Synthesis of (+)-muconin isolated from Rollinia mucosa (Annonaceae) was achieved. Stereoselective construction of a tetrahydrofuran-terahydropyran (THF-THP) ring moiety was performed using diastereoselective oxypalladation in the presence of CuCl2. The cross-coupling reaction of the THF-THP moiety with the γ-lactone portion followed by reduction of the enyne and removal of the protecting groups afforded (+)-muconin.