Denitrogenative Reaction Of Diazo Ester And Its Application In The Synthesis Of Azaindole Derivatives

Visible-light promoted organic reaction of diazo compounds have been widely used in the construction of olefins,heterocycles,cyclopropanes,and other useful molecules over the past few years.The ?-diazo esters have been participated in the transition metal catalyzed reaction in a novel catalytic mode,enabling a variety of denitrogenative reactions.Visible-light catalyzed decarboxylative coupling reaction has become an important chemical conversion because of its wide range of substrates,mild reaction conditions,high efficiency and applicality.Azaindole derivatives have good pharmacological properties in organic synthesis and can be used in the synthesis of natural products and potential central nervous system drugs.This thesis was divided into four sections.Firstly,we developed a visible-light catalyzed denitrogenative & decarboxylative coupling reactions of aryl ?-diazo ester compounds with ?-keto acids.This method provided a synthetic method for the carbonylation of ?-diazo esters with photoredox decarboxylation via the construction of tertiary carbon center under room temperature.The substrate has a wide range and the functional group is well tolerated.This reaction provides a new method for the synthesis of some medicines,functional materials and so on.Then,we developed a visible-light-promoted oxidation reaction of aryl ?-diazo esters under air.The aryl ?-diazo ester can be selectively oxidized by oxygen in the air under the functionalization of an organic visible light catalyst.The denitrogenative ?-oxidation reaction of the aryl ?-diazo ester was carried out by the control of the reaction conditions for the synthesis of 2-oxo-2-arylacetate.Subsequently,visible-light initiated homocoupling reaction of aryl ?-diazo ester has been described.A wide range of substrates are amenable to this protocol with broad functional group tolerance without the addition of photo sensitizer.Finally,the cyclopropane/open-ring/imine cyclization(CRI reaction)reaction of aryl diazo ester has been developed to obtain azaindole derivatives for the synthesis of complex anthracyclines,which may find potential application in the construction of indole homologues.