The first asymmetric total synthesis of new biphenylquinolizidine alkaloids 4''-O-demethyllythridine and 14-epi-4''-O-demethyllythridine isolated from Heimia salicifolia was accomplished. The key steps in the synthesis were a copper(I)-catalyzed asymmetric intramolecular aza-Michael reaction to build a chiral 4-arylquinolizidine unit and an intramolecular Suzuki-Miyaura cross-coupling reaction to construct a macrolactone ring comprising a biphenyl moiety.