High-valent iodine promoted Rhodium-catalyzed C-H bond alkynylation of arene

• 1、School of Chemistry and Chemical Engineering,Chongqing University, Chongqing 401331

Abstract：With the explosive progress in experimental aspect, computational study of Rh-catalyzed C-H functionalization has also achieved great accomplishment. The advances in computational methods and computing power make theoretical calculation a practical yet powerful tool for mechanistic study. Both the detailed reaction pathway and origin of selectivity in transition metal-catalyzed transformations could be gained through computational study. Furthermore, predictions about the reactivity of new substrates and catalysts are also available for further experimental investigations. Our research mainly focused on the theoretical study of Rh-catalyzed C-H functionalization. This paper includes theoretical calculation was used to study Rh(III)-catalyzed C?H alkynylation of arenes under the hypervalent iodine reagents assistance. The catalytic cycle includeed deprotonation of arenes under chelation assistance, alkyne insertion andα-iodine elimination. Moreover, the origin of selectivity and effects of hypervalent iodine reagents were also illuminated by theoretical calculation. The calculated results are in good agreement with the experimental results.

Keywords： Rhodium catalysis, Theoretical study, Mechanism, Selectivity