Intramolecular silicon-assisted cross-coupling: Total synthesis of (+)-brasilenyne

The first, total synthesis of (+)-brasilenyne (1) has been achieved in 19 steps from l-(S)-malic acid. The key elements of this approach are a highly diastereoselective ring-opening of a 1,3-dioxolanone with bis(trimethylsilyl)acetylene) promoted by TiCl₄ to set a propargylic stereocenter and the successful application of the sequential ring closing metathesis/silicon-assisted intramolecular cross-coupling reaction for construction of the oxonin core structure of 1.