Ruthenium in Organic Synthesis. Edited by Shun-Ichi Murahashi.
2
Ruthenium in Organic Synthesis Edited by Shun-Ichi Murahashi. Wiley- VCH, Weinheim 2004. 383 pp., hardcover, E 129.00.—ISBN 3-527-30692-7 The use of transition-metals in organic synthesis has increased dramati- cally in the last two decades. Transition metal catalysts provide new opportuni- ties for performing highly selective reac- tions that are not achievable by tradi- tional synthetic methods. Many com- pounds or molecular frameworks that were impossible to make two decades ago can now be synthesized efficiently by the use of transition-metal catalysts. According to a search in SciFinder, among the many different transition- metal catalysts, the metal complexes of palladium, nickel, cobalt, rhodium, and ruthenium are the top five transition metals that are most frequently used to catalyze organic reactions. The develop- ment of ruthenium-catalyzed reactions has become an emerging field during the last decade. With the wide range of oxidation states (from 2 to + + 8) and several different coordination geome- tries, ruthenium catalysts can form a variety of intermediates, such as p-allyl- ruthenium, ruthenium-carbene, and ruthenacycle species. Although certain ruthenium-catalyzed reactions have been reviewed separately, there is at present no comprehensive book availa- ble that describes the recent develop- ments in the field of ruthenium catalysis. It is, therefore, most timely and welcome that Shun-Ichi Murahashi has compiled the book Ruthenium in Organic Synthe- sis . It consists of 14 chapters in which 23 leading experts cover all the most important aspects of current research in ruthenium catalysis. Following a concise introduction by the editor, S.-I. Murahashi, in Chapter 1, M. Kitamura and R. Noyori discuss hydrogenation and transfer hydrogena- tion reactions in Chapter 2. As one expects, the chapter is mainly devoted to asymmetric hydrogenation of various functional groups, including unfunction- alized and functionalized olefins, ketones and aldehydes, and imines. Chapter 3, by S.-I. Murahashi and N. Komiya, is concerned with oxidation reactions catalyzed by ruthenium com- plexes. Two classes of oxidation pro- cesses are described: dehydrogenative oxidations by low-valent ruthenium complexes, and oxygenation with high- valent ruthenium-oxo and ruthenium- hydroperoxo species. The next two chapters are concerned with carbon–carbon bond-forming reac- tions. Y. Yamamoto and K. Itoh discuss carbon–carbon bond formation via ruth- enacycle intermediates (Chapter 4), and T. Kondo and T. Mitsudo describe carbon–carbon bond formation via p- allylruthenium intermediates (Chap- ter 5). Chapter 6, by R. H. Grubbs and T. M. Trnka, is devoted to ruthenium- catalyzed olefin metathesis. Following a brief description of olefin metathesis, catalyst developments, and mechanistic considerations, this chapter focuses on ring-closing metathesis and cross meta- thesis reactions. The contribution by H. Nishiyama in Chapter 7 deals with ruthenium-cata- lyzed cyclopropanation reactions, cover- ing both normal and asymmetric cata- lytic cyclopropanation. In Chapter 8, C. Fischmeister, C. Bruneau, and P. H. Dixneuf report on progress in the area of nucleophilic addi- tions to alkynes and reactions via vinyl- idene intermediates. They describe ruthenium-catalyzed nucleophilic addi- tions of oxygen-containing nucleophiles such as water, alcohols, carboxylic acids, carbamates, and carbonates, and of nitrogen- and phosphorus-containing nucleophiles, to alkynes. Developments in hydrosilylation and addition to C–H bonds are also reported. In Chapter 9, F. Kakiuchi and N. Chatani turn to the subject of ruthe- nium-catalyzed reactions by activation of C–H and C–halogen bonds. By using various ruthenium catalysts, sp, sp 2 , and sp 3 C–H bonds, as well as carbon–halo- gen bonds, can be activated, leading to useful transformations. R. F. R Jazzar and E. P. Kɒndig give a comprehensive review in Chapter 10 on ruthenium Lewis acid catalyzed reac- tions. Various processes catalyzed or promoted by ruthenium-based Lewis acids are described, for example: ring- opening of epoxides, Mukaiyama and Sakurai reactions, stereoselective sul- foxidation, and various cycloaddition reactions, including Diels–Alder reac- tions, 1,3-dipolar cycloadditions, and hetero-ene reactions. Chapter 11, by T. Mitsudo and T. Kondo, describes ruthenium-catalyzed reactions with CO and CO 2 . The authors show how these C1 building blocks (CO and CO 2 ) can be converted into high- value organic compounds using ruthe- nium catalysis. In Chapter 12, H. Suzuki and T. Takao report on isomerization of organic substrates catalyzed by ruthe- nium complexes. Isomerizations of alkenyl alcohols, propargyl alcohols, alkenes, enynes, and dienes are descri- bed. Mechanistic information about these processes that is presented by the authors gives a very good picture of how the reactions proceed. Chapter 13, by H. Nagashima, is concerned with ruthenium-promoted radical reactions. After giving a histori- cal background of the development of this area of research, the author describes several radical processes pro- moted by ruthenium complexes, includ- ing intramolecular Kharasch addition, addition of sulfonyl chlorides to alkenes, and addition of organic halides or sulfo- nyl chlorides in polymer synthesis. In Chapter 14, S. Komiya and M. Hirano describe ruthenium-catalyzed bond cleavage reactions. There is some overlap of the material in this chapter with the chapter by F. Kakiuchi and N. Chatani (Chapter 9), but the examples used are clearly quite different. The book presents an interesting overview of a fascinating area of Angewandte Chemie Books 6269 Angew. Chem. Int. Ed. 2005, 44, 6269 – 6270 # 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Transcript of Ruthenium in Organic Synthesis. Edited by Shun-Ichi Murahashi.
Ruthenium in Organic Synthesis
Edited by Shun-IchiMurahashi. Wiley-VCH, Weinheim2004. 383 pp.,hardcover,E 129.00.—ISBN3-527-30692-7
The use of transition-metals inorganic synthesis has increased dramati-cally in the last two decades. Transitionmetal catalysts provide new opportuni-ties for performing highly selective reac-tions that are not achievable by tradi-tional synthetic methods. Many com-pounds or molecular frameworks thatwere impossible to make two decadesago can now be synthesized efficientlyby the use of transition-metal catalysts.According to a search in SciFinder,among the many different transition-metal catalysts, the metal complexes ofpalladium, nickel, cobalt, rhodium, andruthenium are the top five transitionmetals that are most frequently used tocatalyze organic reactions. The develop-ment of ruthenium-catalyzed reactionshas become an emerging field duringthe last decade. With the wide range ofoxidation states (from �2 to ++ 8) andseveral different coordination geome-tries, ruthenium catalysts can form avariety of intermediates, such as p-allyl-ruthenium, ruthenium-carbene, andruthenacycle species. Although certainruthenium-catalyzed reactions havebeen reviewed separately, there is atpresent no comprehensive book availa-ble that describes the recent develop-ments in the field of ruthenium catalysis.
It is, therefore, most timely and welcomethat Shun-Ichi Murahashi has compiledthe book Ruthenium in Organic Synthe-sis. It consists of 14 chapters in which 23leading experts cover all the mostimportant aspects of current researchin ruthenium catalysis.
Following a concise introduction bythe editor, S.-I. Murahashi, in Chapter 1,M. Kitamura and R. Noyori discusshydrogenation and transfer hydrogena-tion reactions in Chapter 2. As oneexpects, the chapter is mainly devotedto asymmetric hydrogenation of variousfunctional groups, including unfunction-alized and functionalized olefins,ketones and aldehydes, and imines.
Chapter 3, by S.-I. Murahashi and N.Komiya, is concerned with oxidationreactions catalyzed by ruthenium com-plexes. Two classes of oxidation pro-cesses are described: dehydrogenativeoxidations by low-valent rutheniumcomplexes, and oxygenation with high-valent ruthenium-oxo and ruthenium-hydroperoxo species.
The next two chapters are concernedwith carbon–carbon bond-forming reac-tions. Y. Yamamoto and K. Itoh discusscarbon–carbon bond formation via ruth-enacycle intermediates (Chapter 4), andT. Kondo and T. Mitsudo describecarbon–carbon bond formation via p-allylruthenium intermediates (Chap-ter 5).
Chapter 6, by R. H. Grubbs andT. M. Trnka, is devoted to ruthenium-catalyzed olefin metathesis. Followinga brief description of olefin metathesis,catalyst developments, and mechanisticconsiderations, this chapter focuses onring-closing metathesis and cross meta-thesis reactions.
The contribution by H. Nishiyama inChapter 7 deals with ruthenium-cata-lyzed cyclopropanation reactions, cover-ing both normal and asymmetric cata-lytic cyclopropanation.
In Chapter 8, C. Fischmeister, C.Bruneau, and P. H. Dixneuf report onprogress in the area of nucleophilic addi-tions to alkynes and reactions via vinyl-idene intermediates. They describeruthenium-catalyzed nucleophilic addi-tions of oxygen-containing nucleophilessuch as water, alcohols, carboxylicacids, carbamates, and carbonates, andof nitrogen- and phosphorus-containingnucleophiles, to alkynes. Developments
in hydrosilylation and addition to C–Hbonds are also reported.
In Chapter 9, F. Kakiuchi and N.Chatani turn to the subject of ruthe-nium-catalyzed reactions by activationof C–H and C–halogen bonds. By usingvarious ruthenium catalysts, sp, sp2, andsp3 C–H bonds, as well as carbon–halo-gen bonds, can be activated, leading touseful transformations.
R. F. R Jazzar and E. P. K>ndig givea comprehensive review in Chapter 10on ruthenium Lewis acid catalyzed reac-tions. Various processes catalyzed orpromoted by ruthenium-based Lewisacids are described, for example: ring-opening of epoxides, Mukaiyama andSakurai reactions, stereoselective sul-foxidation, and various cycloadditionreactions, including Diels–Alder reac-tions, 1,3-dipolar cycloadditions, andhetero-ene reactions.
Chapter 11, by T. Mitsudo and T.Kondo, describes ruthenium-catalyzedreactions with CO and CO2. The authorsshow how these C1 building blocks (COand CO2) can be converted into high-value organic compounds using ruthe-nium catalysis.
In Chapter 12, H. Suzuki and T.Takao report on isomerization oforganic substrates catalyzed by ruthe-nium complexes. Isomerizations ofalkenyl alcohols, propargyl alcohols,alkenes, enynes, and dienes are descri-bed. Mechanistic information aboutthese processes that is presented by theauthors gives a very good picture ofhow the reactions proceed.
Chapter 13, by H. Nagashima, isconcerned with ruthenium-promotedradical reactions. After giving a histori-cal background of the development ofthis area of research, the authordescribes several radical processes pro-moted by ruthenium complexes, includ-ing intramolecular Kharasch addition,addition of sulfonyl chlorides to alkenes,and addition of organic halides or sulfo-nyl chlorides in polymer synthesis.
In Chapter 14, S. Komiya and M.Hirano describe ruthenium-catalyzedbond cleavage reactions. There is someoverlap of the material in this chapterwith the chapter by F. Kakiuchi and N.Chatani (Chapter 9), but the examplesused are clearly quite different.
The book presents an interestingoverview of a fascinating area of
AngewandteChemieBooks
6269Angew. Chem. Int. Ed. 2005, 44, 6269 – 6270 ) 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
research. The chapters are of high qual-ity in terms of their content, and are wellwritten, although attentive readers willfind several typographical and grammat-ical errors. With regard to literature cita-tions, there are approximately 1350 ref-erences, of which over 80% belong to
the years 1995–2003. In conclusion, thisbook has definite value and is stronglyrecommended, both for experiencedorganic chemists who wish to learnabout recent developments in the fieldof ruthenium catalysis, and for otherreaders who would like to understand
some fundamental chemistry of ruthe-nium catalysis.
William TamDepartment of ChemistryUniversity of Guelph, Ontario (Canada)
DOI: 10.1002/anie.200485282
Books
6270 www.angewandte.org ) 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2005, 44, 6269 – 6270
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