Allylzinc reagents were used to access highly functionalized tertiary carbinamine
derivatives in high yields from cyanoesters and cyanocarbonates. While the monoaddition
of organometallics on nitriles is generally observed, in this work the nucleophilic
allylation occurs twice, due to an intermediate transfer of the carbonyl moiety onto
the nitrogen atom. The chemoselectivity of the reaction allows the presence of various
functionalities and in the case of carbonate derivatives, the nature of the final
product was modulated by kinetic control, giving selectively hydroxyamides or cyclic
carbamates.
Key words
allylation - nitriles - nucleophilic addition - organometallic reagents - tertiary
carbinamines - zinc
