Carbonyl Group-directed C-h Alkenylation And Amination By Transition Metal Catalysis

The construction of carbon-carbon bonds and carbon-nitrogen bonds are a very important.The 1,3-dienes and anilines prepared by trasition-metal-catalyzed C-C and C-N bond formation are key structural motifs in natural product synthesis,medicinal chemistry,crop protection,and material sciences,and they represent versatile intermediates in organic synthesis.Selective C(sp~2)-H alkenylation and imidation represent efficient ways to obtain conjugated dienes and anilines.This thesis is divided into three chapters:In the first chapter,various chelation-assisted C(alkenyl)-H activation by transition metal catalysis are introduced,including ketone,ester,amino,carboxyl,hydroxyl-directed alkenyl C-H alkenylation and aromatic C-H amination.The research progress of amide-directed C-H alkenylation and imidation is highlighted.In the second chapter,we developed an iridium-catalyzed region-and stereo-selective cross-coupling of alkenes and alkynes to construct butadienes,proceeded by NH-Ts amide-directed C(alkenyl)-H activation.The synthetic method exhibited the advantages such as mild reaction conditions,broad substrate scope,efficiency,simple operation and oxidant-free conditions.Particularly,this method is successfully applied to C-H functionalization of perillic acid and artemisinic acid derivated amides.In the last chapter,we have developed a ruthenium-catalyzed and acylsilane-directed aromatic C-H imidation.In this method,ortho C-H amination occurred smoothly-using an azide or amide as nitrogen source to afford aniline derivatives.The synthetic method has the advantages of mild reaction conditions and wide applicability of the substrate.