Handbook of FunctionalizedOrganometallics

Applications inSynthesis, two vol-umes. Edited byPaul Knochel. Wiley-VCH, Weinheim2005. 671 pp.,hardcoverE 249.00.—ISBN3-527-31131-9

Organometallic reagents fulfill indis-pensable roles in organic synthesis.They are used in syntheses of a greatvariety of organic molecules, rangingfrom biologically active molecules to p-conjugated functional organic materials,on both a laboratory and an industrialscale. Nowadays, the structures of suchorganic molecules are mostly complexand highly functionalized. Thus, veryefficient and straightforward synthesesof the desired organic molecules, with-out the use of protecting groups ifpossible, are in great demand. Function-alized organometallic compounds arepowerful tools for achieving suchdream syntheses. The chemistry of func-tionalized organometallics is growing sorapidly that one cannot keep up with theprogress. Although there are somereviews on the subject, it is quite diffi-cult to get a comprehensive overview ofthe significant impact of functionalizedorganometallics. The Handbook ofFunctionalized Organometallics isnicely compiled by Paul Knochel to

bring the chaotic situation into orderso far as possible.

The book consists of two volumes,with 15 chapters altogether. It beginswith a brief introductory section thatsummarizes the history of functionalizedorganometallics. In Chapter 2, M. Yusand F. Foubelo classify functionalizedorganolithium reagents by their struc-tures, and describe the reactions of eachclass of reagents. This chapter containsmore organolithium reagents than Iexpected, which is clear evidence ofthe synthetic advantages of functional-ized organolithium reagents. Chapter 3deals with functionalized organobor-anes, the most important family oforganometallic reagents in recentcross-coupling reactions. It would beimpossible to cover all the papersrelated to functionalized organoboranesin this chapter. Therefore, Knochel andhis co-authors have comprehensivelysummarized all the methods for thepreparation of functionalized organo-boranes and, in addition, have selecteddozens of outstandingly excellent appli-cations, such as the syntheses of bio-logically interesting compounds as com-plex as (�)-gambierol and epothilones.Chapter 4, by Knochel et al. , illustratesthe utility of magnesium reagents, whichhave gained in importance from a prac-tical point of view. The first half of thechapter describes the preparation offunctionalized organomagnesiumreagents, and the second covers theirapplications in organic synthesis. InChapter 5, M. Shimizu and T. Hiyamapresent a concise survey of the synthesesand reactions of allyl-, alkenyl-, andalkylsilanes, many of which are quitecomplex. This chapter gives a clearimpression of the importance of organo-silicon reagents in state-of-the-artorganic synthesis, and of their futurepotential. Functionalized organotinreagents (Chapter 6) are also useful forstereo-, regio-, and chemoselective syn-theses, including cross-coupling reac-tions, nucleophilic carbonyl additions,free-radical reactions, and transmetala-tions. In this chapter, E. Fouquet and A.Herve give an impressive description ofthe capabilities of organotin reagents,with 375 references. Polyfunctionalorganozinc organometallics are dis-cussed in Chapter 7, which is the longestin the book. This chapter, by Knochel

and co-workers, has a structure similarto that of Chapter 4, and the reactionsthat are described provide impressiveevidence of the power of functionalizedorganozinc compounds. Readers will beconvinced that organozincs are ideal forthe synthesis of complex organic mole-cules.

Volume 2 begins with Chapter 8 byS. Matsubara, which focuses on 1,1-dimetalated alkanes. Special attentionis devoted to dizinc and dichromiumreagents. Readers learn at a glance fromthis chapter that these reagents are verysmall in size, yet full of wonder inside.Despite the importance of copperreagents in organic synthesis, Chapter 9,on functionalized organocopperreagents, is rather brief. However, thisshort chapter is filled with useful infor-mation, and should stimulate syntheticorganic chemists to make further effortson the development of functionalizedcopper chemistry. Although organo-nickel compounds are generally toounstable to store as reagents, function-alized organonickel compounds areimportant intermediates in nickel-cata-lyzed reactions. In Chapter 10, T.-Y. Luhand L.-F. Huang highlight the advan-tages of nickel catalysts that make itpossible to construct complex organicmolecules. In Chapter 11, D<tz et al.present an overview of the use ofFischer-type Group 6 metal carbenecomplexes in organic synthesis. Thischapter covers not only functionalizedmetal carbenes for organic synthesis, butalso their applications to supramolec-ular chemistry. Chapter 12, by I. Marek,focuses on the rich chemistry of func-tionalized organozirconium and organo-titanium reagents. In Chapter 13, by G.Cahiez, the reader can take a close lookat the reactions of organomanganesereagents, and discovers that the chemis-try of these reagents is still in its infancyand needs to be explored. Chapter 14,by C. R. Stephenson, deals with func-tionalized multihapto-organometallicsfor organic synthesis. This chapter con-tains both basic chemistry and applica-tions, and might therefore be regardedas a “textbook” of multihapto-organo-metallics. The last chapter, by J. PAri-chon and C. Gosmini, presents a usefuldiscussion of electrochemicalapproaches to functionalized organo-metallics.

Books

194 + 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2006, 45, 194 – 195

The book is well-structured, and theindividual chapters have been written byleading chemists in each area. Theeditor has coordinated the largeamount of information effectively. Allthe chapters deal with up-to-date topicsand are of high quality except for ascattering of typos. The index is detailed

and allows for easy access to the topics.This useful book should be bought bygraduate students as well as industrialand academic researchers interested inorganic synthesis. It will also providestimulating ideas for open-minded orga-nometallic chemists who seek new orga-

nometallic reagents for novel and usefultransformations.

Hideki YorimitsuDepartment of Material ChemistryKyoto University (Japan)

DOI: 10.1002/anie.200585352

AngewandteChemie

195Angew. Chem. Int. Ed. 2006, 45, 194 – 195 + 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org