Convergent total syntheses of the aryl C-glycoside antibiotics gilvocarcin M (1a) and gilvocarcin V (1b) have been accomplished. Key steps include (1) contrasteric coupling of D-fucofuranosyl acetate 27 with iodophenol 26, which was achieved by employing Cp(2)HfCl(2)-AgClO4 or the related organosilane-derived reagents, and (2) regioselective [4+2] cycloaddition of a sugar-bearing benzyne species, generated by treatment of o-haloaryl triflate 33-alpha with n-BuLi at -78 degrees C, with 2-methoxyfuran (6). The naphthol derivative 34, selectively synthesized by these two tactics, served as the common intermediate to both 1a and 1b. Acylation of 34 with benzoic acid derivative 39 followed by Pd-catalyzed cyclization gave gilvocarcin M (1a), and a similar synthetic sequence starting with the coupling of 34 with 49 led to the first total synthesis of gilvocarcin V (1b).