Application to Organic Synthesis

The Organometallic Chemistry of the Dransition Metals, Fourth Edition, by Robert H. Crabtree Copyright 200S John Wiley Sons, Inc. 

Organometallic methods, both main group and transition metal, have risen to dominance in organic synthesis. 

Catalytic chemistry is increasingly being adopted over stoichiometric chemistry, where possible. 

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STEREOSELECTIVE HENRY REACTIONS AND APPLICATIONS TO ORGANIC SYNTHESIS... 

Davies SG (1982) In Organotransition metal chemistry application to organic synthesis, Pergamon Press, Oxford... 

Few other examples of such reaction sequences have been described to date. Oh has reported the palladium-catalyzed reductive cyclizations of 1,6-enynes in the presence of formic acid or triethylsilane via an alkylpalladium intermediate and its application to organic synthesis. Palladium complexes also catalyze the conversion of a range of enynes to cyclic 6,7-unsaturated carboxylic acids in the presence of CO.260... 

As seen in the vanadium chemistry (Schemes 46 and 47), activation of isocyanides is one of the key mechanisms in organotantalum chemistry. Scheme 55 generalizes the examples where organotantalum chemistry of isocyanides leads to the formation of products. Although these products remain coordinated to tantalum, these reactions provide insight into the potential for applications to organic synthesis. Methyltantalum species allow formation of... 

S.G. Davies, "Organotransition Metal Chemistry Application to Organic Synthesis", Pergamon Press, Oxford, 1982, pp. 166-169... 

IV. Thione-Thiol Tautomerism and Its Application to Organic Synthesis. 43... 

Stereoselective Rhodium(l)-Catalyzed Hydroformylatlon and Silylformylation Reactions and their Application to Organic Synthesis... 

Carbonyl ylides (1) are highly reactive dipoles that have been proposed as key intermediates in a variety of reactions since the 1960s (Fig. 4.1). Since these early reports, there has been a virtual explosion in the study of these unstable intermediates both at the theoretical level and more recently in their application to organic synthesis. This chapter will focus on the structure, generation, and chemical reactions of carbonyl ylides and will review the literature since 1984. 

In sharp contrast to a fully developed asymmetric palladium-catalyzed allylic substitution as described in the previous sections of this chapter, similar reactions using transition metal complexes other than palladium have not yet been fully investigated and their application to organic synthesis is quite limited at the present. In this section, examples of Cu-, Ni-, Pt-, Rh-, Ir-, Ru-, Mo-, and W-catalyzed allylic alkylation are summarized including recent developments in this field. 

Electrochemical reduction and oxidation processes offer several advantages over conventional methods in their application to organic synthesis. For example, selective transformations can be carried out on specific groups in a multifunctional, valuable compound under the usually mild reaction conditions. Independence of a reagent will result in drastically diminished environmental problems by spent reagents. Electrochemistry also allows the application of alternative feedstocks and better use of raw materials. Product isolation and continuous processing are simplified. 

Reviews (a) V. Dave and E. W. Wamhoff, The Reactions of Diazoacetic Esters with Alkenes, Alkynes, Heterocyclic and Aromatic Compounds, in W. G. Dauben, ed., Organic Reactions, Vol. 18, Chap. 3, John Wiley Sons, New York, 1970. (b) G. Maas, Top. Curr. Chem., 137, 75 (1987). (c) J. Salaun, Chem. Rev., 89, 1247 (1989). (d) A. Demonceau, A. J. Hubert, and A. F. Noels, Basic Principles in Carbene Chemistry and Applications to Organic Synthesis, in A. F. Noels, M. Graziani, and A. J. Hubert, eds., Metal Promoted Selectivity in Organic Synthesis, p. 237, Kluwer Academic, Dordrecht, 1991. 

S. G. Davies, Organotransition Metal Chemistry Applications to Organic Synthesis , Pergamon, Oxford, 1982, p. 304. 

Applications to Organic Synthesis Pergamon Oxford, 1982 Chapter 7. (e) Colquhoun, H. M. Holton, J. Thompson, D. J. Twigg, M. V. In New Pathways for Organic Synthesis, Plenum New York, 1984 Chapter 5. 

DAVIES Organotransition Metal Chemistry Applications to Organic Synthesis Volume 3... 

CA, 1987 (c) S. G. Davies, Organotransition Metal Chemistry Application to Organic Synthesis, Pergamon Press, Oxford, 1989 (d) L. S. Hegedus, Transition Metals in the Synthesis of Complex Organic Molecules, 2nd edn., University Science Books, Sausalito, CA, 1999 (e) J. Tsuji, Transition Metal Reagents and Catalysts, Innovations in Organic Synthesis, Wiley, Chichester, 2000. 

The preparation of a-lithio aldehydes, o -lithio ketones, and related compounds and their applications to organic synthesis has been reviewed.10 The Tsuji-Trost allylic alkylation with ketone enolates has been highlighted.11... 

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