202 Organometallics, Vol. 2, No. 1, 1983 of the references are to Japanese language publications. This reflects the volume of Japanese research in this field but unfortunately highlights these works’ inaccessibility, except through such reviews, to the almost totally monolingual English world. It is also regrettable that this 1982 book, with very few exceptions, taps the literature only through 1978. The authors of this book have produced a readable, well-written work with very few language problems or “typos”. The various chapters are good reviews of the respective areas for scientists new to the field. There is a useful, detailed Table of Contents and a small index. A much expanded index would greatly facilitate retrieval of information from otherwise not cross-referenced chapters dealing with the same subjects. A chapter on organic syntheses with carbon dioxide by E. Haruki reviews, in detail, “recent” organic chemistry with C 0 2 . This chapter provides good detailed discussions with copious references. Haruki discusses the Friedel-Crafts reaction of aromatics carboxylation with C 0 2 in the presence of AlCl, but does not mention the increasing volume of research on the COZ/H2 methanol Fischer-Tropsch type reactions. This chapter includes sections on the Kolbe-Schmitt reaction and reaction of C 0 2 with amines, among various other reaction types. The next chapter by T. Ito and A. Yamamoto on “Organometallic Reactions of Carbon Dioxide” summarizes the literature in this area-through approximately 1978. There are a number of good, more recent research reports that unfortunately were not included. The first table and associated text in this chapter purport to present many thermodynamically favorable reactions utilizing C02,but only favorable enthalpy changes are shown and the harmful entropy changes are not mentioned. Consideration of AG’, not just AH,shrinks the list of favorable reactions drastically. Thus, the proposed direct carboxylation of aromatic or olefinic hydrocarbons discussed later is not viable. This chapter does summarize well the wealth of non-transition metal, transition metal, and catalytic reactions involving C02 The chapter would be well served by discussing, a t least briefly, not just organometallic chemistry starting with carbon dioxide but also the extensive CO C 0 2 work such as J. Lewis et al’s Os cluster bound C 0 2 and the numerous water-gas shift studies. As discussed in this chapter, readers should beware that most claimed COz “adducts” are poorly characterized and may be other types of complexes. This chapter states that a necessary step in the catalytic utilization of C 0 2 is its preliminary insertion into a M-A (A = H, C, N, or 0)bond. Not so. The authors do subsequently cite work by M. H. Chisholm et. al. which demonstrates another pathway. Chapter 4 by S. Yamazaki, F. Higashi, and S.Inoue is on “Syntheses of Macromolecules from Carbon Dioxide”. Condensation, ring-opening, and addition polymerizations are reviewed. This is followed by a chapter by K. Asada on “Biological Carboxylations” which reviews photosynthetic carboxylations. The last chapter on “Model Reactions of Biochemical Carbon Dioxide Fixations” by S. Inoue includes discussion of carbonic anhydrase, biotin, and related systems and urea formation. These chapters treat, in an introductory fashion, these research areas. T. Herskovitz, E. I. d u Pont de Nemours and Company
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Book Reviews contains two chapters: a long one (344 pages) on “Allylic and Benzylic Carbanions Substituted by Heteroatoms”, by J.-F. Biellmann and J.-B. Ducep, and a short one (46 pages) on “Palladium-Catalyzed Vinylation of Organic Halides”, by R. F. Heck. The first chapter deals with active metal reagents whose allylic or benzylic groups contain C-halogen, C-0, C-N, C-S, C-Se, C-Te, C-P, C-Si, or C-B bonds and encompasses a broad range of functional groups. The discussion covers the basicity of these reagents, their structures in solution, their preparation (principally by metalation reactions), modes of decomposition, their reactions with electrophiles, the regioselectivity and the stereochemistry of their reactions, transformations of derived products, and applications in synthesis. The most vexing problem in their use is regioselectivity control since so many fadom are important: nature of the heteroatom-containing group, other substituents on the allylic system, the nature of the conjugated system, the counterion, the solvent, the electrophile, and the reaction temperature. Although there is still much to be learned on this subject, it is very useful to have what is known summarized in this manner. Six detailed experimental procedures gleaned from the literature follow the discussion, and these seem to have been chosen to illustrate the use of different metalating agents. A 268-page tabular survey of examples of the applications of heteroatomsubstituted allylic and benzylic metal reagents follows. A total of 630 references are cited in this chapter, with a literature cutoff of December 1979. The authors may be congratulated on accomplishing what must have been a tedious task of winkling out all of these examples. While some are easily found in papers devoted to this specific topic, probably many more are hidden away in synthetic papers in which such reactions are used but do not receive special emphasis. The second chapter cites 75 references and is devoted to a much more restricted topic: the Pd-catalyzed vinylation of organic (mostly aryl, vinyl, and benzyl) halides.
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Organic Reactions. Volume 27. W. G. Dauben, editor-in-chief. Wiley, New York. 1982. vii 405 pages. $45.00.
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Volume 27 of this well-established and well-received series
This is a reaction which the author pioneered. The discussion of mechanism is followed by a survey of scope and limitations, eight selected experimental procedures from the literature, and a 24-page tabular survey of the applications of this reaction in the synthesis of substituted olefins. Within its limitations, this is a useful reaction which accomplishes its task in one step, often in good yield. This volume of “Organic Reactions” should be of interest to many readers of this journal since both chapters deal with organometallic topics. The authors have done their job well and have provided two useful additions to the organometallic review literature. Three indexes are provided: a subject index for the present volume, a chapter and topic index, and an author index for all 27 “Organic Reactions” volumes. The price of this book is reasonable, compared with the high prices of many other monographs which are being published these days. Dietmar Seyferth, Massachusetts Institute of Technology
