Aromatic CH Bond Functionalization with Carbene Precursors

Abstract

Metal carbene‐based cross‐coupling reactions have been established as a highly efficient approach for constructing carbon–carbon bonds. In the past decade, this type of newly developed cross‐coupling reaction has been successfully merged into CH bond activations. This article summarizes the recent developments in aromatic CH bond functionalizations with carbene precursors. All the transformations shown in this article are mechanistically related, with the common feature of metal carbene formation and subsequent migratory insertion. The article is mainly divided into two parts according to the formation of the products: namely the CH bond transformations without cyclization or with cyclization.

Photoinduced Copper-Catalyzed Cross-Coupling of Acylsilanes with Azoles

“…Metal carbenes have emerged as highly versatile intermediates, involving in many efficient reactions, such as cyclopropanation, C-H and C-X bonds insertion reactions, tandem cyclization etc. [1][2][3][4] In view of the great success in this context, metal carbene species with an electron-deficient (carbonyl, nitro group etc.) and electron-neutral (aryl, alkenyl, alkynyl group etc.)…”

“…substituents have been well established due to the readily accessibility of corresponding stable carbene precursors including diazo compounds and their analogs (N-tosylhydrazones). [1][2][3][4] In sharp contrast, the investigations on catalytic reactions involving the metal carbene species bearing electron-rich heteroatom (O, N, S etc.) substituents are considerably limited, primarily due to the lack of readily available and stable metal carbene precursors.…”