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Synthesis of bridged inside-outside bicyclic ethers through oxidative transannular cyclization reactions.

ABSTRACT: 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.

SUBMITTER: Han X

PROVIDER: S-EPMC3498537 | biostudies-other | 2012 Jul

REPOSITORIES: biostudies-other

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Synthesis of bridged inside-outside bicyclic ethers through oxidative transannular cyclization reactions.

Han Xun X Floreancig Paul E PE

Organic letters 20120711 14

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. ...[more]

PMID: 22783950

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