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Study On The Asymmetric Addition Reaction Of Binary Metal-Catalyzed Aromatic Halogenates To Electron-deficient Olefin

Posted on:2019-10-21Degree:MasterType:Thesis
Country:ChinaCandidate:C R FanFull Text:PDF
GTID:2371330548461300Subject:Chemical engineering
Abstract/Summary:PDF Full Text Request
The Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to an appropriate receptor has been a growing area of research over the last decade.The main acceptors for this 1,4-addition reaction are α,β-unsaturated ketones,esters,amides,aldehydes,sulfoxides and so on.This reaction in the presence of chiral rhodium complexes introduce the aryl and alkenyl groups at the b-position of the above electron poor olefins,enantioselectively.Chiral Rh complexes similar to other transition metals can be added to some electron poor olefins,in turn making them viable to attack by various organometallic reagents for highly enantioselective C-C bond formation.Chiral dienes are a new class of highly effective ligands,developed independently by Hayashi and Carriera et al.,thathave shown great promise in the field of asymmetric catalysis for reactions catalysed by rhodium and iridium.A range of synthetically useful transformations have been realized in excellent yield and enantiomeric excess using C1-symmetric and C2-symmetric dienes.The asymmetric 1,4-addition reaction of rhodium-catalyzed arylboronic acids with a,β-unsaturated ketones has been successfully applied to C2-symmetrical bicyclic diene ligands containing phenyl,benzyl and substituted phenyl groups.High enantioselectivity as well as high catalytic activity was observed in the addition to both cyclic and linear substrates.Firstly,a series of synthetic chiral diene ligands have been reported in the literature to synthesize dicycloalkene ligands with high catalytic activity and enantioselectivity,and then complex with metal rhodium to prepare chiral catalysts for catalysis symmetric 1,4-addition reaction.This project plans to use the recent report of the catalytic synthesis of arylboronic acid methodologies,one-pot method starting from the aryl halide substituted nickel catalyst in-situ synthesis of boronic acid intermediates continue to be asymmetric addition of rhodium catalyst to the electron-poor olefin,The target product was obtained with higher yield and enantioselectivity,the reaction process was saved and the reaction steps were saved.
Keywords/Search Tags:Synthesis of chiral ligands, Asymmetric 1,4-conjugate addition, Formation of C-C bond
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