A new Pd/Cu-catalyzed carbonylation and borylation of alkynes with aryldiazonium salts toward α-unsubstituted β-boryl ketones with complete regioselectivity has been developed. This transformation shows broad substrate scope and excellent functional-group...

A copper-catalyzed three-component coupling reaction has been developed allowing the rapid building of valuable complex highly functionalized β-polychloromethyl amines from simple styrenes, arylamines, and dichloromethane/chloroform. Using aryldiazonium salts as a radical initiator, a series of corresponding products are obtained with moderate to good yields under a carbon dioxide or nitrogen atmosphere (50 psi). In addition, good functional group tolerance can be observed.

A convenient four-component reaction has been developed that allows for the direct transformation of aryl iodides with alkyl halides into the corresponding aromatic esters and diesters via palladium-catalyzed carbonylation with water as solvent. Various esters and diesters were isolated in moderate to good yields with broad functional group tolerance.

An unprecedented and challenging multicomponent reaction has been developed that allows for the direct transformation of acyl chlorides with alkynes into the corresponding saturated β-boryl ketones via Pd/Cu-catalyzed coupling and boration with ethyl acetate as the hydrogen sources. Various βboryl ketones were synthesized in good to excellent yields with broad functional group tolerance. In addition, the introduction of boron groups into the products provides substantial opportunities for further conversions.

We report the development of Pd/Cu‐catalyzed selective 2,1‐borocarbonylation reactions of aliphatic terminal alkynes with aryldiazonium salts and B2Pin2 to prepare gem‐bis(boryl) ketones in one‐pot. A series of corresponding products are obtained with good to excellent yields under a carbon monoxide atmosphere (10 bar). In addition, wide functional‐group tolerance can be observed. Preliminary mechanistic studies reveal that ethyl acetate serves as a proton source in the reaction.