Font Size: a A A

Cu (I) / Bpy Catalytic Atom Transfer Radical Addition Reaction And Catalytic Reaction Of Au (I) / Chiral Phosphoric Acid

Posted on:2016-01-15Degree:DoctorType:Dissertation
Country:ChinaCandidate:B D R X T A B L K M AFull Text:PDF
GTID:1101330470970178Subject:Organic Chemistry
Abstract/Summary:PDF Full Text Request
In this dissertation we were mainly focuses on four aspects works:Developed the catalytic system that consisting from gold (I) complexes with chiral phosphoric acid; High efficient way to synthesize different type of chiral spiro ketal compounds; The atom transfer radical addition reaction under the CuCl/bpy catalytic reaction system; Reduction reaction of (trichloromethyl) ketone compounds under the mild reaction condition and good results were obtained in all the research topics.Spiroacetals as useful building blocks for the synthesis of a variety of biologically active compounds are important motif that widely presented in a wide range of natural products exhibiting interesting bioactivity, which make great contributions to the drug discovery. Although synthetic methodologies have been well established for the synthesis of various spiroacetals, most of the approaches reported previously depended on the diastereoselective spiroacetalizations from optically pure starting matierals. we will report an asymmetric catalytic synthesis of optically active spiroacetals in excellent yields and high enantioselectivities under the relay catalysis of gold complex and chiral Bronsted acid. In this reaction, the gold(â… ) catalyst in situ generated from a methylgold complex and phosphoric acid to catalyze the initial cyclization reaction of alkynyl glycols while the chiral Bronsted acid dominantly catalyzed the following spiroacetalization and controlled the stereoselectivity.The addition of unsaturated carbon-carbon bonds is one of the most powerful tools for the construction of new carbon-carbon and carbon-hetero bonds. As one important member of them, atom transfer radical addition (ATRA) has emerged as a very specific but reliable procedure. In this work, we want report an efficient copper-mediated intermolecular ATRA reaction between a,a,a-trichloromethyl ketones and alkenes, presenting a good example of intermolecular ATRA reactions. we will report a copper-mediated atom transfer radical addition reaction between a,a,a-trichloromethyl ketones and alkenes is reported, which presents a good example of intermolecular atom transfer radical addition reactions.Recently, the (dichloromethyl) ketone compounds (-COCHCI2) has an increasingly important role in agricultural and medicinal chemistry. Therefore, extensive studies have been conducted on synthesize of (dichloromethyl) ketone compounds, and many synthesis routes have been developed so far. But most of these methods were use chlorine gas, different inorganic or organic chlorination agents. Remarkably is that the method could not be applied for the containing aromatic rings substrates. In this work we was reported the easily and efficient strategy to synthesis of aromatic (dichloromethyl) ketone compounds by the reduction reaction of aromatic (trichloromethyl) ketone compounds under the mild reaction condition.
Keywords/Search Tags:Kharasch reaction, CuCl/bpy System, ATRA, a,a-Dichlorocarbonyls group, relay catalysis, gold(I) complex, Spiroacetals, asymmetric catalysis
PDF Full Text Request
Related items