Catalyst Engineering through Heterobidentate (N–X-Type) Ligand Design for Iridium-Catalyzed Borylation

Abstract

Iridium-catalyzed C–H activation and borylation reactions operate under mild conditions that enable easy and atom-economical installation of the versatile boronate ester group in (het)arenes and alkanes. The standard catalytic system for iridium-catalyzed borylation uses [Ir(cod)(OMe)]₂ as a precatalyst, a bipyridine type ligand, and B₂pin₂ or HBpin as the borylating agent. Initially, a bipyridine-ligated trisboryl–iridium complex is generated that enables the borylation reaction and the regioselectivity is mainly governed by the sterics of substituents present on the ring. As a result, monosubstituted and 1,2-disubstituted arenes give mixtures of isomers. Significant efforts by several research groups have overcome the selectivity issue for directed proximal C–H borylation by introducing a directing group and newly developed ligands. This short review aims to summarize recent elegant discoveries in directed C(sp²)–H and C(sp³)–H borylation by using heterobidentate ligand (P/N–Si, N–B, and N–C) coordinated iridium catalysts.

1 Introduction

2 Iridium-Catalyzed Directed C–H Borylation of C(sp²)–H Bonds

3 Iridium-Catalyzed Directed C–H Borylation of C(sp³)–H Bonds

4 Conclusions

Key words

C–H bond activation - ligand development - directing groups - heterobidentate ligand - iridium catalyst

Publication History

Received: 07 March 2022

Accepted after revision: 04 April 2022

Accepted Manuscript online:
04 April 2022

Article published online:
16 May 2022

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