Deuterium labelling alkyl chloride

This experiment also suggests a convenient method to produce deuterium-labelled alkyl chloride from the corresponding aldehyde/ketone. 

In a first example of cyclopropane formation from allylpalladium complexes the reaction of dimeric 7t-allylpalladium chloride (1, R = H) with the enolate of methyl cyclohexanecarboxylate (2) was found to give the normal allylic alkylation product 3 only in low yields ( 20%) if the reaction was carried out in tetrahydrofuran in the presence of triphenylphosphane at room temperature, whereas with triethylamine in hexamethylphosphoramide the cyclopropane product 4 is formed in 70% yield. Deuterium labelling of the allyl moiety indicates that the reaction proceeds via nucleophilic attack of the enolate at the central allylic carbon followed by reductive elimination of the cyclopropane product. 

Nucleophilic attack of stabilized carbon nucleophiles on coordinated olefins is also known. Hegedus developed the alkylation of olefins shown in Equation 11.31. The (olefin)palladium(II) chloride complexes did not react with malonate nucleophiles, but the triethylamine adduct does react with this carbon nucleophile to provide the alkylation product. This reaction has recently been incorporated into a catalytic alkylation of olefins by Widenhoefer. - Intramolecular reaction of the 1,3-dicarbonyl compounds with pendant olefins in the presence of (GHjCNl PdCl occurs to generate cyclic products containing a new C-C bond (Equation 11.32). Some intermolecular reactions with ethylene and propylene have also been developed by this group. Deuterium labeling studies (Equation 11.32) have shown that the addition occurs by external attack on the coordinated olefin. ... 

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