Ligand-Controlled Direct γ-C-H Arylation of Aldehydes

Abstract

The first example of Pd^II -catalyzed γ-C(sp³ )-H functionalization of aliphatic and benzoheteroaryl aldehydes has been developed using a transient ligand and an external ligand, concurrently. A wide array of γ-arylated aldehydes were readily accessed without preinstalling internal directing groups. The catalytic mechanism was studied by performing deuterium-labelling experiments, which indicated that the γ-C(sp³ )-H bond cleavage is the rate-limiting step during the reaction process. This reaction could be performed on a gram scale, and also demonstrated its potential application in the synthesis of new mechanofluorochromic materials with blue-shifted mechanochromic properties.

Keywords: C−H activation; aldehydes; mechanochromism; palladium; reaction mechanisms.