Organic Mechanisms Reactions, Methodology, and Biological Applications

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  • Format: Hardcover
  • Copyright: 2013-07-10
  • Publisher: Wiley

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Instills a deeper understanding of how and why organic reactions happen

Integrating reaction mechanisms, synthetic methodology, and biological applications, Organic Mechanisms gives organic chemists the tools needed to perform seamless organic reactions. By explaining the underlying mechanisms of organic reactions, author Xiaoping Sun makes it possible for readers to gain a deeper understanding of not only chemical phenomena, but also the ability to develop new synthetic methods. Moreover, by emphasizing biological applications, this book enables readers to master both advanced organic chemistry theory and practice.

Organic Mechanisms consists of ten chapters, beginning with a review of fundamental physicochemical principles that are essential for understanding the nature of organic mechanisms. Each one of the remaining chapters is devoted to a major class of organic reactions, including:

  • Aliphatic C–H bond functionalization
  • Functionalization of the alkene C=C bond by cycloaddition reactions
  • Nucleophilic substitutions on sp3-hybridized carbons
  • Nucleophilic additions and substitutions on carbonyl groups
  • Reactivity of the α-hydrogen to carbonyl groups
  • Rearrangements

A brief review of basic organic chemistry begins each chapter, helping readers move from fundamental concepts to an advanced understanding of reaction mechanisms. Key mechanisms are illustrated by expertly drawn figures highlighting microscopic details. End-of-chapter problems enable readers to put their newfound knowledge into practice by solving key problems in organic reactions with the use of mechanistic studies, and a Solutions Manual is available online for course instructors.

Thoroughly referenced and current with recent findings in organic reaction mechanisms, Organic Mechanisms is recommended for upper-level undergraduates and graduate students in advanced organic chemistry, as well as for practicing chemists who want to further explore the mechanistic aspects of organic reactions.

Author Biography

XIAOPING SUN, PhD, is Professor of Chemistry at the University of Charleston. Dr. Sun has more than ten years of experience teaching advanced organic chemistry and biochemistry. His research focuses on studying the mechanisms of chemical reactions. Dr. Sun is the recipient of a research grant from the National Science Foundation.

Table of Contents

Chapter 1 Fundamental Principles

1.1 Reaction mechanisms and their importance

1.2 Elementary (concerted) and stepwise reactions

1.3 Molecularity

1.4 Kinetics

1.5 Thermodynamics

1.6 The transition state

1.7 The molecular orbital theory

1.8 Electrophiles/nucleophiles versus acids/bases

1.9 Isotope labeling



Chapter 2 The Aliphatic C–H Bond Functionalization

2.1 Alkyl radicals: Bonding and their relative stability

2.2 Radical halogenations of the C–H bonds on sp3-hybridized carbons: Mechanism and nature of the transition states

2.3 Energetics of the radical halogenations of alkanes and their regioselectivity

2.4 Kinetics of radical halogenations of alkanes

2.5 Radical initiators

2.6 Transition-metal-compounds catalyzed alkane C–H bond activation and functionalization

2.7 Superacids catalyzed alkane C–H bond activation and functionalization

2.8 Nitration of aliphatic C–H bonds via the nitronium NO2+ ion

2.9 Enzyme catalyzed alkane C–H bond activation and functionalization: Biochemical methods



Chapter 3 Functionalization of the Alkene C=C Bond by Electrophilic Additions

3.1 Markovnikov additions via intermediate carbocations

3.2 Electrophilic addition of hydrogen halides to conjugated dienes

3.3 Non-Markovnikov radical addition

3.4 Hydroboration: Concerted, Non-Markovnikov syn-addition

3.5 Transition-metal catalyzed hydrogenation of the alkene C=C bond (syn-addition)

3.6 Halogenation of the alkene C=C bond (Anti-addition): Mechanism and its stereochemistry



Chapter 4 Functionalization of the Alkene C=C Bond by Cycloaddition Reactions

4.1 Cycloadditions of the alkene C=C bond to form three-membered rings

4.2 Cycloadditions to form four-membered rings

4.3 Deals-Alder cycloadditions of the alkene C=C bond to form six-membered rings

4.4 1,3-Dipolar cycloadditions of the C=C and other multiple bonds to form five-membered rings

4.5 Pericyclic reactions



Chapter 5 The Aromatic C-H bond Functionalization and Related Reactions

5.1 Aromatic nitration: All reaction intermediates and full mechanism for the aromatic C-H bond substitution by nitronium (NO2+) and related electrophiles

5.2 Mechanisms and synthetic utility for aromatic C-H bond substitutions by other related electrophiles

5.3 The electrophilic aromatic C–H bond substitution reactions via SN1 and SN2 mechanisms

5.4 Substituent effects on the electrophilic aromatic substitution reactions

5.5 Isomerizations effected by the electrophilic aromatic substitution reactions

5.6 Electrophilic substitution reactions on the aromatic carbon-metal bonds: Mechanisms and synthetic applications

5.7 Nucleophilic aromatic substitution via a benzyne (aryne) intermediate: Functional group transformations on aromatic rings

5.8 Nucleophilic aromatic substitution via an anionic Meisenheimer complex

5.9 Biological applications of functionalized aromatic compounds



Chapter 6 Nucleophilic Substitutions on sp3-Hybridized Carbons: Functional Group Transformations

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



Chapter 7 Eliminations

7.1 E2 Elimination: Bimolecular b-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 b-elimination of H/LG via an intermediate carbocation and its rate-law

7.6 Special b-elimination reactions

7.7 Elimination of LG1/LG2 in the compounds that contain two functional groups

7.8 a-Elimination giving a carbene: A mechanistic analysis using symmetry rules and molecular orbital theory

7.9 E1cb elimination and its biological applications



Chapter 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



Chapter 9 Reactivity of the a-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 Roles of enolates in metabolic processes in living organisms



Chapter 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 Photochemical isomerization of alkenes and its biological applications

10.7 Rearrangement of carbon-nitrogen-sulfur containing heterocycles



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