Concise total syntheses of bouvardin (1) and O-methylbouvardin (2) are described based on the asymmetric synthesis of the N-methyl-erythro-beta-hydroxy-L-4-iodophenylalanine derivative 24, its coupling with the selectively protected N,O-4-dimethyl-L-DOPA methyl ester to provide 40, and subsequent incorporation into a surprisingly successful key Ullmann macrocyclization reaction for preparation of the 14-membered 13 (S)-hydroxycycloisodityrosine subunit 15 of the bicyclic hexapeptides. Coupling of 15 with BOCNH-D-Ala-Ala-NMe-Tyr(OMe)-Ala-OC6F5 followed by 18-membered-ring macrocyclization strategically conducted with formation of a secondary amide at a D-amino acid amine terminus (C-2-N-3 amide) provided O-methylbouvardin (2). Selective demethylation (BBr3) of 2 provided bouvardin (1) in excellent conversion (86%). The extensions of the studies to the preparation of O-methyl-N-9-desmethylbouvardin (51) are detailed and its solution-phase conformational properties examined by H-1 NMR in efforts which confirm that the additional minor conformation of 1 and 2 (ca. 10-15%) observed in nonpolar solvents (CDCl3, THF-d(8)), arise from a cis N-9-C-8 N-methylamide conformation.