistic studies characterize the crucial roles of the two tertiary amines(4-pyrrolidinopyridine and diisopropylethylamine),as well as dichloromethane solvent.
