Chapter 9, by K. Fagnou, is devotedto the rhodium-catalyzed ring-openingof strained oxygen and nitrogen hetero-cycles by nucleophiles. The emphasis ofthe discussion is clearly on the develop-ment of an asymmetric variant of thereaction, which, starting from prochiralbicyclic compounds, offers a route forthe stereoselective synthesis of a,b-difunctionalized carbacycles. Separatesections of the chapter are devoted todetailed discussions of mechanistichypotheses and modeling studies.

Next, in Chapter 10, D. K. Leahyand P. A. Evans discuss allylic substitu-tion. This reaction is commonly associ-ated only with palladium, but the useof rhodium catalysts can often giveexcellent regio- and stereoselectivities.From a synthetic standpoint, the strongpreference of the nucleophilic attacktowards the more highly substitutedend of the allylic system is a very attrac-tive feature, as it leads to a terminal ole-finic group. The authors describe manyexamples to show that rhodium-cata-lyzed allylic substitution, in combinationwith ring-closing olefin metathesis, is aneffective method for synthesizing regio-and stereochemically pure carbacyclesand heterocycles. The next three chap-ters cover the broad field of rhodium-catalyzed cycloadditions. The article byN. Jeong (Chapter 11) is concernedwith reactions that yield cyclopente-nones. These molecules are accessibleeither by a [2 + 2 + 1] cyclization,which can be regarded as a Pauson–Khand type reaction, or by a [4 + 1] cyc-lization from vinyl allenes and carbonmonoxide. In Chapter 12, J. E. Robin-son discusses rhodium-catalyzed routesto six-ring carbacycles by a [4 + 2]cycli-zation, and to eight-ring carbacyclesthrough a [4 + 2 + 2] cycloaddition.This group of chapters on cycloadditionsis completed by a contribution fromP. A. Wender, G. G. Gamber, and T. J.Williams on the synthesis of seven-mem-bered and eight-membered ring systemsfrom vinyl cyclopropanes and vinylcyclobutanones, by using [5 + 2], [5 +

2 + 1], and [6 + 2] strategies.Cycloadditions also occupy a large

part of Chapter 14 (H. M. L. Daviesand A. M. Walji), but instead thecommon element of the reactionsdescribed here is the involvement ofrhodium-stabilized carbenoids with

donor–acceptor functionality. Theauthors begin with strategies for the syn-thesis of cyclopropanes, cyclohepta-dienes, and cyclopentenes by cycloaddi-tion reactions. The second part of theirarticle deals with reactions for insertingthese carbenoids into element�H bonds.

Chapter 15, by M. P. Doyle, is alsoconcerned with rhodium-stabilized car-benoids. Here the topic is the develop-ment and use of asymmetric cyclopropa-nation and C�H insertion reactions thatare catalyzed by chiral rhodium-carbox-imidate complexes. The applications ofboth reactions are illustrated by manyexamples.

In Chapter 16, D. F. Taber and P. V.Joshi report on progress in the area ofstereoselective synthesis of cyclopen-tanes by the rhodium-catalyzed inser-tion of carbenoids into C�H bonds. Aux-iliary control and ways of developing anefficient chiral catalyst are discussed onthe basis of theoretical analyses.

The following chapter, by C. G.Espino and J. Du Bois, describes oxida-tive amination reactions. These involvethe intramolecular insertion of nitrogenfunctionalities such as carbamates, sulfa-mates, and sulfonamides into C�Hbonds. It is very likely that the reactionmechanism involves nitrenes. Theauthors describe mechanistic studiesalong these lines, as well as applicationsto the synthesis of target molecules.

Chapter 18 returns to the subject ofthe chemistry of rhodium-stabilized car-benes. F. G. West describes processes inwhich the primary reaction of the rho-dium-stabilized carbene gives an oxo-nium or ammonium ylide. Under certainconditions, these reactive intermediatescan undergo rearrangement to givefunctionalized heterocycles. Examplesof applications to natural products syn-theses are described.

In Chapter 19, R. M. Savizky andD. J. Austin discuss the formation of1,3 dipoles by the rhodium-catalyzeddecomposition of diazo compounds,and the synthetic applications of suchreactions. The dipoles generated in thisway can be used to synthesize a greatvariety of complex functionalized het-erocycles by 1,3 dipolar cycloaddition.The authors illustrate this by manyexamples in the areas of natural prod-ucts and drugs.

In this volume, P. Andrew Evans andthe authors of the individual contribu-tions have succeeded in bringing orderto the field of rhodium-catalyzed reac-tions, which can otherwise be very con-fusing (at least for nonspecialists). Thechapters are of high quality, both asregards their content and the standardof production (especially the figures),and they provide a good overview ofrecent developments in the area. Thatis helped by the detailed list of contentsand the good keyword index. Despitethe large number of authors and theoften close relationship between thetopics of different chapters, there isonly a very small amount of overlap,which is a testimony to the editor�s effi-cient work. Experienced syntheticchemists who wish to learn aboutrecent developments in the field of rho-dium-catalyzed reactions will benefitespecially from reading the book. How-ever, other readers who would also liketo know about the basic principles ofthis area of work should find it useful,as the introductions to the chapters usu-ally provide concise background infor-mation and references to importantreview articles.

Bernd SchmidtInstitut f�r Organische ChemieUniversit�t Dortmund (Germany)

Acetylene Chemistry

Chemistry, Biologyand Materials Sci-ence. By Fran�oisDiederich, Peter J.Stang and Rik R.Tykwinski. Wiley-VCH, Weinheim2005. 508 pp.,hardcoverE 149.00.—ISBN3-527-30781-8

The publication ten years ago of thebook Modern Acetylene Chemistry,edited by P. J. Stang and F. Diederich,

AngewandteChemie

3803Angew. Chem. Int. Ed. 2005, 44, 3802 – 3804 www.angewandte.org � 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

left no room for doubt that acetylenechemistry has recently been undergoinga revival, and that molecules containingC�C bonds are of great interest formodern synthetic chemistry, for bio-chemistry, and for the development ofnew molecular materials. That trendhas become even more pronounced inthe last ten years. Acetylenes are nowa class of compounds that are of greatimportance in all areas of chemistryand the materials sciences. Therefore,it is appropriate and very welcome thatF. Diederich, P. J. Stang, and R. R. Tyk-winski have now edited a successor tothat book with the title AcetyleneChemistry—Chemistry, Biology andMaterials Science. It consists of 11 chap-ters in which 18 leading experts cover allthe most important aspects of currentacetylenes research. It must be empha-sized that this book is not a new editionof Modern Acetylene Chemistry, but isthe second part of a series, in whichthe topics covered constitute a logicalextension from those in the earlierwork. This is clear from several charac-teristics of the book, in particular achoice of topics that is complementaryto the previous collection, and a com-pletely new team of authors.

The first chapter, “Theoretical Stud-ies on Acetylenic Scaffolds”, gives avery good overview of theoretical stud-ies on a wide variety of acetylenic archi-tectures, such as linear chains, cyclicstructures, star-shaped systems, and therecently synthesized cage compoundswith an expanded cubane-type struc-ture. Computer-based theoretical chem-ical studies of this kind are very impor-tant, as they provide reliable informa-tion about electronic and geometricalproperties, even for compounds thathave not yet been shown to exist, suchas the hypothetical linear hydrocarboncarbyne. This chapter also demonstrateshow theoretical studies can lead to afundamental understanding of impor-tant materials properties, such as thebehavior of oligoynes as molecularwires.

Chapter 2, “Synthesis of Heterocy-cles and Carbocycles by ElectrophilicCyclization of Alkynes”, Chapter 3,“Addition of Terminal Acetylides toCO and CN Electrophiles”, and Chap-ter 5, “Acetylenosaccharides”, providevery impressive evidence of the greatpotential of acetylenes as buildingblocks for the development of new syn-thetic methods, and for the synthesis ofheterocycles, natural products, and newhybrid molecules. Many of the reactionsdescribed here are still relatively new,and the authors show that they oftenopen up surprisingly easy routes forthe synthesis of very interesting mole-cules. The chemistry of acetylides ofthe early transition metals is also ofgreat interest, as is shown in Chapter 4,“Transition Metal Acetylides”.

In the field of molecular electronics,there has recently been much interest inpolymers that are made up of conju-gated alkynyl–aryl units. These materi-als, which show interesting electron-transfer properties and are also highlystable, are described in Chapter 4,“Semiconducting Poly(arylene ethyny-lene)s”. The chapter covers the synthe-sis of such polymers and their electronicand photophysical properties, and alsodescribes the first applications in thearea of sensors, as well as experimentson the production of ordered long-range structures.

An important current area ofresearch in acetylene chemistry is thatconcerned with the development ofmolecular wires and the synthesis ofpolyynes and other alkyne-rich architec-tures as model systems for new carbonallotropes. Chapter 7, “Polyynes viaAlkylidene Carbenes and Carbenoids”,and Chapter 9, “Carbon-Rich Com-pounds: Acetylene-Based Carbon Allo-tropes”, describe in detail methods forthe synthesis of these intriguing mole-cules, and report on the investigationof their physical properties. The inspira-tion for many of these studies has comefrom the discovery of the fullerenes andcarbon nanotubes, and one of the aims is

to make new carbon allotropes by usingorganic synthetic methods.

Two topics related to the above aretreated in Chapters 8 and 10, “Macrocy-cles Based on Phenylacetylene Scaffold-ing” and “Shape-Persistent AcetylenicMacrocycles for Ordered Systems”.Aspects discussed in these chaptersinclude the construction of very exten-sive polycyclic carbon networks, tem-plate-guided syntheses of phenylacety-lene macrocycles, and the preparationof clathrates by introducing sugars, full-erenes, or other guest molecules intosuch macrocycles. Finally, Chapter 11,“Chiral Acetylenic Polymers”, describesthe synthesis of some remarkable archi-tectures containing binaphthylyne units,which leads to relatively rigid chiralpolymers or macrocycles. These havepotential applications as, for example,asymmetric catalysts, enantioselectivefluoroescence sensors, or nonlinear opti-cal materials.

The book presents an interestingoverview of a fascinating area ofresearch. Moreover, the detailed labora-tory procedures that are given at theends of the chapters for preparing mate-rials as typical examples of the variousclasses of compounds are extremelyuseful. The clear formula schemesenable one to quickly grasp the detailsof the molecular structures, which areoften complex and extensive, and atthe same time esthetically pleasing.The list of contents and the extensivesubject index afford easy access to thecontents. The book should be availablein every library concerned with thesefields. The verdict: strongly recom-mended.

Andreas HirschInstitut f�r Organische ChemieUniversit�t Erlangen-N�rnbergErlangen (Germany)

DOI: 10.1002/anie.200585280

Books

3804 � 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org Angew. Chem. Int. Ed. 2005, 44, 3802 – 3804