Rhodium-catalyzed The C-H Alkenylation/Annulation Of 1,3-diynes

1,3-Enynes,3H-pyrrolo[1,2-a]indol-3-ones and benzofurans are very important structural units in medicinal chemistry,organic synthesis and materials science,and the construction of such structures have always been the focus of research by chemists.In recent years,transitionmetal-catalyzed C-H activation has been widely used in organic synthesis,among which transition-metal-catalyzed C-H activation of 1,3-diynes is one of the important synthesis methods for the synthesis of 1,3-enynes and heterocyclic compounds.The first chapter of the paper reviews the C-H activation reaction catalyzed by transition metals with 1,3-diynes,involving C-H alkenylation and C-H annulation,and discusses the reaction of regional selectivity,stereochemical selectivity,scope of substrates,and reaction mechanism.The second chapter of the paper is rhodium-catalyzed C-H alkenylation/directing group migration and [3+2] cycloaddition between N-carbamoyl indoles and 1,3-diynes.This reaction achieved the additive-controlled divergent synthesis of tetrasubstituted 1,3-enynes and C2-alkynylated 3H-pyrrolo[1,2-a]indol-3-ones via rhodium-catalyzed C-H alkenylation/ directing group migration and [3+2] cycloaddition between N-carbamoyl indoles and 1,3-diynes,respectively.In addition to acting as a directing group,the carbamoyl group also achieves intramolecular migration and acts as an acylation reagent,in the C-H alkenylation/directing group migration reaction.Notably,this is the first time that intramolecular migration of the directing group has been achieved in the C-H activation involving 1,3-diynes.This method features excellent regio-and stereoselectivity,broad substrate scope,moderate to high yields,good tolerance of functional groups and mild reaction conditions.The third chapter of the paper is rhodium-catalyzed C-H alkenylation/directing group migration and [3+2] cycloaddition between N-phenoxyamides and 1,3-diynes.This reaction achieved the additives/solvents-controlled divergent synthesis of tetrasubstituted 1,3-enynes and alkynylated benzofurans via rhodium-catalyzed C-H alkenylation/directing group migration and [3+2] cycloaddition between N-phenoxyamides and 1,3-diynes,respectively.This method features excellent regio-and stereoselectivity,good tolerance of functional groups and no deed for external oxidants.