The first total syntheses of littoralisone (1) and brasoside (2) have been achieved in 13 overall steps. Both natural products are forged from a common intermediate which is rapidly assembled using organocatalytic technology, including a proline-catalyzed α-aminoxylation and a contra-thermodynamic intramolecular Michael addition. Application of the two-step carbohydrate synthesis technology has enabled to access a selectively substituted glucose derivative for use as an intramolecular cycloaddition tether. This synthesis culminates with an intramolecular [2+2] photocycloaddition that serves to support the proposed biosynthetic origins of 1 from 2
