Oxalyl Amide-directed C-C Bond Formation Reactions For Amine Substrates

Transition metal-catalyzed C-H functionalization is one of the most powerful and efficient methods for the construction of a variety of chemical bonds?C-C,C-N,C-O?,which has been widely used for the synthesis of pharmaceuticals,natural products,pesticides and advanced materials.In particular,directing group-assisted C-H functionalization has caused people's attention and becoming current research hotspot in organic synthesis,owing to some obvious advantages,such as high selectivity?regioselectivity,chemoselectivity,and stereoselectivity?,high activity,mild reaction conditions and high atom economy.Amines are an important class of organic compounds.Introducing different directing groups,various C-H bonds of amine substrates could be activated,and it could offer a simple,convenient and efficient synthesis of functionalized derivatives,which is attractive and meaningful in organic synthesis.The thesis mainly focused on the oxalyl amide assisted C?sp²?-H and C?sp³?-H functionalization reactions of amine substrates.The contents were listed as follows:1.A successful protocol has been developed for?-arylation of?-arylethamines at the ortho position under mild conditions.The newly developed methodology first presents broad substrate scope,great functional group tolerance,and good to excellent yields in the synthesis of substituted?-arylethylamines.The transformation represents a practical advantage of oxalyl amide in assistance with C-H functionalization at a remote position.2.The first bidentate directing group assisted highly selective meta-arylation of?-arylethylamine derivatives via palladium/norbornene catalysis is reported.The scope of the aryl iodide coupling partner tolerated a wide range of electron-donating and-withdrawing substituents in good to excellent yields.This meta-arylation also proceeds well with thiophene derivatives,giving the corresponding products in satisfactory yields.3.Sequential,controllable,palladium-catalyzed C–H functionalization of?-arylethylamine for the construction of polysubstituted arenes is reported with the assitance of oxalyl amide.4.A method for palladium-catalyzed oxalyl amide-directed arylation of aliphatic amines with aryl iodides has been developed.A wide variety of aryl iodides are tolerated in this transformation,affording various?-arylpropylamine derivatives.Heterocyclic iodides can also be competent reagents in this?-C?sp³?-H bonds transformation.5.Pd-catalyzed regioselective coupling of?-C-?sp³?-H bonds of oxalyl amide-protected amino acids with aryl and heteroaryl iodides in mild conditions is reported.Both unactivated?-CH₃ and-CH₂ bonds of various oxalyl amide-protected amino acids are activated,offering a practical method for constructing non-natural amino acid derivatives.6.An efficient synthesis of isoindolin-1-ones from oxalyl amide-protected benzylamines,through ruthenium-catalyzed intramolecular C?sp²?-H carbonylation,has been developed.This is the first example where Ru?II?-catalyzed carbonylation of C?sp²?-H using isocyanate as a commercially available carbonyl source.