Palladium-Catalyzed Decarboxylative Aza-Michael Addition−Allylation Reactions between Allyl Carbamates and Activated Olefins. Generation of Quaternary Carbon Adjacent to Secondary Amine Carbon Center

The reaction of allyl carbamates with activated olefins in the presence of Pd(PPh3)4 catalyst in THF
proceeded smoothly at room temperature to give the corresponding β,α-bisadducts, β-amino-α-allylated
products, in high yields. Not only highly activated olefins containing two cyano groups but also 2-cyano
enones underwent facile aza-Michael addition−allylation with various allylic carbamates giving the
corresponding products in high yields and with high diastereoselectivities. The stereochemistry of the
singly formed product was confirmed with the help of X-ray crystallographic technique. It is an excellent
method for creating β-amino α-allyl ketones having two contiguous stereocenters:  quaternary carbon
adjacent to secondary amine carbon center.