Study On The Coupling Reaction Of Organoboron Reagents,Aryl Halides And Acetylation Of Phenols Under Microwave Irradiation

The chemical reactions catalyzed by organometal compounds are one of the most attractive areas in organic synthesis. In recent years, a lot of very effective methods for formation of C-C C-Ns C-O C-Ss C-B bonds, which include using a variety of organometal compounds to catalyze the coupling reactions. Generally the catalysts have high activity and good selectivity. At present the coupling reactions of organoborahes with terminal olefins s acid chlorides and aryl halides play an important synthetic approaches in organoborane chemical. The catalysts can be used by many kinds of organometal compounds such as: irons cobalt nickel ruthenium rhodium palladiums titaniums zirconiums tins indium and lithium organic compounds; The achievement has been amazed in preparing of unsaturated or saturated compounds and in synthesizing of natural products bioactive molecules and chiral compounds.The study destination of this thesis is to probe into the metal compounds catalyzed coupling reaction of sodium tetraphenylborate (NaBPh4) with carboxylic anhydrides phenylboronic acid with benzyl halides and aryl halides with terminal olefins under microwave irradiation. We obtained phenyl ketones, diarylmethanes, substituted olefins and modified the Suzuki reaction made it more simple rapid and selective and broadened the scope of microwave technology in organometallic catalyzed reactions. We also study the non-catalytic acetylation of alcohols with acetic anhydride using microwave under solvent-free condition and obtained the satisfaction result.This thesis includes five parts:Chapter One: The Advance of Organic Boronic acids and Boronate in the Organic SynthesisIn this section we introduced the new advances and applications of aryl boronic acidss alkyl boronic acids and organic boronate in the organic synthesis.Chapter Two: Palladium (II)-Catalyzed Cross Coupling Reaction of Sodium Tetraphenylborate with Carboxylic Anhydrides under Microwave IrradiationThe Suzuki reaction, the coupling of organoborate compounds with organicelectrophiles catalyzed by Palladium complexes, is one of the most, fundamental reactions in organic chemistry. The reaction has been drawing increased attention in that the reaction permit the use of organoboron compounds that are thermally stable and inert to water and oxygen.In this section microwave promoted Suzuki reaction of Sodium tetraphenylborate (NaBPh4) with carboxylic anhydrides catalyzed by Pd(PPh3)2Cl2 in THF was first reported. Taking the coupling reaction of NaBPh4 with benzoic anhydrides as an example, we investigated the effects of irradiation power time and various solvents on the reaction. It was found that the highest yield of compounds is obtained at a power level of 525 W for 12 minutes in THF continuous irradiation. The coupling of organborate compounds with organic electrophiles catalyzed by Palladium complexes has been realized under microwave irradiation and the reaction has following advantages: simple fast and excellent yields of products.Chapter Three : Palladium(II)-Catalyzed Cross Coupling Reaction of Phenylboronic Acid with Benzyl Halides under Microwave IrradiationCarbon-carbon bond formation is one of the most fundamental reactions in organic chemistry. The Suzuki reaction, the coupling of organoborate compounds with organic electrophiles catalyzed by Palladium complexes, is a valuable Csp2-Csp bond forming reaction. The reaction has been drawing increased attention in that the reaction permit the use of organoboron compounds that are thermally stable and inert to water and oxygen.In this section microwave promoted Suzuki reaction of phenylboronic acid with benzyl halides catalyzed by Pd(PPh3)2Cl2 DMF/H2O(v/v=10 : 2) was first reported. Taking the coupling reaction of phenylboronic acid with bromomethylnaphthalene as an example, we investigated the effects of irradiation power time and bases on the reaction. It was found that the highest yield of compounds is obtained at a power level of 675 W for 13 minutes in DMF/H2O (v/v=1...