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Side Reactions in Organic Synthesis

Sample Chapter

Florencio Zaragoza Dörwald

Softcover, 374 Pages
First Edition, 2004
ISBN: 3-527-31021-5
Wiley-VCH

Description

Most syntheses in the chemical research laboratory fail and usually require several attempts before proceeding satisfactorily. Failed syntheses are not only discouraging and frustrating, but also cost a lot of time and money. Many failures may, however, be avoided by understanding the structure-reactivity relationship of organic compounds.

This textbook highlights the competing processes and limitations of the most important reactions used in organic synthesis. By allowing chemists to quickly recognize potential problems this book will help to improve their efficiency and success-rate. A must for every graduate student but also for every chemist in industry and academia.

Editorial Review

There are several reactions in organic chemistry that come up time and again. Combinatorial chemistry and drug development work is often based on a small basis set of well-optimized, versatile synthetic methods, such as alkylation, acylation, and palladium-catalyzed cross-coupling, which can be applied to a broad range of reactants. In principle, the goal is to find the best available method within the limitations of selectivity (in multifunctional molecules) and reactivity (in sterically hindered molecules), but there is often not enough time to optimize individual transformations.

The monograph "Side Reactions in Organic Synthesis" focuses on a small number of reactions, which are explained through case studies of how the transformation can go awry. This work can readily be used as a textbook, since it combines theoretical explanations with concrete examples to help solidify the reader’s understanding. It can also serve as a guidebook for those situations where a standard method simply fails in the laboratory.

"Side Reactions in Organic Synthesis" will appeal both to advanced students who wish to revisit the underlying concepts, as well as to practitioners who need to find a quick alternative when a problem arises. The book is quite pithy, and the selection of subjects and chapters has resulted in a rather successful contribution.

Contents

ORGANIC SYNTHESIS: GENERAL REMARKS
Introduction
Synthesis Design
Hard and Soft Acids and Bases
The Curtin-Hammett Principle
STEREOELECTRONIC EFFECTS AND REACTIVITY
Hyperconjugation with sigma Bonds
Hyperconjugation with Lone Electron Pairs
Hyperconjugation and Reactivity
Conclusion
THE STABILITY OF ORGANIC COMPOUNDS
Introduction
Strained Bonds
Incompatible Functional Groups
Conjugation and Hyperconjugation of Incompatible Functional Groups
Stability towards Oxygen
Detonations
ALIPHATIC NUCLEOPHILIC SUBSTITUTIONS: PROBLEMATIC ELECTROPHILES
Mechanisms of Nucleophilic Substitution
Structure of the Leaving Group
Structure of the Electrophile
THE ALKYLATION OF CARBANIONS
Introduction
The Kinetics of Deprotonations
Regioselectivity of Deprotonations and Alkylations
The Stability of Carbanions
THE ALKYLATION OF HETEROATOMS
Alkylation of Fluoride
Alkylation of Aliphatic Amines
Alkylation of Anilines
Alkylation of Alcohols
Alkylation of Phenols
Alkylation of Amides
Alkylation of Carbamates and Ureas
Alkylation of Amidines and Guanidines
Alkylation of Carboxylates
THE ACYLATION OF HETEROATOMS
Problematic Carboxylic Acids
Problematic Amines
Problematic Alcohols
PALLADIUM-CATALYZED C-C BOND FORMATION
Introduction
Chemical Properties of Organopalladium Compounds
Mechanisms of Pd-Catalyzed C--C Bond Formation
Homocoupling and Reduction of the Organyl Halide
Homocoupling and Oxidation of the Carbon Nucleophile
Transfer of Aryl Groups from the Phosphine Ligand
Ipso- vs Cine-Substitution at Vinylboron and -tin Derivatives
Allylic Arylation and Hydrogenation as Side Reactions of the Heck Reaction
Protodemetalation of the Carbon Nucleophile
Sterically Hindered Substrates
Cyclometalation
Chelate Formation
CYCLIZATION
Introduction
Baldwin's Cyclization Rules
Structural Features of the Chain
Ring Size
Heterocycles
MONOFUNCTIONALIZATION OF SYMMETRIC DIFUNCTIONAL SUBSTRATES
Introduction
Monofunctionalization of Dicarboxylic Acids
Monofunctionalization of Diols
Monofunctionalization of Diamines
Monoalkylation of C,H-Acidic Compounds
Monoderivatization of Dihalides