Synthesis of Alkyl and Aryl Boronate Esters via CeO2-Catalyzed Borylation of Alkyl and Aryl Electrophiles Including Alkyl Chlorides

A recyclable protocol using a CeO2-nanorod catalyst for borylation of alkyl halides with B2pin2 (pin = OCMe2CMe2O) is reported. A wide range of synthetically useful alkyl boronate esters are readily obtained from primary and secondary alkyl electrophiles, including unactivated alkyl chlorides, demonstrating broad utility and functional group tolerance. Preliminary investigation revealed an involvement of in situ formed catalytically active boryl species. The catalyst can be reused for up to six runs without appreciable loss in activity. In addition, we have demonstrated the use of this recyclable catalyst for the borylation of aryl halides with B2pin2, providing valuable aryl boronate esters under neat conditions.

Automated summary

A recyclable protocol using CeO2-nanorod catalyst for the borylation of alkyl halides with B2pin2 is reported. The catalyst showed broad utility and functional group tolerance, and could be reused up to six times without significant loss of activity.