The concept of concerted mechanisms was formulated nearly 90 years ago and virtually all general organic chemistry texts mention it. Until now, however, no monograph has addressed the concept explicitly. Over the last two decades, substantial advancements made in the development of precise methods for elucidating concerted mechanisms have heightened the need for a comprehensive text on the subject.
Concerted Organic and Bio-organic Mechanisms gathers the salient materials related to this emerging field into a single text. It sets forth the precise definition of concertedness-along with working sub-definitions-and describes rigorous experimental tools chemists can use to diagnose the existence or absence of concerted mechanisms.
Advances in our understanding of concerted mechanisms lead to further questions. Concerted Organic and Bio-organic Mechanisms provides the background and the tools researchers need to consider these important questions and further advance the frontiers of reactions, synthesis, and catalysis.
Table of Contents
Origin of the Concept
Mechanism and its Description
The Definition of Concertedness
Bond Order and Coupling
Potential energy or Free Energy?
Classes of Concerted Reactions
Detection of Intermediates
Exclusion of Stepwise Mechanisms
Transition State Structure
Proton Transfer between Bases
Proton Transfer and Displacement Reactions at Saturated Carbon Centers
Proton Transfer and Double Bond Changes
NUCLEOPHILIC DISPLACEMENTS AT UNSATURATED CARBON
Displacements at the Carbonyl Group
Vinyl Group Transfer
Nucleophilic Aromatic Substitution
Nucleophilic Substitution at Diagonal Carbon
NUCLEOPHILIC DISPLACEMENTS AT SATURATED CARBON
The Carbenium Ion
The Concerted Mechanism
DISPLACEMENT REACTIONS AT HETEROATOMS
Electophilic Displacement at Hydrogen
Nucleophilic Displacement at Saturated Nitrogen
Nucleophilc Displacement at Silicon
Nuleophilic Displacement at Phosphorus(V)
Displacement at Sulfur
Carbon-Carbon Bond Formation
"This is an excellent and authoritative book that covers not only concerted reactions but also stepwise reactions originally posed to be concerted. The book is very densely written, with much information, and with a careful reasoning style that demands concentration from the reader…offers a concise guide to a wide range of mechanistic studies. It will reward the careful student or researcher."
--Charles L. Perrin, University of California, San Diego, American Chemical Society Journal