Organic Mechanisms. Xiaoping Sun
BIOLOGICAL APPLICATIONS OF FUNCTIONALIZED AROMATIC COMPOUNDS PROBLEMS REFERENCES
12 6 NUCLEOPHILIC SUBSTITUTIONS ON SP3‐HYBRIDIZED CARBONS 6.1 NUCLEOPHILIC SUBSTITUTION ON MONO‐FUNCTIONALIZED SP3‐HYBRIDIZED CARBON 6.2 FUNCTIONAL GROUPS WHICH ARE GOOD AND POOR LEAVING GROUPS 6.3 GOOD AND POOR NUCLEOPHILES 6.4 SN2 REACTIONS: KINETICS, MECHANISM, AND STEREOCHEMISTRY 6.5 ANALYSIS OF THE SN2 MECHANISM USING SYMMETRY RULES AND MOLECULAR ORBITAL THEORY 6.6 SN1 REACTIONS: KINETICS, MECHANISM, AND PRODUCT DEVELOPMENT 6.7 COMPETITIONS BETWEEN SN1 AND SN2 REACTIONS 6.8 SOME USEFUL SN1 AND SN2 REACTIONS: MECHANISMS AND SYNTHETIC PERSPECTIVES 6.9 BIOLOGICAL APPLICATIONS OF NUCLEOPHILIC SUBSTITUTION REACTIONS PROBLEMS REFERENCES
13 7 ELIMINATIONS 7.1 E2 ELIMINATION: BIMOLECULAR β‐ELIMINATION OF H/LG AND ITS REGIOCHEMISTRY AND STEREOCHEMISTRY 7.2 ANALYSIS OF THE E2 MECHANISM USING SYMMETRY RULES AND MOLECULAR ORBITAL THEORY 7.3 BASICITY VERSUS NUCLEOPHILICITY FOR VARIOUS ANIONS 7.4 COMPETITION OF E2 AND SN2 REACTIONS 7.5 E1 ELIMINATION: STEPWISE β‐ELIMINATION OF H/LG VIA AN INTERMEDIATE CARBOCATION AND ITS RATE‐LAW 7.6 ENERGY PROFILES FOR E1 REACTIONS 7.7 THE E1 ELIMINATION OF ETHERS 7.8 INTRAMOLECULAR (UNIMOLECULAR) ELIMINATIONS VIA CYCLIC TRANSITION STATES 7.9 MECHANISMS FOR REDUCTIVE ELIMINATION OF LG1/LG2 (TWO FUNCTIONAL GROUPS) ON ADJACENT CARBONS 7.10 THE α‐ELIMINATION GIVING A CARBENE: A MECHANISTIC ANALYSIS USING SYMMETRY RULES AND MOLECULAR ORBITAL THEORY 7.11 E1cb ELIMINATION 7.12 BIOLOGICAL APPLICATIONS: ENZYME‐CATALYZED BIOLOGICAL ELIMINATION REACTIONS REFERENCES
14 8 NUCLEOPHILIC ADDITIONS AND SUBSTITUTIONS ON CARBONYL GROUPS 8.1 NUCLEOPHILIC ADDITIONS AND SUBSTITUTIONS OF CARBONYL COMPOUNDS 8.2 NUCLEOPHILIC ADDITIONS OF ALDEHYDES AND KETONES AND THEIR BIOLOGICAL APPLICATIONS 8.3 BIOLOGICAL HYDRIDE DONORS NAD(P)H AND FADH2 8.4 ACTIVATION OF CARBOXYLIC ACIDS VIA NUCLEOPHILIC SUBSTITUTIONS ON THE CARBONYL CARBONS 8.5 NUCLEOPHILIC SUBSTITUTIONS OF ACYL DERIVATIVES AND THEIR BIOLOGICAL APPLICATIONS 8.6 REDUCTION OF ACYL DERIVATIVES BY HYDRIDE DONORS 8.7 KINETICS OF THE NUCLEOPHILIC ADDITION AND SUBSTITUTION OF ACYL DERIVATIVES PROBLEMS REFERENCES
15 9 REACTIVITY OF THE α‐HYDROGEN TO CARBONYL GROUPS 9.1 FORMATION OF ENOLATES AND THEIR NUCLEOPHILICITY 9.2 ALKYLATION OF CARBONYL COMPOUNDS (ALDEHYDES, KETONES, AND ESTERS) VIA ENOLATES AND HYDRAZONES 9.3 ALDOL REACTIONS 9.4 ACYLATION REACTIONS OF ESTERS VIA ENOLATES: MECHANISM AND SYNTHETIC UTILITY 9.5 BIOLOGICAL APPLICATIONS: ROLES OF ENOLATES IN METABOLIC PROCESSES IN LIVING ORGANISMS REFERENCES
16 10 REARRANGEMENTS 10.1 MAJOR TYPES OF REARRANGEMENTS 10.2 REARRANGEMENT OF CARBOCATIONS: 1,2‐SHIFT 10.3 NEIGHBORING LEAVING GROUP FACILITATED 1,2‐REARRANGEMENT 10.4 CARBENE REARRANGEMENT: 1,2‐REARRANGEMENT OF HYDROGEN FACILITATED BY A LONE PAIR OF ELECTRONS 10.5 CLAISEN REARRANGEMENT 10.6 CLAISEN REARRANGEMENT IN WATER: THE GREEN CHEMISTRY METHODS 10.7 PHOTOCHEMICAL ISOMERIZATION OF ALKENES AND ITS BIOLOGICAL APPLICATIONS 10.8 REARRANGEMENT OF CARBON–NITROGEN–SULFUR CONTAINING HETEROCYCLES PROBLEMS REFERENCES
17 INDEX
List of Tables
1 Chapter 2TABLE 2.1 Regioselectivity of Radical Chlorination of 2‐MethylbutaneTABLE 2.2 Regioselectivity of Radical Bromination of 2‐Methylbutane
2 Chapter 6TABLE 6.1 Quantitative Strengths of Various NucleophilesTABLE 6.2 Factors that Determine the Reaction Mechanisms: Competition Between SN2...