The Investigation of OrganicReactions and their Mechanisms

Edited by HowardMaskill. Blackwell,Oxford 2006.392 pp., hardcover£ 99.50.—ISBN1-4051-3142-1

The spectacular progress of organic andorganometallic syntheses in recent dec-ades would not have been possible with-out the understanding of chemical reac-tivity that was developed by the mech-anistic investigations in the middle ofthe 20th century. Today we regard it as amatter of course that modern textbooksgenerally adopt a mechanistic approachto organic chemistry. In spite of that, thedetermination of reaction mechanismsplays only a subordinate role in thecurricula of many universities, and somegraduates feel lost when trying to eluci-date the mechanism of a reaction. Thisbook aims to provide a remedy for that,as the editor, Howard Maskill, explainsin the preface (Chapter 1): “This book isto help chemists who do not have astrong background in physical/mecha-nistic organic chemistry but who want tocharacterize an organic chemical reac-tion and investigate its mechanism. Theymay be in the chemical or pharmaceut-ical manufacturing industry and needreaction data to help identify reactionconditions for an improved yield or ashorter reaction time, or to devise saferreaction conditions. Another potentialuser could be a synthetic chemist whowants to investigate the mechanism of a

newly discovered reaction in order, forexample, to optimize reaction conditionsand avoid troublesome side reactions.”Maskill, who is the author of the

highly esteemedmonographThe PhysicalBasis of Organic Chemistry (1985), hassucceeded in assembling a team of verycompetent authors for the present book,and in the chapters that I feel competentto evaluate I found no significant mis-takes. The text includes numerous inter-esting and timely references, and readingthis book stimulatedme to offer a class onthe determination of reaction mecha-nisms, which I intend to base on this text.However, I find the structure of this

12-chapter book incomprehensible. Themain text begins with three chapters thatcan be summarized as “methods fordetermining reaction mechanisms”.These are: T. W. Bentley.s Chapter 2on “Investigation of Reaction Mecha-nisms by Product Studies” and Chap-ters 3, “Experimental Methods for Inves-tigating Kinetics”, and 4, “The Relation-ship Between Mechanism and RateLaw”, which are both co-authored byH. Maskill, M. Canle, and J. A. Santa-balla. These chapters are intimatelyrelated to C. I. F. Watt.s contribution,“The Detection and Characterization ofIntermediates in Chemical Reactions”,which follows much later (Chapter 9).All these chapters are interesting andworthwhile reading for somebody who isalready familiar with the topic and doesnot get confused when the lines of argu-ments are interrupted with references toother chapters. However, for the readersmentioned in the preface it would havebeen helpful if a coordinating editor hadstructured these four chapters in such away as to provide a manual for thesystematic determination of reactionmechanisms. In that way, the numerousinstances of overlapping between thesechapters could have been avoided.Whereas Chapters 2, 3, 4, and 9

teach about the general tools, otherchapters deal with more special aspects.In Chapter 5, “Reaction Kinetics inMultiphase Systems”, J. H. Athertondescribes the problems encountered inmultiphase systems, which are of partic-ular importance in industrial processes.In the following chapter, “Electrochem-ical Methods of Investigating ReactionMechanisms”, O. Hammerich meets theneeds of readers who are not familiar

with electrochemical methods and givesmany practical hints. Chapter 7, by P. R.Schreiner, on “Computational Chemis-try and the Elucidation of Mechanism”,provides a concise overview of thecapabilities of the most commonly usedtheoretical methods, and discusses therotational barriers of ethane and thestructure of the norbornyl cation. In thefollowing chapter, “Calorimetric Meth-ods of Investigating Organic Reac-tions”, U. Fischer and K. Hungerb>hlerdescribe the fundamentals of reactioncalorimetry and its applications to thedetermination of reaction kinetics, aswell as IR–ATR spectroscopy and itscoupling with calorimetry. It is hard tounderstand why computational chemis-try was squeezed in between electro-chemistry and calorimetry.Chapters 10–12 demonstrate how the

tools introduced in Chapters 2–4 and 9can be used to investigate the mecha-nisms of certain types of reactions and toidentify their intermediates. F. Aldab-bagh, W. R. Bowman, and J. M. D. Storeyreport on the “Investigation of ReactionsInvolving Radical Intermediates” (Chap-ter 10). In Chapter 11, “Investigation ofCatalysis by Acids, Bases, Other SmallMolecules and Enzymes”, A. Williamssuccessfully bridges the gap betweenclassical organic chemistry and biology.In the final chapter, “Catalysis by Orga-nometallic Compounds”, G. C. Lloyd-Jones discusses recent mechanistic inves-tigations of rhodium-catalyzed additionsof organoboronic acids to enones, palla-dium-catalyzed cycloisomerizations ofdienes, and olefin metatheses; he com-ments that many “mechanisms” of orga-nometallic chemistry should be consid-ered as “working models” rather thanestablished knowledge.Conclusion: Even though it is often

difficult to find the thread through thisbook, the excellent expertise of theindividual contributions, as well as thetreatment of recent methodologicaldevelopments and of topics of currentinterest, make it a valuable contributionto contemporary chemical literature.

Herbert MayrDepartment Chemie und BiochemieLudwig-Maximilians Universit0t M1nchen(Germany)

DOI: 10.1002/anie.200685497

AngewandteChemieBooks

5053Angew. Chem. Int. Ed. 2007, 46, 5053 – 5054 6 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim