Dissertation > Excellent graduate degree dissertation topics show

Study of Ferrier Rearrangement Reaction (TYPE Ⅰ)Promoted by Metal Lewis Acid

Author: LinLei
Tutor: ChenPeiRan
School: Donghua University
Course: Organic Chemistry
Keywords: Ferrier rerrangement(Ⅰ type) 2,3-unsaturated glycoside triflatetitanium trichloride ruthenium trichloride unsaturated carbohydrates stereoselectivity
CLC: O621.251
Type: Master's thesis
Year: 2014
Downloads: 10
Quote: 0
Read: Download Dissertation

Abstract


2,3-Unsaturated-glycosides are of great importance in synthesis and have been widely used as chiral intermediates in the preparation of biologically active compounds and functional materials since they could provide the regio-and stereo-varieties for the subsequent reactions. One of the most useful procedures to achieve2,3-unsaturated glycosides directly and efficiently is Type I Ferrier rearrangement, in which glycal is reacted with nucleophile with the catalysis of various Lewis acid catalysts.A wide range of Lewis acid catalysts have been reported in the literatures. However, some of those reaction systems suffered from the drawbacks in terms of large excess of nucleophile, stoichiometric amount of catalyst, harsh reaction conditions, and low yields, which leading to extensive work up. We therefore have interest in finding new efficient catalyst for this reaction for milder and more efficient synthetic process with good anomeric selectivity and yield by using stoichiometric amount of nucleophile under low catalyst load.In this dissertation, two Lewis acid-catalyzed Ferrier rearrangement reaction system have been investigated.1) An efficient Type I Ferrier rearrangement reaction system for the synthesis of2,3-unsaturated-O-glycosides has been established by using TiCl3(OTf) as the catalyst. A series of2,3-unsaturated-O-glucosides were prepared from3,4,6-tri-O-acetyl--D-glucal in good yield and high anomeric selectivity.2) With RuCl3·3H2O as catalyst, an improved method for the synthesis of2,3-unsaturated-glycosides has been established. A series of2,3-unsaturated-glucosides were obtained from2,4,6-tri-O-acetyl-D-glucal or3,4-Di-O-acetyl-6-deoxy-L-glucal in good yield and high anomeric selectivity. By using TiCl3(OTf) or RuCl3·3H2O as catalyst, a series of alcohols and thiols were reacted with glucal donor affording2,3-unsaturated glycosides in high yield and good anomeric selectivity. The influence of the inductive and the steric effects of the nucleophiles on the reaction results has also been examined. This reaction system has also demonstrated its applicability in the synthesis of natural product analogs of biological interest by the Ferrier rearrangement.

Related Dissertations

  1. With functional groups of organic zinc halide reagents with aromatic aldehydes double alkylation reaction of alkenyl,O621.25
  2. Synthesis of (E)-α-Iodovinyltellurides and (Z)-α-Arylsulfenylvinyltellurides and Their Applications in Highly Selective Synthetic Reactions,O621.3
  3. Amberlyst 15 catalyzed glycosidation reaction,R914
  4. Chiral Separation and Pharmacological Profile of Doxazosin Enantiomers,O658.9
  5. Asymmetric dihydroxylation reaction of new recycling and reuse of chiral ligands,R914
  6. The Research on Enzyme-Linked Immunosorbent Assay for S-Bioallethrin,S482.35
  7. Studies on Some Fluorine Chemistry and Free Radical Addition Reactions Ofallenes,O621.256.7
  8. Studies on the Analysis, Environmental Behaviors, and Toxicity of Typical Chiral Triazole Fungicide Enantiomers,S482.2
  9. Study on the Synthesis of α-epoxycedrane,TQ655
  10. Synthesis of Chiral Aminoalkylphenols,O625.31
  11. Theoretical Studies on Metal-Bisoxazoline Catalyzed Asymmetric 1,3-Dipolar Cycloaddition Reactions,O643.32
  12. Chiral Bisoxazoline Metal Complexes on the 1,3-Dipolar Cycloaddition Reaction of Nitrone,O621.25
  13. Ziegler-Natta catalysts for olefin polymerization reaction theory,O631.5
  14. Quantum Chemistry Studies on the Stereoselectivity of Diffierent Aldehydes in the Direct Aldol Reactions,O621.25
  15. Stereoselectivity in Trans-tramadol Metabolism and Trans-O-demethyltramadol Formation in Rat Liver Microsomes,R96
  16. Stereoselective Synthesis of Functionalized 1, 3-Dienes Containing Silicon,O623.121
  17. Enantioselective Binding of Chiral Drugs, Mexiletine and Ketoprofen, to Plasma Proteins,R96
  18. Study on Transmetal Catalysts for Hydrosilylation of Olefins,O643.36
  19. Application of Ionic Liquids and Small-molecule Catalysis in Organic Synthesis,O643.32
  20. The Stereoselective Metabolism Study of Fluoxetine Catalized by Recombinant Human Cytochrome P450 Enzymes,R96

CLC: > Mathematical sciences and chemical > Chemistry > Organic Chemistry > Organic Chemistry general issues > Properties of organic compounds > Chemical properties of organic reactions > Organic catalysis
© 2012 www.DissertationTopic.Net  Mobile