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Journal of Organometallic Chemistry 595 (2000) 304–306

Book Review

Transition Metals for Organic Synthesis, 7olumes 1 and2, Building Blocks and Fine Chemicals, Edited by M.Beller, C. Bolm, Wiley–VCH, Weinheim, 1998, pp.1066. DM 798 (hbk), ISBN-3-521-29501-1

More than 100 authors (about one third from Ger-many) from 15 countries have contributed to this 1066page, two-volume publication. Many of the chaptersare from practitioners in the field and the stated aim ofthe editors is ‘to provide the reader with the basicpossibilities of organometallic chemistry for organicsynthesis’, to justify their claim that ‘really new discov-eries’ will result from this rapidly developing area. Thisbook comes hard on the heels of the similarly priced,excellent two-volume ‘Applied Homogeneous Catalysiswith Organometallic Compounds: A ComprehensiveHandbook’ edited by B. Cornils and W.A. Herrmann,(1996) from the same publishers and inevitably thereare several areas of overlap. Likewise, the Wiley publi-cation ‘Palladium Reagents and Catalysts, Innovationsin Organic Synthesis’ by J. Tsuji (1996) gives a muchmore in-depth account of organopalladium chemistrythan is attempted in the present publication.

A comprehensive coverage of the vast area of en-deavour suggested by the title ‘Transition Metals forOrganic Synthesis’ is clearly out of the question, but theeditors, Beller and Bolm, have selected what they feelare the most important transition-metal-catalysed (or-mediated) reactions and the resulting contributionscover the literature up to 1997. The organisation of thebook into two volumes enables Volume 1 to deallargely with methods of making carbon�carbon bonds,whereas Volume 2 concentrates mainly on oxidationand reduction reactions but also briefly mentions somefurther specialised topics. The subject matter in the twovolumes is dealt with by the individual authors inwidely varying degrees of detail and it seems likely thatthe readership will dip into the book for the specificinformation they require rather than read it from coverto cover.

The general standard of production is very high, withclearly printed text, figures, tables and schemes. How-ever, the use of multidigit section numbering occasion-ally gets out of hand. For example, in Chapter 2.13 ofVolume 2 the introduction labelled 2.13.2. in the list of

contents has no subsequent entries although the textcontains additional sections up to 2.13.2.5. etc. The useof the same numbering system for the chapters in bothVolumes 1 and 2 also leads to unnecessary additionalconfusion.

The first chapter of Volume 1, entitled ‘Basic aspectsof organic synthesis with transition metals’, is a per-sonal view by one of the leading experts in the field(Trost), who sets out the ground-rules that are encoun-tered throughout the two-volume series. This is anexemplary, albeit short, introduction which highlightsthe importance of chemoselectivity, regioselectivity,diastereoselectivity, enantioselectivity, and atom econ-omy. The second introductory chapter (by Keim) suc-cinctly summarises the concepts for the use of transitionmetals in the industrial syntheses of fine chemicals,touching on both economic and environmental con-cerns. The remainder of Volume 1 details the morespecific transition-metal-catalysed (section 2) or metal-mediated (section 3) reactions as outlined below.

In section 2, Botteghi, Marchetti, and Paganelli dis-cuss hydroformylation reactions, particularly in thecontext of synthesising pharmaceuticals, natural prod-ucts and agrochemicals, while El Ali and Alper coverhydrocarboxylation and hydroesterification reactions.The uses of Pd and/or Pd–Co catalysts for the car-bonylation of allylic and propargylic compounds andamidocarbonylations are discussed by (i) Tsuji and Kijiand (ii) Kuhlein and Geissler, respectively. Mechanisticdetails figure prominently and the reader is providedwith further information in the reviews cited in thereferences. Transition-metal-catalysed alkene andalkyne hydrocyanation (including asymmetric hydro-cyanation) is covered by Casalnuovo and RajanBabu;likewise the field of cyclopropanation is well describedby Pfaltz, although the treatment of the Simmons-Smith reaction is rather brief.

Bonnemann and Brijoux give an authoritative ac-count of the very important area of cyclomerisation ofalkynes, and focus in particular on the formation ofsix-membered carbocycles, and extensions to the syn-thesis of the related nitrogen containing heterocycles.Crowe describes synthetic routes to the construction ofcyclopentane ring systems by intramolecular hydroacyl-ation and reductive cyclisation, and a fairly brief

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overview of alkene isomerisation reactions is presentedby Otsuka and Tani, two very active pioneers in thisarea.

Geissler’s coverage of palladium- and nickel-catalysed cross-coupling reactions includes not onlyorganoboron (Suzuki reactions) and organotin (Stillereactions), but also organo-copper, -aluminium, -zirco-nium, -magnesium, -lithium and -silicon compounds.Both C�N and C�O bond-formation reactions are de-tailed by Beller and Riermeier. The use of chiral ansa-bridged metallocenes for the enantioselective alkylationof alkenes is very briefly discussed by Hoveyda, whoalso provides information on the kinetic resolution ofunsaturated heterocycles and cyclic allyl ethers.

Recent developments in the versatile Heck reaction,first discovered in the late 1960s, are described byBeller, Riermeier, and Stark, mechanistically and withan emphasis on the use of chiral Pd catalysts. There isan interesting coverage of applications for the synthesisof natural products, pharmaceuticals and a variety ofcomplex organic building blocks, together with a usefulbibliography. Related coupling reactions involving C�Hactivation represent a recently developing field and arereviewed by Dyker. Palladium-catalysed allylic substitu-tion reactions are discussed by Heumann, who citesmore than 100 references, while Takahashi, Doi, andYamamoto review the Pd-catalysed cyclisation of allylicacetates with alkenes and allenes.

I had expected a rather more in-depth coverage in thechapter on the applications of olefin metathesis (Schus-ter and Blechert) than the fairly brief summary pro-vided, although the article does contain severalimportant references up to 1997. Some further informa-tion is contained in the chapter in section 3 by Petasis,mainly concerned with titanium�carbene-mediated re-actions, and both these chapters describe briefly ring-opening metathesis polymerisation (ROMP). The finalchapters in section 2 are devoted to quite an extensivecoverage of the synthetic use of both homo- and hetero-metallic lanthanide compounds (Kobayashi, Shibasakiand Sasai) and a very short account by Oguni of themetal-catalysed addition of cyanides to aldehydes.

The third section of Volume 1 is concerned withstoichiometric systems and begins with articles byDoetz and Pfeiffer on the reactivity of Fischer-typecarbenes, followed by titanium�carbene-mediated sys-tems (Petasis), featuring the Tebbe reagent. The cover-age includes aldol and Michael addition reactions,cyclo-additions, cyclopropanation and metathesis reac-tions and carbene�CO coupling. Reactions of ti-tanocenes with alkynes and nitriles are considered, butno mention is made of the rapidly developing relatedfield of phospha�alkyne chemistry.

The McMurray reaction, involving low-oxidation-state titanium-promoted coupling of aldehydes or ke-tones to alkenes, is covered by Furstner who includes a

short selection of different applications. Vanadium-me-diated couplings are described by Jendralla, who alsoalludes very briefly to related niobium systems, and thisis followed by useful discussions of chromium(II)-,(Hodgson and Comina) and samarium II-mediatedcoupling reactions (Gu and Curran). This last chapteralso refers briefly to radical and cascade reactions. Theoxidative radical cyclisation reactions based on man-ganese(III) (Snider) is followed by a chapter byDuthaler and Hafner concerned with chiral, titanium-mediated reactions involving addition of nucleophilesto aldehydes, and cycloaddition reactions.

Zinc-mediated reactions are covered in some detailby Knochel in a chapter containing over 200 references,and applications range from asymmetric synthesis tocombinatorial chemistry. The role of zinc is also dealtwith in the short chapter by Marek and Normantcovering carbometalation reactions. Enantioselectiveconjugate addition reactions are the main theme of thevery short chapter by Alexakis and the volume endswith the chemistry of iron–acyl complexes, (Ruck–Braun), iron–diene compounds (Knolker), chromium–arene complexes (Schmalz and Siegel), andPauson–Khand chemistry (Jeong). Here the treatmentof the iron systems is fairly brief and predictable, theemphasis in the iron–acyl chapter being largely onderivatives chiral at iron. The iron–diene chapter fo-cuses on cyclopentadienenone synthesis, applications ofbutadiene and cyclohexadiene systems, alkaloid synthe-sis, and diastereoselective spiroannulations. Nucleo-philic additions, ring lithiation and side-chain activa-tion form the main topics in the very short descriptionof the chemistry of arene–chromium complexes. Thecoverage of Pauson–Khand chemistry includes bothstoichiometric and catalytic aspects. Topics presentedinclude regioselectivity and promoter-assisted reactionsas well as synthetic strategies in which the Pauson–Khand reaction figures prominently.

Section 1 of Volume 2, which also contains manychapters by experienced researchers, begins by address-ing the vast area of organic reduction reactions. This issubdivided into chapters on homogeneous and hetero-geneous hydrogenation reactions, transfer hydrogena-tions, hydrosilylations, metal-catalysed hydroboration,and transition-metal hydride reduction of imines andenamines. Following a very brief outline by Borner andHolz of mono- and poly-olefin hydrogenation, includ-ing diastereoselective and asymmetric hydrogenation,Burk and Bienewald consider unnatural a-amino acidformation via asymmetric hydrogenation of enamides.Ohkuma and Noyori give an informative account of thevery important area of hydrogenation of carbonyl com-pounds, with 160 references cited. Useful tables of dataon hydrogenation of ketones, aldehydes, CO2 and car-boxylic acids are presented. The following section bySpindler and Blaser addresses the enantioselective re-

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duction by dihydrogen of C�N bonds and gives anassessment of Rh, Ir, and Ru catalysts.

The section devoted to heterogeneous hydrogenationbegins with a useful overview by Blaser, Steiner, andStuder of catalytic suppliers, catalyst choice, reactionmedia and conditions, details of apparatus and proce-dures, before a consideration of selected reactions.Transfer hydrogenations are dealt with by Gladiali andMestroni in a 20-page review, covering mechanisms andrelative merits of metals and promoters, before a dis-cussion of substrates for which H-transfers are assessedas being particularly useful. The important area ofhydrosilylation is described by Yamamoto andHayashi, augmented by a short contribution fromBrunner dealing with carbonyl compounds. Fu gives avery brief treatment of metal-catalysed hydroborationsand the final aspect of this topic, by Singaram andGoralski, concentrates on the reduction of imines andenamines. Curiously, although the title of the chapterrefers only to transition-metal hydrides, the subjectmatter concerns hydrides of boron, aluminium, silicon,tin, and tellurium.

Section 2 of Volume 2 is devoted to oxidation, andfollowing Jorgensen’s description of the basics, thereare important contributions by Meunier on C�H bondoxidations (including discussions of mono-oxgenasesand cytochrome P-450 models) and allylic oxidationsby Schlingloff, Bolm, Grennberg and Backvall. A veryshort account of metal-catalysed Baeyer–Villiger reac-tions (Bolm, Beckmann, and Khanh Luong) is followedby authoritative discussions on both asymmetric dihy-droxylation and aminohydroxylation reactions by Kolband Sharpless.

Various aspects of epoxidations involving titanium,manganese, rhenium, and other transition metals, aswell as metalloporphyrins, are considered in some detailby a number of authors in Chapter 2.7 (Katsuki, Mu-niz–Fernandez, Bolm, Herrmann, Fischer, Weskamp,Thiel, and Halterman) but for some reason a further

treatment of rhenium-catalysed epoxidations by Fischerand Herrmann appears in Chapter 2.11 following thediscussions of Wacker oxidation (Feringa), hydroami-nation of alkenes and alkynes (Muller and Beller) and abrief discourse on heteropolyanions (Neumann). Theremaining chapters of section 2 concern aerobic, metal-catalysed oxidation of alcohols, (Marko, Giles,Tsukazaki, Brown, and Urch), the oxidation of het-eroatoms (Kagan and Luukas) and amine oxidation(Murahashi and Imada). Section 3 of Volume 2 isdevoted to six special topics treated roughly equally,namely, supported metal catalysts (Basset, Candy, andSantini), two-phase catalysis (Sinou), photocatalysis(Hennig), applications of ultrasound (Peters), mi-crowaves (Herwig and Trainor), and high pressure(Reiser).

In a compendium of this complexity, with such awealth of information, there is obviously something foreveryone, but I suspect that the more active researchersmay find the sections they are already familiar with tobe too brief to be of real use. However, newcomers tothe field, and students, will find the two volumes ex-tremely useful in drawing their attention to the vastarmoury that organic chemists now have at their dis-posal in the pursuit of synthetic objectives. This newtwo-volume production should certainly join the com-prehensive handbook edited by Cornils and Herrmannmentioned above on the shelves of all industrial andacademic libraries. Regrettably the high price will al-most certainly limit the number of individually ownedcopies.

John F. NixonSchool of Chemistry,

Physics and En6ironmental Science,Uni6ersity of Sussex,

Brighton BN1 9QJ,UK

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