Study On The Suzuki Reaction Of Carbonylation Without Transition Metal Catalysis And The Air Oxyalkylene Reaction Catalyzed By Iron

Diarylmethanone and diarylethanone compounds are two important kinds of organic intermediates,were widely used in medicine and other fields.However,a versatile,efficient,environmentally friendly and preparation method using metal-free catalyst has not been reported yet.Ketones of olefin oxidation are widely used in the synthesis of natural products,pharmaceuticals and chemicals.Our work mainly includes three parts:(1)the development of transition-metal-free catalyzed carbonylative Suzuki coupling reaction under atmospheric pressure in green solvent to synthesize diarylmethanone.(2)the development of metal-free catalyzed carbonylative coupling reactions of benzyl chlorides with aryl potassium fluoroborates under an atmosphere of carbon monoxide(3)the development of iron catalyzed air oxidation of alkylene reaction under an atmospheric.Our main research results are summarized as follows:1.We have developed transition-metal-free catalyzed carbonylation of aryl potassium fluoroborate with aryl iodide to synthesize diarylmethanone.Under the model reaction of 4-chloro-iodobenzene and phenyl potassium fluoroborate,we optimized acid,base,solvent,and temperature.By using pivalic acid(PivOH)as the acid,Na2CO3 as the base,polyethylene glycol-400 as the solvent,and the reaction at 100?.we obtained the optimum result.Under the optimized conditions,aryl potassium fluoroborates and aryl iodides were extended respectively,most of which resulted in over 80%yields.And synthetic drug fenofibrate under the reaction conditions.2.We demonstrated a metal-free catalyzed carbonylation of benzyl chloride,aryl potassium fluoroborate to synthesize diarylethanone analogues.Under the model reaction of 3,4-dichloro-benzyl chloride and phenyl potassium fluoroborate,we optimized the base,solvent and catalyst.By using TBAI as the catalyst,Na2C03 as the base and polyethylene glycol-400 as the solvent,we obtained the optimum result.Under the optimized conditions,the reactants aryl potassium fluoroborates and benzyl chlorides was extended respectively to synthesize a series of diarylethanone.We also proceeded a preliminary study of the reaction mechanism.3.We have developed of an inexpensive metal-catalyzed air oxidation of alkylene reaction.Under the model reaction of Cinnamic alcohol,we optimized catalyst,reaction gas,reductant,amount of reductant and solvent.By using FeCl2 as the catalyst,air as the Oxidant,PMHS as the reductant,the amount of PMHS is 3 equiv,and ethanol as the solvent,we obtained the optimum result.Under the optimized conditions,respectively,terminal olefin and internal olefins extended synthesized a series of ketones.