On the synthesis of Z-gamma-amino-alpha,beta-unsaturated esters via Ru-catalyzed coupling

[formula: see text] A synthesis of gamma-amino acids and their cyclic derivatives, 3-pyrrolinones, from alpha-amino acids employs a ruthenium-catalyzed Alder ene reaction as a key step in the sequence. Cyclopentadienylruthenium (1,4-cyclooctadiene) chloride catalyzes the addition of gamma-amido-alpha,beta-alkynoate esters with monosubstituted alkenes. The major product arises from C-C bond formation at the alpha-carbon of the alkynoate. The reaction exhibits high chemoselectivity. The ruthenium-catalyzed addition occurs in preference to a Diels-Alder reaction. The two new double bonds are created with complete geometrical control. The initial gamma-amido-alpha,beta-unsaturated ester can be cyclized to the pyrrolinones with a tin catalyst.