Synthesis of bridged inside-outside bicyclic ethers through oxidative transannular cyclization reactions.
The classical geometry of the 6-endo transition state for nucleophilic additions into oxocarbenium ions can be perturbed by incorporating the reactive groups into medium-sized rings, leading to the formation of 2,6-trans-dialkyl tetrahydropyrans. The bicyclic products exhibit inside-outside stereoisomerism, as seen in numerous macrolide natural products.
Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15260, United States.
Xun
X
Han
Paul E
PE
Floreancig
D003500:Cyclization; D004988:Ethers, Cyclic / Q000737:chemistry*; D018942:Macrolides / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D004988:Ethers, Cyclic; D018942:Macrolides