Online Thesis Search Results

TITLE
CERTIFICATE
DECLARATION
ACKNOWLEDGEMENT
CONTENTS
LIST OF PATENTS /PUBLICATIONS AND CONFERENCE PROCEEDINGS
ABSTRACT
I. Tuning of Borane Reagents for Selective Carboxylate and Related Carbonyl Reductions
I.1 Background and Scope of the Thesis
I.1.1 Introduction
I.1.2 (2S, 3S) and (2S, 3R) - Tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylic acids (1 & 2)
I.1.3 Chirons obtained from (2S, 3S) and (2S, 3R) - tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylic acid
I.2 Tuning of Borane Reagents for Selective Carboxylate and Related Carbonyl Reductions: a Review
I.2.1 Directed Borane and Borohydride reductions
I.2.2 Selective reduction of Carboxylic acids
I.2.3 Selective reduction of Ester and Lactone Carboxylate
I.2.4 Selective reduction of Carboxylates in presence of reducible groups like -NO2, -CN and Halogens
I.2.5 Selective reduction of Arnides / lmides
I.2.6 Selective reduction of Anhydrides
I.3 Conclusions
II. Synthesis of Biologically Significant Chiral Bis Lactone Skeleton
II.1 Biologically active γ-butyrolactones and bislactones
Il.1.1 Avenaciolide and related bislactones
II.1.2 Canadensolide and related bislactones
II.1.3 Cis and Trans Whisky and Cognac lactones
II.1.4 Funebrine & Funebral
II.1.5 PLA2 inhibitors Cinatrin C2 and C3
II.1.6 Methylenolactocin and Protolichesterinic acid
II.2 Synthesis of Avenaciolide
II.3 Results and Discussion
II.3.1 Isolation of (2S, 3s) -Tetrahydro-3-hydroxy-5-oxo-2, 3furandicarboxylic acid (1)
II.3.2 lsolation of (2S, 3R) -Tetrahydro-3-hydroxy-5-oxo-2, 3 furandicarboxylic acid (2)
II.3.3 Enantiomeric Purity of (PS, 3S) -Tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylic acid: Analysis by Vibrational Circular Dichroism (VCD)
II.3.4 Enantiomeric Purity of (2S, 3R) -Tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylic acid: Analysis by Vibrational Circular Dichroism (VCD)
II.3.5 Strategy for the Synthesis of Core Structure of Avenaciolide and Related Molecules
II.3.6 Efficient Site Selective Reduction Employing BH3SMe2 and Catalytic NaBH4
II.3.7 Limitations of Saitos Reaction
II.3.8 Preparation of Dirnethyl (2S, 3S) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylates (10)
II.3.9 Selective Reduction of Dirnethyl (2S, 3S) -Tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylate
II.3.10 Mechanism of Selective Reduction
II.3.11 Methyl (2S, 3R) -terahydro-3-acetyloxy-3-acetyloxymethyl-5-oxo- furan-2-carboxylate (219)
II.3.12 Synthesis of (3aR, 6aS) -3a-hydroxytetrahydrofuro[3, 4-b] furan-2, 6-dione (221)
II.3.13 Applications of Methyl (2S, 3R) -terahydro-3-hydroxy-3-hydroxymethyl-5-oxo-furan-2-carboxylate (206)
II.3.14 Selective Reduction of Dimethyl (2S, 3R) -Tetrahydro-3-Hydroxy-5-oxo-2, 3-furandicarboxyiate (14)
II.3.1 5 Methyl (2S, 3S) -terahydro-3-acetyloxy-3-[ (acetyloxy) methyl]-5-oxo-furan-2-carboxylate and Methyl (2R, 3R) -terahydro-3-acetyloxy-2-[ (acetyloxy) methyl]-5-oxo-furan-3-carboxylate (234 & 235)
II.3.16 Conversion of Methyl (2S, 3s) -terahydro-3-hydroxy-3-hydroxymethyl-5-oxo-furan-2-carboxylate to (3aS, 6aS) -3a -hydroxytetrahydrofuro[3, 4-b]furan-2, 6-dione (236)
II.4 Conformational analysis of Intermediates (208, 209, 232 & 233)
II.4.1 Analysis of 208 and 209
II.4.2 1, 3 diaxial interactions
II.4.3 Spatial separation of the methyl groups in the side chains at C2, C3 positions
II.4.4 Ring strain
II.4.5 Dipole moment
II.4.6 Boron-oxygen distances
II.4.7 Analysis of 232 and 233
II.4.8 Conclusions
II.5 General Experimental Details
II.5.1 Experimental procedures for the theoretical study
II.6 Experimental
II.6.1 (2S, 3S) -Tetrahydro-3hydroxy-5-oxo-2, 3-furandicarboxylic acid (1)
II.6.2 (2S, 3R) -Tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylic acid (2)
II.6.3 Dimethyl (2S, 3s) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylate (10)
II.6.4 Dimethyl (2S, 3R) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylate (14)
II.6.5 Methyl (25 3R) -terahydro-3-hydroxy-3-hydroxymethyl-5-oxo-furan-2-carboxylate (206)
II.6.6 Methyl (2S, 3R) -terahydro-3-acetyloxy-3-acetyloxymethyl-5-oxo-furan-2-carboxylate (220)
II.6.7 (3aR, 6aS) -3a-hydroxytetrahydrofuro[3, 4-b]furan-2, 6-dione (221)
II.6.8 Methyl (2S, 3S) -terahydro-3-acetyloxy-3-[ (acetyloxy) methyl]-5-oxo-furan-2-carboxylate and Methyl (2R, 3R) -terahydro-3-acetyloxy-2-[ (acetyloxy) methyl]-5-oxo-furan-3-carboxylate (234 & 235)
III. Chiral Functionalized Butenolides from (2S, 3s) -Tetrahydro-3-hydroxy-5-OxO-2, 3-furandicarboxylic acid
III.1 Introduction
III.2 Results and Discussion
III.2.1 Preparation of Dialkyl (2S, 3s) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylates (11-1 3)
III.2.2 Preparation of Chiral Butenolides from Dialkyl (2S, 3S) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylates (265-267)
III.2.3 Preparation of Chiral Butenolide from Diisopropyl (2S, 3S) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylates (269)
III.3 Experimental
III.3.1 Disodium (2S, 3S) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylate (6)
III.3.2 Diethyl (2S, 3S) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylate (11)
III.3.3 Diisopropyl (2S, 3S) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylate (12)
III.3.4 Dibenzyl (2S, 3S) -tetrahydro-3-hydroxy-5-oxo-2, 3-furandicarboxylate (13)
III.3.5 Dimethyl 3-methoxy 2 (5H) furanone 4, 5 dicarboxyiate (265)
III.3.6 Diethyl 3-methoxy 2 (5H) furanone 4, 5 dicarboxylate (266)
III.3.7 Dibenzyl 3-methoxy 2- (5H) furanone 4, 5-dicarboxylate (267)
III.3.8 Diisopropyl 3-methoxy- 2- (5H) furanone 4, 5- dicarboxylate (269)
IV. Synthesis of Enantiomerically pure Trialkyl (1S, 2S) and (I S, 2R) -1, 2-dihydroxy-l, 2, 3-propanetricarboxylates and Their Application in Asymmetric Catalysis
IV.1 introduction
IV.1.1 Synthetic Applications of 1, 2 diols
IV.2 Results and Discussion
IV.2.1 Asymmetric Epoxidation Employing Novel Trialkyl (1S, 2R) and (1S, 2R) -1, 2-dihydroxy-1, 2, 3-propanetricarboxylates
IV.2.2 Mechanism of Sharpless Asymmetric Epoxidation reaction
IV.2.3 Asymmetric Oxidation of Sulphides to Sulphoxides Employing novel Trialkyl (1S, 2S) and (1S, 2R) -1, 2-dihydroxy-1, 2, 3-propanetricarboxylates
IV.2.4 Mechanistic explanation for Enantioselective Sulfoxidation
IV.3 Experimental
IV.3.1 Trisodium (1S, 2S) -1, 2-dihydroxy-1, 2, 3-propanetricarboxylate (18)
IV.3.2 Trimethyl (1S, 2S) -1, 2-dihydroxy-1, 2, 3-propanetricarboxylate (20)
IV.3.3 Triethyl (1S, 2S) -1, 2 dihydroxy-1, 2, 3-propanetricarboxylate (21)
IV.3.4 Triisopropyl (1S, 2S) -1, 2 dihydroxy-1, 2, 3-propanetricarboxylate (22)
IV.3.5 Trisodium (1S, 2R) -1, 2-dihydroxy-1, 2, 3-propanetricarboxylate (19)
IV.3.6 Trimethyl (1S, 2R) -1, 2-dihydroxy-1, 2, 3-propanetricarboxylate (23)
IV.3.7 Triethyl (1S, 2R) -1, 2 dihydroxy-1, 2, 3-propanetricarboxylate (24)
IV.3.8 Triisopropyl (1S, 2R) -1, 2 dihydroxy-1, 2, 3propanetricarboxylate (25)
IV.3.9 Epoxygeraniol (276) Employing (20) as chiral ligand
lV.3.10 Methyl p-tolyl sulphoxide (290) (Employing as (20) chiral ligand)
V. Summary of the Thesis
References