Functionalization Of Cyclic Ketimines And Enamines

Amines and N-heterocycles are found in numerous of biologically active molecules,and the nitrogen atom plays an important role in their physical,chemical,and biological properties.A direct and feasible method for the construction of these compounds is transformation of ketimines and the functionalization of enamines.Based on the construction of amine and N-heterocycle compounds,organocatalyzed asymmetric Mannich reactions of cyclic sulfonyl ketimines,phosphorylation of enamines and aza Diels-Alder reactions of tetrahydrocarbazoles have been developed in this paper.In the first part,by using a saccharide-derived chiral tertiary amino-thiourea catalyst,allylic benzosultams with two stereocentres could be constructed by an organocatalytic asymmetric Mannich reaction of allylic ketones with cyclic ketimines.This protocol provides a wide range of tetrasubstituted?-amino esters with high regio-,diastereo-,and enantioselectivities.What's more,the mode reaction could be carried out on a one gram scale.In addition,hydroboration-oxidation of the mode reaction and subsequent Mitsunobu cyclization provided tricyclic product in good yield with high ee value.Secondly,via C-H activation,we have developed a direct cross coupling for C-P bond formation to access to a wide variety of?-amino vinylphosphonates,which are rarely to synthesis.In the presence of palladium acetate and silver oxide,a wide range ofenamineincludingcyclo,?-alkyl/aryl,?-alkyl/aryl-?-alkyl/carbonyl,?-alkyl-?-alkyl/aryl and?-carbonyl-?-aryl enamines could produce the corresponding dehydrogenation coupling product in 25-98%yield.In addition,?-carbonyl-?-aryl enamines give the product in E selectivity and other product are major in Z selectivity.Meanwhile,in the presence of silver oxide,some of?2-amidoaryl?phosphonate were obtained in 74-91%yield.What's more,reduction of clclo-?-amino vinylphosphonates with H₂ on PtO₂ provide trans-?2-aminocyclohexyl?phosphonate.Thirdly,we developed an aza Diels-Alder reactions of indoles to N-?ortho-Chloromethyl?aryl amides.In the presence of Na₂CO₃ and TBAI,the aza Diels-Alder reactions of indoles and N-?ortho-Chloromethyl?aryl amides was achieved the product in high yield with excellent regioselective.The?-?-induced effect might play a key role in the regioselective.