1,2,3-Thiadiazole as a Modifiable and Scalable Directing Group for ortho-C-H Functionalization.

Abstract

In the last few decades, directed C-H bond functionalization has had enormous applicability in academia and industry. The development of a novel, readily accessible, and scalable directing group with modifiable ability is highly desirable in C-H functionalization. Herein, we report the 1,2,3-thiadiazole as a modifiable directing group for C-H amidation and alkynylation with dioxazolones, p-toluenesulfonyl azide, and bromoalkynes in high yield. The densely functionalized 1,2,3-thiadiazole products are modified into thioamide, multisubstituted furan, γ-thiapyrone, thiazole, and various alkynyl sulfides through simple and one-step reactions. The competition experiments reveal that the directing ability of 1,2,3-thiadiazole is slightly weaker than pyridine and bidentate amide but stronger than the widely used carboxylate.