# Heterobenzyl Chlorides as Linchpins for C–H Arylation via Sequential C–H Chlorination/Cross-Electrophile Coupling

## TL;DR

A new method for C–H arylation uses heterobenzyl chlorides to enable efficient cross-coupling reactions with aryl iodides.

## Contribution

A general strategy for C–H arylation using heterobenzyl chlorides as linchpins in Ni-catalyzed cross-electrophile coupling.

## Key findings

- Heterobenzyl chlorides enable C–H arylation via Ni-catalyzed cross-electrophile coupling.
- Primary and secondary heterobenzyl chlorides show distinct reactivity patterns.
- The method works with various heterobenzyl chlorides and aryl iodides.

## Abstract

Synthetic methods
that use C­(sp3)–H bonds in
carbon–carbon cross-coupling reactions are limited and often
lack generality, particularly with substrates containing basic heterocycles.
Here, we demonstrate the arylation of heterobenzylic C–H bonds
by using heterobenzyl chlorides as linchpins that can undergo Ni-catalyzed
cross-electrophile coupling with aryl iodides. The results show different
reactivity for primary and secondary heterobenzyl chlorides and also
show differences among secondary heterobenzyl chlorides at different
positions on the heteroaromatic ring. The Ni-catalyzed conditions
identified for each of these substrate classes ensure that the rate
of heterobenzyl chloride activation complements the rate of aryl iodide
activation. These methods are demonstrated with series of heterobenzyl
chlorides and (hetero)­aryl iodides, providing a general strategy for
C­(sp3)–H arylation.