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Convergent and stereodivergent synthesis of complex 1-aza-7-oxabicyclo[2.2.1]heptanes.

ABSTRACT: A convergent and stereodivergent pathway to highly substituted 1-aza-7-oxabicyclo[2.2.1]heptanes is described. It begins with a coupling reaction involving allylic alcohol, aldehyde, and LiHMDS to produce stereodefined primary homoallylic amines. Subsequent N-oxidation and condensation with formaldehyde or glyoxylate defines a convenient entry to densely functionalized homoallylic nitrones whose intramolecular annulation can be controlled to deliver one of two distinct heterocyclic skeletons, each with ≥20:1 stereoselection. Control of the stereochemistry in these reactions results from both control of the nitrone geometry and selective partitioning of the reaction pathway between direct [3 + 2] cycloaddition and tandem [3,3] rearrangement/[3 + 2] cycloaddition.

SUBMITTER: Yang D 

PROVIDER: S-EPMC3116711 | biostudies-literature | 2011 Jun

REPOSITORIES: biostudies-literature

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Convergent and stereodivergent synthesis of complex 1-aza-7-oxabicyclo[2.2.1]heptanes.

Yang Dexi D   Micalizio Glenn C GC  

Journal of the American Chemical Society 20110523 24

A convergent and stereodivergent pathway to highly substituted 1-aza-7-oxabicyclo[2.2.1]heptanes is described. It begins with a coupling reaction involving allylic alcohol, aldehyde, and LiHMDS to produce stereodefined primary homoallylic amines. Subsequent N-oxidation and condensation with formaldehyde or glyoxylate defines a convenient entry to densely functionalized homoallylic nitrones whose intramolecular annulation can be controlled to deliver one of two distinct heterocyclic skeletons, ea  ...[more]