Two Competitive but Switchable Organocatalytic Cascade Reaction Pathways: The Diversified Synthesis of Chiral Acetal-Containing Bridged Cyclic Compounds.

The organocatalytic enantioselective synthesis of methanobenzodioxepine derivatives bearing a 6,6,5-bridged ring system is presented. The m-CPBA-triggered in situ α-oxidation of β-oxoesters to provide the required but unstable α-hydroxy-β-dicarbonyl substrates is the key to this three-step sequence, providing the desired cyclic acetals with excellent stereoselectivities containing two bridgehead and one fully substituted stereocenters. It is noteworthy that the absence of m-CPBA furnished the acetal products bearing a 6,6,6-bridged ring system with similar good results from the same starting materials.