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 beta,alpha-bisadducts, beta-amino-alpha-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 beta-amino alpha-allyl ketones having two contiguous stereocenters: quaternary carbon adjacent to secondary amine carbon center.