Substrate‐Controlled Asymmetric Total Synthesis and Structure Revision of (+)‐Itomanallene A

In control: The first asymmetric total synthesis of (+)-itomanallene A (revised structure) has been accomplished starting from commercially available (S)-glycidol in a substrate-controlled fashion. The approach yields α,α′-cis- or α,α′-trans-tetrahydrofuran isomers by intramolecular alkylation with either an amide enolate or a nitrile anion, respectively.