Ru(II)-Catalyzed Weakly Coordinating Carbonyl-Assisted Dialkynylation of (Hetero)Aryl Ketones.

Abstract

Functionalized aryl(heteroaryl) ketones are present in many natural products as key structural components and serve as basic synthetic building blocks for various organic transformation reactions. Therefore, the development of an effective and sustainable route for making these classes of compounds remains challenging yet highly desirable. Herein, we report a simple and efficient catalytic system for dialkynylation of aromatic/heteroaromatic ketones via a double C-H bond activation in the presence of less expensive ruthenium(II)-salt as a catalyst using the weakly and native carbonyl group as the desired directing group. The developed protocol is highly compatible, tolerant, and sustainable toward various functional groups. The synthetic utility of the developed protocol has been demonstrated through the scale-up synthesis and functional group transformation. Control experiments support the involvement of the base-assisted internal electrophilic substitution (BIES) reaction pathway.