DescriptionDisclosed are studies in allene methodology, total synthesis and computational modeling. These include (1) an efficient approach to synthesize highly functionalized allenes stereospecifically; (2) the first catalytic stereoselective allene oxidation method using iminium salts to give synthetically useful furan/pyran building blocks; (3) a unified and concise route towards the total syntheses of withanolides; (4) a new mechanistic theory to understand face selectivity; and (5) a structural revision of brosimum allene.