Total Syntheses of (−)-Englerins A/B, (+)-Orientalols E/F, and (−)-Oxyphyllol

(−)-Englerin A was synthesized in 20 steps from the commercially available material (<i>R</i>)-(+)-limonene. In addition, (−)-englerin B, (+)-orientalol E/F and (−)-oxyphyllol were obtained from the intermediate in the route. The key steps include a hydroxyl-directing stereoselective and regioselective intramolecular cyclopropanation and a multi-gram-scale stereoselective formal intramolecular [3 + 2] cross cycloaddition ([3 + 2]-IMCC) of a cyclopropane 1,1-diester with a carbonyl. A precursor of 7,10-diastereoisomer of englerins was also obtained