Divergent Enantioselective Synthesis of (Nor)illudalane Sesquiterpenes via Pd<sup>0</sup>‑Catalyzed Asymmetric C(sp<sup>3</sup>)–H Activation

A divergent enantioselective synthesis of (nor)­illudalane sesquiterpenes was designed by using a Pd<sup>0</sup>-catalyzed asymmetric C­(sp<sup>3</sup>)–H arylation as a key step to control the isolated, highly symmetric quaternary stereocenter of the target molecules. A matched combination of chiral substrate and catalyst proved optimal to reach good levels of stereoselectivity. This approach enabled the synthesis of three (nor)­illudalanes, including (<i>S</i>)-deliquinone and (<i>S</i>)-russujaponol F, which are synthesized for the first time in enantioenriched form.