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A Simple Nickel Metal–Organic Framework-Catalyzed Borylation of Aryl Chlorides and Bromides

Aishwarya Prakash, Suma Basappa, Bhavya Jeebula, D. H. Nagaraju, Rajendra S. Dhayal, Shubhankar Kumar Bose

2024Organic Letters12 citationsDOI

Abstract

We report a recyclable and efficient catalyst system based on a nickel-benzene tricarboxylic acid metal–organic framework (Ni-BTC MOF) for the borylation of aryl halides, including aryl chlorides, with bis (pinacolato)diboron, affording aryl boronate esters in high yields (up to >99% yield) with high selectivity. This protocol demonstrates broad functional group tolerance. Catalyst can be recyclable up to four times, and gram-scale reactions further highlights the usefulness of this method. In situ EPR experiments confirmed the formation of catalytically active Ni(I) species.

Topics & Concepts

BorylationChemistryArylCatalysisNickelYield (engineering)HalideBenzeneCombinatorial chemistryFunctional groupOrganic chemistryAlkylMetallurgyMaterials sciencePolymerOrganoboron and organosilicon chemistryMetal-Organic Frameworks: Synthesis and ApplicationsCatalytic Cross-Coupling Reactions