Metal-allyl complexes Nucleophilic addition

The complementary approach, activation of unsaturated hydrocarbons toward electrophilic attack by complexation with electron-rich metal fragments, has seen limited investigation. Although there are certainly opportunities in this area which have not been exploited, the electrophilic reactions present a more complex problem relative to nucleophilic addition. For example, consider the nucleophilic versus electrophilic addition to a terminal carbon of a saturated 18-electron metal-diene complex. Nucleophilic addition generates a stable 18-electron saturated ir-allyl complex. In contrast, electrophilic addition at carbon results in removal of two valence electrons from the metal and formation of an unstable ir-allyl unsaturated 16-electron complex (Scheme 1). 

A wide range of transition metal-allyl complexes are known to react with many types of nucleophiles. In most cases, these reactions occur between cationic allyl complexes and amines or stabilized, anionic carbon nucleophiles. The reaction typically occurs between the nucleophile and the form of the allyl complex, and attack usually occurs at the face of the allyl ligand opposite the metal. However, there are exceptions to these trends. For example, several experiments suggest that unstabilized carbon nucleophiles react first at the metal center, and C-C bond formation occurs between the alkyl and the allyl group by reductive elimination. In addition, a recent study has shown through deuterium labeling that attack of malonate anion on a molybdenum-allyl complex occurs with retention of configuration. ... 

Finally, intermediate cationic allyl complexes of palladium15,16 and ruthenium17, produced from allylic esters by the action of substoichiometric amounts of the metal catalyst, have been electronically inverted by reduction to become nucleophilic anion equivalents, which are capable of carbonyl addition. 

Palladium(II) is one of the most important transition metals in catalytic oxidations of allenes [1], Scheme 17.1 shows the most common reactions. Transformations involving oxidative addition of palladium(O) to aryl and vinyl halides do not afford an oxidized product and are discussed in previous chapters. The mechanistically very similar reactions, initiated by nucleophilic attack by bromide ion on a (jt-allene)pal-ladium(II) complex, do afford products with higher oxidation state and are discussed below. These reactions proceed via a fairly stable (jt-allyl)palladium intermediate. Mechanistically, the reaction involves three discrete steps (1) generation of the jt-allyl complex from allene, halide ion and palladium(II) [2] (2) occasional isomeriza-... 

The development of methods to effect nucleophilic addition to carbon-carbon double bonds by prior activation with metal cations has been applied, at least in a preliminary way, as a method of pyrrole ring closure. The conversion of butadienes to N-substituted pyrroles can be accomplished in two stages. In acetic add, 1,4-dienes react with PdnCl2 to give tr-allyl complexes with introduction of acetate at C-4. The ir-allyl complexes then react with amines to give a l-amino-4-acetoxy-2-butene (equation 70). When the addition of the amine is carried out in the presence of a silver salt and triphenylphosphine, a pyrrole is isolated, probably by cyclization of the amino-substituted allyl-Pd complex (equation 71) (81CC59). Although this procedure is attractive in terms of the simplicity of the... 

In addition to direct determination of the stereochemistry of the allylation process, alternative means of classification of nucleophiles as to those that proceed by ligand or metal addition have been advanced. In one case the classification is made based on the regiochemistry of addition to a specific unsymmetri-cal allyl complex,383 and in a second by the ability of a particular allyl complex to react only by ligand addition,386 and therefore to be inert to nucleophiles that add via attack at the metal. 

Loss of stereospecificity in the addition of soft carbon nucleophiles can occur if the rate of nucleophilic attack is slow, due, for example, to extreme steric bulk, e.g. NaCH(SChPh>2,167 of the nucleophile (equation 154). In this case, the initially displaced OAc has sufficient time to return and attack the ir-allyl complex. Acetate anions (vide infra) are capable of either ligand or metal addition, thus scrambling the stereochemistry of the starting allyl acetate. 

The loss of stereospecificity in the addition of bis(sulfone) anions to cyclohexenyl allylic acetates was attributed to a scrambling of the stereochemistry of the starting acetate. The ability of Pd° catalyst to effect this epimerization was confirmed in the absence of added nucleophile. This epimerization was attributed to the ability of the acetate to return to add to the ir-allyl complex via attack at the metal center (equation 177).167 This suggestion was confirmed by treatment of a preformed allylpalladium acetate dimer with CO, which resulted in cis migration of the acetate from Pd to the allyl ligand (equation 178).164... 

The addition of Grignards and organolithium reagents proceeds by attack at the metal center in ir-allylpalladium complexes. The regiochemical selectivity exhibited by these hard carbon nucleophiles with ir-allyl complexes substituted at the termini with alkyl or aryl groups is comparable to the soft carbon nucleophiles (ligand attack) in most cases, with addition occurring predominantly at the less substituted terminus (equations 248 and 249).1591387... 

As noted in the introduction, in contrast to attack by nucleophiles, attack of electrophiles on saturated alkene-, polyene- or polyenyl-metal complexes creates special problems in that normally unstable 16-electron, unsaturated species are formed. To be isolated, these species must be stabilized by intramolecular coordination or via intermolecular addition of a ligand. Nevertheless, as illustrated in this chapter, reactions of significant synthetic utility can be developed with attention to these points. It is likely that this area will see considerable development in the future. In addition to refinement of electrophilic reactions of metal-diene complexes, synthetic applications may evolve from the coupling of carbon electrophiles with electron-rich transition metal complexes of alkenes, alkynes and polyenes, as well as allyl- and dienyl-metal complexes. Sequential addition of electrophiles followed by nucleophiles is also viable to rapidly assemble complex structures. 

Both stoichiometric and catalytic reactions of allylic compounds via 7r-allyl complexes are known. Reactions of nucleophilic 71-allyl complexes with electrophiles involve oxidation of metals and hence constitutes stoichiometric reactions. 7i-Allyl complexes of Ni, Fe, Mo, Co and others are nucleophilic and undergo the stoichiometric reaction with electrophiles. However, electrophilic 71-allyl complexes react with nucleophiles, accompanying reduction of metals. For example, 71-allylnickel chloride (2) reacts with electrophiles such as aldehydes, generating Ni(II), and hence the reaction is stoichiometric. In contrast, electrophilic 7i-allylpalladium chloride (3) reacts with nucleophiles such as malonate and Pd(0) is generated. Thus repeated oxidative addition of allylic compounds to Pd(0) constitutes a catalytic reaction. 

An alternative mode of reactivity is observed for [Os]-naphthalene when the nucleophile for the tandem addition is built into the electrophile. The normal mode of reactivity results in the formation of cis-l,4-dihydronaphthalenes (vide supra), but when a solution of the methyl vinyl ketone Michael addition product 24 in methanol (Table 6, entry 1) and a catalytic amount of triflic acid are allowed to react, the complexed hydrophenanthrenone 25 is isolated in 89 % yield [18]. This reactivity results from the pendant ketone undergoing a tauto-merization to form an enol, which can then attack the allyl cation at C2. The stereochemistry of the nucleophilic addition is still anti to the face involved in the metal coordination, but the... 

The reaction of [Cp (PMe3)M( -All)]+ (M = Rh, Ir) with alkali metal enolates has been demonstrated to be a reversible nucleophilic addition. There is a kinetic preference for addition to the central carbon of the allyl ligand to give the 3-(C-enolato)metallacyclo-butane 53. The thermodynamically more stable product is the lower valent metal-olefin jt complex, 54. 

This reaction constitutes a special type of process in which a hydrogen atom and a nucleophile are added across the diene with fonnation of a carbon-hydrogen bond in the 1-position and a carbon-Nu bond in the 4-position. Some examples of such reactions are hydrosilylation [12-18], hydrostannation [19,20] amination [21,22], and addition of active methylene compounds [21 a,23,24], These reactions are initiated by an oxidative addition of H-Nu to the palladium(0) catalyst, which produces a palladium hydride species 1 where the nucleophile is coordinated to the metal (Scheme 8-1). The mechanism commonly accepted for these reactions involves insertion of the double bond into the palladium-hydride bond (hydride addition to the diene), which gives a (jr-allyl)palladium intermediate. Now depending on the nature of the nucleophile (Nu) the attack on the jr-allyl complex may occur either by external trans-aVtBck (path A) or via a cw-migration from palladium to carbon (path B). 

This chapter will focus on the nucleophilic addition reactions of transition metal vinylidenes and allyl complexes with Grignard reagents. Reactions with transition metal vinylidenes will be discussed initially, and then a brief review of allyl complexes with Grignard reagents will conclude the chapter. The synthesis and some general reactions of these vinylidene and allyl complexes will be presented. A more detailed description of the chemistry of these metal complexes can be found in the literature [1]. 

Trimetallic complexes with two identical cr,7r-bridging ring ligands having different ring sizes and numbers of tt attachments have been studied. The complexes with two bridging cyclohexadienyl (19a), cyclohepta-dienyl (19b), and cycloheptatrienyl (19c-f) ligands were synthesized by the nucleophilic addition reactions of dianionic carbonylmetallates, [M(C0)4]- (M = Os, Ru), and two equivalents of the appropriate cationic-metal allyl substrates (82). 

Among the various carbon-carbon and carbon-hetero atom bond forming reactions promoted or catalyzed by transition metals, allylic substitution via electrophilic n-allyl-complexes is of utmost importance. Studies focused on the synthetic potential of alkyl or aryl substituted ( n3-allyl)Fe(CO)4 1+) complexes have shown that nucleophilic attack by soft carbon and hetero atom nucleophiles preferentially proceeds regioselectively at the less or syn-substituted allyl terminus.4 Additionally, polar effects on the regioselectivity of this reaction caused by electron-withdrawing functionalities (e.g., CO2R, CONR2) have been examined by the... 

The mechanism for the carbonylation of allylic substrates is considered to be composed of the following processes (a) oxidative addition involving allylic C-0 bond cleavage to form r 3-allyltransition metal complexes (b) CO insertion into the metal-allylic bond and (c) nucleophilic attack to liberate carboxylic acid derivatives (Scheme 6). 

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