Categories: Organic Chemistry >> Synthesis >> Radicals

Radical Reactions in Organic Synthesis 

Description

Zard provides a description of radical reactions and their applications in organic synthesis. He illustrates that armed with an elementary knowledge of kinetics and some common sense, it is possible to harness radicals into a tremendously powerful tool for solving synthetic problems. The book begins with a brief historical account and presentation of the basics. It then blends the discussion of the properties of radical processes with the now familiar chemistry of stannanes. Radicals being the same entities, whichever method is used to generate them, a study of the various processes for the creation and capture of radicals constitutes the remainder of the book. Silicon and mercury based techniques as well as the Barton and related decarboxylation procedures are discussed in detail, followed by the Kharasch type atom and group transfer reactions. The increasingly important persistent radical effect, also known as the Fischer-Ingold effect, is examined in the context of non-chain reactions. Both the Kharasch based methods and the persistent radical effect have recently been applied in the emerging field of controlled radical polymerisations. Finally, the vast domain of redox processes is presented in a unified manner with the aim of providing a simple rationale for the multitude of possible transformation. The book concludes with a brief overview and some general practical hints for conducting radical reactions. More than 700 references provide access to the primary literature.

Editorial Review

Many chemists have missgivings of synthesis with radicals, because the reactions are usually of low selectivity and are producing, in the worst case, tar. The used reagents are toxic, and in particular tributyltinn hydride causes headache.

Samir Z. Zard tried to eliminate these prejudices with reasonable arguments. Thus one learns in the first chapters the necessary basics, such as mechanisms and kinetics, and will see immediately on the basis of selected examples that factors, such as temperature and dilution, must be observed exactly with radical reactions.

Tributyltinn hydride is the most used reagent. However, it only takes a third of the book. This seems to be logical, because by far harmless reagents - e.g. tris(trimethylsilyl)silane - are since a long time commercially available. The book also convinces through good examples of newer reactions from current literature.

"Radical Reactions in Organic Synthesis" is both, a text book for the advanced students and a companion for research chemist, who did rarely worked with radicals so far. I recommend the reading of the book especially to the last-mentioned group of people. In particular for reductions and ring closure reactions one receives valuable ideas. You will be surprised, which complicated molecules can be synthesized in a single step!

Contents

1 Introduction and some general concepts
2 General principles: chain reactions based on stannane chemistry
3 Further chain reactions of stannanes
4 Organo-silicon, -germanium, and -mercury hydrides
5 The Barton decarboxylation and related reactions
6 Atom and group transfer reactions
7 The persistent radical effect: non-chain processes
8 Redox processes
9 Some concluding remarks