Asymmetric Total Synthesisand Structural Reassignmentof Nervione

We report the asymmetric total synthesis of optically active nervione in both (+) and (−) forms, a natural product initially isolated from Nervilia concolor in 2022. Beginning with commercially available resorcinol, optically pure nervione was synthesized in 10 steps, employing a combination of <i>ortho</i>-directed strategies and a crucial late-stage, Lewis acid-mediated, highly diastereoselective reduction. Discrepancies observed in circular dichroism (CD) spectra prompted the reassignment of nervione’s absolute configuration from (3<i>S</i>, 8<i>R</i>) to (3<i>R</i>, 8<i>S</i>).