Alkanes, addition organometallics with alkyl

Transition State Models. The stoichiometry of aldehyde, dialkylzinc, and the DAIB auxiliary strongly affects reactivity (Scheme 9) (3). Ethylation of benzaldehyde does not occur in toluene at 0°C without added amino alcohol however, addition of 100 mol % of DAIB to diethylzinc does not cause the reaction either. Only the presence of a small amount (a few percent) of the amino alcohol accelerates the organometallic reaction efficiently to give the alkylation product in high yield. Dialkyl-zincs, upon reaction with DAIB, eliminate alkanes to generate alkylzinc alkoxides, which are unable to alkylate aldehydes. Instead, the alkylzinc alkoxides act as excellent catalysts or, more correctly, catalyst dimers (as shown below) for reaction between dialkylzincs and aldehydes. The unique dependence of the reactivity on the stoichiometry indicates that two zinc atoms per aldehyde are responsible for the alkyl transfer reaction. 

Nucleophilic addition see Nucleophilic Addition Rules for Predicting Directioii) of the ligands represents a major methodology for organometallic functional transformation. In order to discern how alkane functionalization takes place in aqueous Pt systems, a water-soluble platinum alkyl, [PtCl5(CH2R)]2- (R = H, CH2OH), is allowed to react with chloride and water. Both kinetics and inversion of stereochemistry support an Sn2 mechanism. Treatment... 

The use of a silica-supported, tantalum alkyhdene as a precursor for alkane metathesis was found to result in a stoichiometric, alkane cross metathesis in which an initial pendant alkyl-alkylidene group was transformed to produce the desired, active species [76, 90]. This reaction was later observed to work with additional, well-defined systems supported on alumina [58] and sihca-alumma [53]. As mentioned previously, this transformation does not occur when the surface organometallic precursor bears no alkyl group. Exposing these supported, metal neopentyl, neopentylidene, and neopentyhdyne complexes to alkane at 150 °C produced alkanes containing a neopentyl fragment (CH jiBu) via cross metathesis. Propane metathesis with these alkyl-alkyhdene surface complexes typically generates stoichiometric amounts of dimethylpropane, 2,2-dimethylbutane, and 2,2-dimethylpentane (Scheme 2.11). 

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