Study On The Transition Metal Catalyzed Carbon-hydrogen Bond Activation Of Quinones

Quinone derivatives are important and common building blocks, and convenientprecursors for many biological compounds. This paper mainly studies the sulfonyl quinonecompounds and aryl quinine speices which bearing important medicinal value. But relatedsynthesis methods is very limited, at the same time there are a lot of problems in a handful ofreports, such as harsh reaction conditions, the experiment complex operation high reactionlimits, high raw material costs and so on. Now transition metal catalyzed carbon-halogenbond activation to construct organic molecules has become the most commonly used method.So this dissertation mainly focused on the study the transition metal catalyzed carbon-halogenbond activation of quinones, the contents are as follows:7. Transition metal-catalyzed direct C-Sulfone formation by C-S coupling of quinoneswith arylsulfonyl chlorideArylsulfonyl Chloride is considered to be a potent inhibitor of β-Ketoacyl-ACP-synthaseIII (FabH), which is a key condensing enzyme in bacterial fatty acid biosynthesis and part ofthe dissociated fatty acid synthase (FAS). The Pd-catalyzed direct C-sulfone formation by C-Scoupling of quinones with arylsulfonyl chloride has been developed. This methodologyprovides an effective, convenient method.2. The Synthesis of aryl-and alkyl-quinones through transition metal-catalyzed C-CcouplingA direct arylation, alkylation of quinones with aryl and alkyl boronic acids throughRh-catalyzed C-C coupling has been developed under mild conditions. More importantly,good to excellent yields were obtained under room temperature and base-free conditions. Thisreaction provides a practical, efficient method for the synthesis of aryl and alkyl quinones.3. Synthesis of aryl substituted quinones through quinones with aryl halidesThe simple, ligand-free direct arylation of quinones with aryl halides was described byusing Pd(OAc)2as catalyst through Heck reaction. This reaction provided an easy andconvenient method to synthesize aryl-substituted quinones.8. Transition metal-free direct C-H activation of quinones with diaryliodonium saltsA novel ligand-free, transition metal-free direct C-H activation of quinones withdiaryliodonium salts has been developed for the first time. The transformation was promotedonly through the use of a base and gave aryl quinone derivatives with moderate to good yields.This methodology provided an effective and easy way to synthesize aryl quinones.5. Silver-Mediated phosphorylation of C(sp2)-H bonds with P-H bondsHeteroaryl phosphonates are a class of biologically important compounds, medicinalmolecules, photoelectric materials. A novel and high efficient silver-mediated C-Hphosphorylation reaction has been developed with an easy removable amide groups as adirecting group. This C-P coupling of C(sp2)-H bonds with P-H bonds was only with silver aspromoter without any expensive metal.