Asymmetric Synthesis of the Alkaloids mayfoline and N(1)-acetyl-N(1)-deoxymayfoline

The total syntheses of the spermidine alkaloids (?)-mayfoline ( 11 ) and (+)-N(1)-acetyl-N(1)-deoxymayfoline ( 12 ) are described. These macrocyclic lactams belong to the most interesting conjugates of the polyamine derivatives very commonly found in nature. The enantioselective syntheses were achieved through resolution of the methyl 3-amino-3-phenylpropanoate ( 2 ) by recrystallization of its (+)-L -tartrate salt. Construction of the 13-membered ring ensued through condensation, reductive ring expansion (internal bond cleavage), and finally a transamidation reaction involving a second ring expansion.