Reactivity of a nickelacycle derived from aspartic acid: Alkylations, insertions, and oxidations

Article abstract of DOI:10.1021/om00018a020

The five-membered nickelacycle derived from aspartic acid by oxidative addition followed by decarbonylation reacts with alkyl iodides and bromides to give α-amino acids, after hydrolysis of the reaction products. Carbonylation products were, however, observed with benzyl or allyl bromide. The involvement of radicals in the alkylation reaction pathway has also been explored. Oxidation of the nickelacycle with N-methylmorpholine N-oxide or dioxygen gave N-protected serine. On the other hand, benzoyl peroxide promoted the insertion of carbon monoxide or isocyanides into the Ni-C bond. Phenylacetylene and 1-octyne also insert into the Ni-C bond of the nickelacycle to give alkenyl or alkynyl products.