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

Ramesh Bhawar; Suresh Saini; Kiran S Patil; D H Nagaraju; Shubhankar Kumar Bose

doi:10.1021/acs.joc.3c01755

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

J Org Chem. 2023 Dec 1;88(23):16270-16279. doi: 10.1021/acs.joc.3c01755. Epub 2023 Nov 13.

Authors

Ramesh Bhawar¹, Suresh Saini¹, Kiran S Patil¹, D H Nagaraju², Shubhankar Kumar Bose¹

Affiliations

¹ Centre for Nano and Material Sciences (CNMS), JAIN (Deemed-to-be University), Jain Global Campus, Bangalore, 562112, India.
² Department of Chemistry, School of Applied Sciences, Reva University, Bangalore, 560064, India.

PMID: 37957832
DOI: 10.1021/acs.joc.3c01755

Abstract

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.