A carbometallation is any reaction where a carbon-metal bond reacts with a carbon-carbon π-bond to produce a new carbon-carbon σ-bond and a carbon-metal σ-bond. The resulting carbon-metal bond can undergo further carbometallation reactions (oligomerization or polymerization see Ziegler-Natta polymerization) or it can be reacted with a variety of electrophiles including halogenating reagents, carbonyls, oxygen, and inorganic salts to produce different organometallic reagents. Carbometallations can be performed on alkynes and alkenes to form products with high geometric purity or enantioselectivity, respectively. Some metals prefer to give the anti-addition product with high selectivity and some yield the syn-addition product. The outcome of syn and anti- addition products is determined by the mechanism of the carbometallation.
Carboboration
Carboboration is one of the most versatile carbometallation reactions. See Carboboration.
Carboalumination
The carboalumination reaction is most commonly catalyzed by zirconocene dichloride (or related catalyst). Some carboaluminations are performed with titanocene complexes. This reaction is sometimes referred to as the Zr- catalyzed asymmetric carboalumination of alkenes (ZACA) or the Zr-catalyzed methylalumination of alkynes (ZMA).
The most common trialkyl aluminum reagents for this transformation are trimethylaluminium, triethylaluminium, and sometimes triisobutylaluminium. When using trialkylaluminum reagents that have beta-hydrides, eliminations and hydroaluminum reactions become competing processes. The general mechanism of the ZMA reaction can be described as first the formation of the active catalytic species from the pre-catalyst zirconocene dichloride through its reaction with trimethyl aluminum. First transmetalation of a methyl from the aluminum to the zirconium occurs. Next, chloride abstraction by aluminum creates a cationic zirconium species that is closely associated with an anionic aluminum complex. This zirconium cation can coordinate an alkene or alkyne where migratory insertion of a methyl then takes place. The resultant vinyl or alkyl zirconium species can undergo a reversible, but stereoretentive transmetalation with an organoaluminum to provide the carboalumination product and regeneration of the zirconcene dichloride catalyst. This process generally provides the syn-addition product; however, conditions exist to provide the anti-addition product though a modified mechanism.
Trimethylsilyl (TMS) protected alkynes, trimethyl germanium alkynes, and terminal alkynes can produce anti-carboalumination products at room temperature or elevated temperatures if a coordinating group is nearby on the substrate. In these reactions, first syn-carboalumination takes place under the previously outlined mechanism. Then, another equivalent of aluminum that is coordinated to the directing group can displace the vinyl aluminum, inverting the geometry at the carbon where displacement takes place.
This forms a thermodynamically favorable metallacycle to prevent subsequent inversions. Formally, this process provides anti-carboalumination products that can be quenched with electrophiles. A limitation of this methodology is that the directing group must be sufficiently close to the carbon-carbon π-bond to form a thermodynamically favorable ring or else mixtures of geometric isomers will form.
The carboalumination of alkenes to form substituted alkanes can be rendered enantioselective if prochiral alkenes are used. In these reactions, a chiral indenyl zirconium catalyst is used to induce enantioselectivity. In these reactions, high enantioselectivities were obtained for several trialkyl aluminum reagents, however, the yield decreases dramatically with each additional carbon of the alkyl chain on the trialkyl aluminum reagent.
