Carbon-Carbon bond forming reactions of organotransition metal enolate complexes

Abstract -Metal enolates play an important role in stereoselective organic synthesis. Their chemistry is affected profoundly by the metal counterion associated with the enolate fragment. In order to expand the potential of replacing main group with transition metal moieties in such species, methods have been developed for the synthesis of a number of stable, characterizable "late" transition metal ql-(C)-enolate complexes having the general structure LM-CH2COR (M = Mo, W, Re). The chemistry of these materials (e.g., functional transformations of the organic carbonyl group, transfer of the enolate moietry to organic substrates such as aldehydes and alkynes) has been investigated. The scope and mechanisms of the enolate reactions will be discussed in detail. The reaction of organic enolates with carbon electrophiles (e.g., alkyl halides, organic carbonyl compounds) gives rise to compounds containing new carbon-carbon bonds; reaction with heteroatom electrophiles results in the formation of oxidized products? There has been much interest recently in developing methods for carrying out these transformations with high stereoselectivity.3 Historically, most enolate research has focused on salts involving alkali metal anions. More recently, research efforts have been extended to enolates associated with organic cations, main group metals, and transition metals. In the transition metal area, enolates involving the so-called "early" metals (to the left of chromium, molybdenum and tungsten) have seen extensive investigationi4 in general these complexes have 0-bonded structures A in Scheme 1. This paper describes the synthesis and chemistry of middle-and late transition metal enolates, which have seen less investigation. It was our hope that such species would be more likely to have Cbound structure B, and also to react with both electrophilic and non-electrophilic species (e.g., by insertion rather than nucleophile-electrophile mechanisms). SYNTHESIS, CHARACTERIZATION AND FUNCTIONAL GROUP TRANSFORMATIONS OF TUNGSTEN AND MOLYBDENUM ENOLATES The well-known nucleophilic anionic metal salts5 Na[(qS-C5R5)(C0)3M] (M = Mo, W, R=H, Me), on treatment with a-chloroketones and esters, provide good yields of enolates 1 -8, as shown in Scheme 2. These are thermally stable complexes that may be isolated by conventional chromatographic and recrystallization methods; they have been characterized fully by elemental analysis and spectroscopic techniques. Preparation of these materials on a multi-gram scale in a one-pot procedure is possible by treatment of W(CO)6 or Mo(C0)6 with NaCp, followed by addition of the a-chlorocarbonyl compound to the resulting metal anion solution. The stability of the tungsten-carbon bond in tungsten ester enolates, fiist suggested several years ago by the work of Green and his coworkers6, has allowed us to carry out a wide range of transformations on the organic carbonyl group. Thus the reactions shown in Scheme 3 proceed in good yield, and lead to stable tungsten enolates containing ester, amide and even carboxylic acid and acid chloride functionality