Nickel(0) induzierte und katalysierte CC-Verknuepfungen von Phenylisocyanat mit funktionalisierten Alkenen

Article abstract of DOI:10.1016/0022-328X(89)85118-6

Monosubstituted alkenes RCH=CH2 (R=OEt (Ia), SPh (Ib), CO2Me (Ic)) react with phenyl isocyanate on (Lig)Ni⁰ systems to form tricyclohexylphosphane-5-azanickelacyclopentan-4-one-derivatives (V).It is shown that the complexes V are intermediates in the catalytic CC coupling reaction.Further reactions by the system is dependent upon the nature of R.Thus when R=OEt (Ia) a β-elimination is induced, which ultimately leads to 3-ethoxyacrylic acid anilide (XIa), the unsaturated product of a 1/1 CC coupling.On the other hand, when R=CO2Me (Ic) further insertion of isocyanate occurs, to give 1,5-diphenyl-2,6-dioxo-hexahydropyrimidine-4-acidmethylester (XII).Characteristic features are descriebed, and the reaction mechanisms are discussed.