The Study Of Regioselectivity And Application About Palladium Catalyzed C-H Direct Functionalization

Transition-metal catalyzed C—H bond direct functionalization is becoming amore and more important strategy in organic synthesis. In this paper, we have studiedthe regioselectivity and application about some palladium-catalyzed C—H bonddirect functionalization. They were palladium-catalyzed meta-selective C—H bonddirect arylation of O-β-naphthyl carbamate, palladium-catalyzed amination with thestudy of new method in tosylindole derivates synthesis, and palladium-catalyzedhalogenation with the study of new method in tosylcarbazole derivates synthesis.First of all, using aryl boric acid as arylation agent, we studied the meta-selectivearylation reaction of (Bi)naphthalen dimethylcarbamate. We investigate the influenceof oxidant and its dosage, additive and its dosage, solvent and temperature onarylation reaction one by one. Under optimal condition, we tested the reactionbetween3kinds of (Bi)naphthalen dimethylcarbamate and10kinds of aryl boric acidand got a series of meta-selective arylation product in good to excellent yield, whichthe isolated yield is up to74%. Compared to the meta C—H bond direct arylationwhich was achieved by using very complicated structure as directing group or usingindirect strategy, we could achieve the meta C—H bond direct arylation of(Bi)naphthol derivative by using dimethylcarbamate as directing group.At the second, we studied the amination between N-aryl sulfonamide and acrylicester under room temperature. We investigate the influence of additive and its dosage,oxidant and solvent on amination reaction one by one. Under optimal condition, we tested the amination reaction between6kinds of N-aryl sulfonamide and3kinds ofacrylic ester and got a series of amination product in good to excellent yield, whichthe isolated yield is up to92%. After that, we studied the transformation fromamination product to tosylindole derivates. We investigate the influence of solvent,oxidant and temprature on this reaction one by one. Under optimal condition,4kindsof bioactive tosylindole derivates were synthesized in up to78%yield.At the last, we studied the directed orth-halogenation of N-aryl sulfonamide atroom temperature which sulfamide group acted as directing group. UsingN-halogensuccinimide as halogenations agent, we investigate the influence of catalystand its dosage, additive and its dosage, solvent and temperature on halogenationreaction one by one. Under optimal condition, we tested the halogenation reactionbetween4kinds of N-aryl sulfonamide and2kinds of N-halogensuccinimide and gota series of halogenation product in good to excellent yield, which the isolated yield isup to96%. Besides,1kind of tosylcarbazole derivate were synthesized by usinghalogenation product as starting materials via two steps reaction in overall75%yield.According to the studies above, we have successfully developed a method formeta-selective C—H bond direct arylation of O-β-naphthyl carbamate, and developednew synthesis methods of tosylindole derivates and tosylcarbazole derivates based onpalladium-catalyzed C—H bond direct functionalization. We hope our works couldprovide some new ideas for transition-metal catalyzed C—H activation andfunctionalization.