Transition-metal catalysis formalisms

Bicyclopropylidene (1) also reacts with activated alkenes under transition-metal catalysis. With electron-deficient alkenes under nickel(O) catalysis, the [2-1-2] cycloadduct 263 was the main component in the reaction mixture [2b, 150]. Under palladium(O) catalysis, formal [3-1-2] cycloaddition of electron-deficient (Scheme 60) as well as strained alkenes can be achieved exclusively... 

A long-standing success in transition metal catalysis is the carbonylation reaction [66], in particular the synthesis of acetic acid [67]. Formally this is the insertion of CO into another bond, in particular into a carbon-halogen bond. After the oxidative addition to the transition metal (the breaking of the carbon-halogen bond), a reaction with a CO ligand takes place. This reaction is often called an insertion. Mechanistic studies have, however, shown that the actual reaction... 

Apart from these two complications, the formalism developed in Chapter 6 for noncatalytic reactions remains applicable as far as rate equations are concerned, but must be combined with modeling of the catalyst equilibria Where rate equations of transition-metal catalysis appeared in examples in earlier chapters, the quantity CMt is the concentration of the free catalyst and may have to be supplied by a catalyst equilibrium model. 

Indeed, the application of transition-metal catalysis in organic synthesis is built around many such formalisms. In addition to the formal oxidation state, these include coordinative unsaturation, coordination number, and coordination geometry, hydride formalism and the 18-electron and 16-18-electron rules, also referred to as electron bookkeeping. 

The transition metal catalysis of this tandem (cascade) reaction involving [3,3]-sigmatropic rearrangement (since it would be the carbonyl oxygen of the acetate forming a new bond to the p-acetylenic atom) followed by the formal Myers-Saito cyclization of allene 3.524 results in the formation of aromatic ketones 3.525 in up to 94% yield (Scheme 3.29) [265]. 

Abstract This chapter describes late transition metal complexes-catalyzed hydroamination, the formal additimi of an H-N bond across a C-C multiple bond. Late transition metal catalysis has been intensely developed in the hydroamination and additions of various kinds of amines to C-C multiple bonds have been achieved. The reaction pathways strrMigly depend on the choice of metal complexes, substrates, and reaction conditions. This chapter is organized primarily based on the difference in the mechanisms of hydroamination reactions, and in the scope section concise summary of the hydroamination reaction is shown. 

Why are transition metals so well suited for catalysis A complete treatment of this critical question lies well beyond the scope of this book, but we can focus on selected aspects of bond activation and reactivity for dihydrogen and alkene bonds as important special cases. Before discussing specific examples that involve formal metal acidity or hypovalency, it is convenient to sketch a more general localized donor-acceptor overview of catalytic interactions in transition-metal complexes involving dihydrogen49 (this section) and alkenes (Section 4.7.4). 

Like so many other reactions, the ene reaction has been given new life by metal catalysis. The use of metals ranges from common Lewis acids, which simply lower the barrier of activation of the hetero-ene reactions to transition metal catalysts which are directly involved in the bond-breaking and -forming events, rendering reactions formal ene processes. This review is meant to serve as a guide to the vast amount of data that have accumulated in this area over the past decade (1994-2004). If a particular subject has been reviewed recently, the citation is provided and only work done since the time of that review is included here. Finally, the examples included within are meant to capture the essence of the field, the scope, limitations, and synthetic utility therefore, this review is not exhaustive. 

This survey of theoretical methods for a qualitative description of homogeneous catalysis would not be complete without a mention to the Hartree-Fock-Slater, or Xot, method [36]. This approach, which can be formulated as a variation of the LDA DFT, was well known before the formal development of density functional theory, and was used as the more accurate alternative to extended Hiickel in the early days of computational transition metal chemistry. 

It is intriguing that analysis of the volcano curve predicts that the apex of the curve occurs at AH(H2)ads = 0 (formally, AG = 0) [26]. This value corresponds to the condition D(M-H) = 1/2D(H-H), that is, forming an M-H bond has the same energetic probability as forming an H2 molecule. This condition is that expressed qualitatively by the Sabatier principle of catalysis and corresponds to the situation of maximum electrocatalytic activity. Interestingly, the experimental picture shows that the group of precious transition metals lies dose to the apex of the curve, with Pt in a dominant position. It is a fact that Pt is the best catalyst for electrochemical H2 evolution however, its use is made impractical by its cost. On the other hand, Pt is the best electrocatalyst on the basis of electronic factors only, other conditions being the same. 

Epoxides can isomerize under the influence of transition metal catalysts. This formal 1,2-hydride shift is a method to prepare unsaturated carbonyl compounds from epoxides (Equation 54) <1998T1361>. This method has been extended as a double epoxide isomerization-intramolecular aldol condensation (Equation 55) <1996JOC7656, 1998TL3107>. m-Epoxides are isomerized to /ra r-epoxides under ruthenium catalysis <2003TL3143>. 

This reaction is superficially understood as a formal delivery of H-MgX element from a Grignard reagent to an olefin under catalysis of such a transition metal complex (Scheme 3). 

In this Scheme, pC stands for pro-catalyst, C for catalyst, CS for a complex between catalyst and substrate, CP for a complex between catalyst and product, I for an initiator. S for a structural variation of the substrate, R for an added reagent. In cases 1.1 and 1.2 the catalysis is based on a coordinative interaction between catalyst and substrate in case 1.1 the product is released to regenerate C (for example by reductive elimination) whereas in case 1.2 the regeneration of CS results from a substitution of the complexed product by S. It should be clear that cases 1.1 and 1.2 do not exhaust the formal possibilities offered to photogenerated catalysis. One may actually imagine a photogeneration of catalyst from a selected pro-catalyst for any of the multiple catalytic cycles identified in homogeneous catalysis centered on transition metal complexes [12]. 

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