A concise enantioselective total synthesis of the neoclerodane diterpene (À )-salvinorin A is reported. The stereogenic center at C-12 was installed by catalytic asymmetric propargylation with excellent enantioselectivity, and the remaining six stereogenic centers were set up highly diastereoselectively under substrate control. As for our previous synthesis of racemic salvinorin A, two intramolecular Diels-Alder reactions were applied to generate the tricyclic core. A chemoselective Mitsunobu inversion of a syn 1,2-diol allowed for further streamlining of the original reaction sequence by two steps. Overall, (À )-salvinorin A was synthesized in only 16 steps starting from 3-furaldehyde with 1.4 % total yield. Furthermore, an alternative intramolecular Diels-Alder strategy employing a 2-bromo-1,3-diene moiety was investigated.

(−)-Isoguaiene was prepared from (S)-citronellal in only 9–10 steps with good overall yields. Either a trienyne or a dienediyne metathesis and highly diastereoselective organocatalytic Michael additions of aldehydes derived from (S)-citronellal served as the key transformations.

We report a study on diol cleavage of cyclic 1,2‐dihydroxysilanes for the preparation of functionalized acylsilanes. Sodium periodate turned out to be an efficient reagent for this transformation, resulting in good to excellent yields. The method is characterized by mild reaction conditions, and sometimes simple aqueous workup of the reaction mixture was sufficient to obtain the acylsilanes in high purity. An acyclic 1,2‐dihydroxysilane was readily cleaved as well.