Dissertation > Excellent graduate degree dissertation topics show

Catalytic Asymmetric Henry and Aza-Henry Reaction

Author: WeiYu
Tutor: HeZuo
School: Fourth Military Medical University
Course: Pharmaceutical Analysis
Keywords: Henry Reaction Aza-Henry reaction Schiff base ligands Copper Complexes Phase transfer catalyst Cinchona alkaloid
CLC: O643.32
Type: Master's thesis
Year: 2011
Downloads: 55
Quote: 0
Read: Download Dissertation

Abstract


The catalytic asymmetric reaction is an economical and efficient method of synthesis of chiral drugs and chiral drug intermediates. Catalytic Asymmetric Henry and Aza-Henry reaction is one of the two important methods to build a new carbon-carbon bond. They are the product of a chiral β-nitro-alcohol β-denitration amine compound can be provided according to the synthesis of needs, be easily converted to the corresponding chiral aldehydes, ketones, carboxylic acids, α-amino alcohols, α-amino acids, alpha, beta-two monoamines such as a series of the synthesis of organic intermediates. The topics for these two types of catalytic asymmetric reactions were carried out in-depth study. The catalyst used in catalytic asymmetric synthesis metal complex catalysts and Organocatalyst two categories, they are in a variety of catalytic asymmetric reaction has a very wide range of applications. \Mainly include the following: 1. Cinchona alkaloid derivatives and hydroxy substituted benzaldehyde synthesis of novel chiral Schiff base ligand with Cu (OAc) 2 ligand investigated the catalytic aldehyde with saltpeter alkane asymmetric Henry reaction. The results show that under optimum reaction conditions in the screened out 75a of Cu (II) / Schiff base complexes could efficiently catalyze various aldehyde substrates include aromatic, isobutyl aromatic and aliphatic aldehydes and nitromethane (or nitro ethane) asymmetric Henry reaction and get up to 99% enantioselectivity, 75:25 stereoselectivity, and 84% yield. This reaction, we have done a preliminary study of the mechanism of a variety of methods by single-crystal X-diffraction, NMR and infrared spectroscopy confirmed the structural characterization of the catalyst and the corresponding ligand coordination mode, and the possible catalytic The transition state a reasonable estimate. 2, with the synthesis of cinchona alkaloid with 2 - (chloromethyl) benzimidazole or 1 - (chloromethyl) benzotriazole 10 kinds of the corresponding quaternary ammonium salt catalyst. These 10 kinds of quaternary ammonium salt phase transfer catalyst is used for catalytic benzene sulfinic acid group-substituted amino compound 90a-u and the asymmetric aza-Henry reaction of nitroalkanes. Experimental results show that the phase transfer catalyst 82a in the aqueous phase under the reaction conditions, it is possible to efficiently catalyze a variety of asymmetric reactions of the aroma, isobutyl aromatic and aliphatic substituents imine up to 94% chemical yield, 99% ee The optical yield. When the amount of catalyst is reduced to 2 mol%, the enantioselectivity of the product yet see reduced. When the extended the nitroalkane substrate by nitromethane nitroethane, still obtain a chemical yield of 78%, greater than 99:1 stereoselectivity and the enantioselectivity 99% ee. The study results show that: we designed and synthesized these two types of cinchona alkaloid derived chiral catalyst energy efficient, high enantioselective catalytic asymmetric Henry and aza-Henry reaction. Two reaction reactant, catalyst synthesis is simple, low cost, low consumption, the product of a very important practical value. The subject for the development of catalytic asymmetric the Henry and aza-Hnery, reaction provides practical catalytic system has broad application prospects.

Related Dissertations

  1. The Design of Chial β-Amino Alcohols and their Application to the Asymmetric Henry Reaction and the Asymmetric Reduction of Prochiral Ketones,O643.32
  2. Henry Reaction to Construct Fluorinated Quaternary Carbon Center,O621.25
  3. Synthesis, Structure and Properties of a New Derivative of B-Type Anderson Polyoxoanions Transition-metal,O611.3
  4. Michael Addition Catalyzed by Chiral Bifunctional Thiourea Organocatalysts Bearing Multiple Hydrogen-bonding Donors,O643.32
  5. Synthesis of New Cinchona Alkaloids Derivatives Catalysts and Their Catalytic Reactions,O643.32
  6. Research of Cinchona Alkaloids Derivative Catalytic Asymmetric Reaction and Its Application in Synthesis of Chiral Drug,O643.32
  7. Microgel supported heteropoly acid quaternary ammonium salt the composite microspheres Preparation and desulfurization research,O613.51
  8. The Application of the Aziridino Alcohol Chiral Ligands in Asymmetric Henry and Reformatsky Reaction,O621.2
  9. β- amino alcohols and their derivatives catalyzed enantioselective aza- Henry reaction and Henry Reaction,O643.32
  10. Design and Synthesis of Functional Polymer with Well-Defined Structure,O631.3
  11. The Synthesis of New Chiral Ligands and the Application in the Henry Reaction,O621.25
  12. Preparation of Polyethylene Glycol Grafted on PEG-GMA/MMA Microspheres and Studies on Its Phase Transfer Catalysis,O631.3
  13. Studies on Synthesis of Chiral β-Amino Alcohols and Their Application in Asymmetric Henry Reactions,O621.25
  14. Study on Synthesis and Properties of All Yl-Terminated Bisphenol-A Polyarylester,O633.14
  15. Catalyst Schiff base - the post - transition metal (d) / mixed metal (df) and ring-opening polymerization of lactide,O631.5
  16. Application of Basic Ionic Liquid [bmim]OH in the Condensation Reactions,O621.25
  17. The Study of Non-enzymatic Cleavage of DNA by Metal Complex,O641.4
  18. Sucrose ester synthesis technology research,O631
  19. Synthesis and Characterization of 2, 2’-Biimidazole Metal Complexes and Study on Their Reaction with DNA,O641.4
  20. Stereso-selective Synthesis of 3-deoxy-3-amino Sugars and C-branched Chain Sugars,O636

CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Chemical kinetics,catalysis > Catalytic > Catalytic reaction
© 2012 www.DissertationTopic.Net  Mobile