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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Enantioselective synthesis of (-)-dihydrocodeinone: a short formal synthesis of (-)-morphine
Kathlyn A Parker1, Demosthenes Fokas
1Department of Chemistry, Brown University, Providence, Rhode Island 02912, USA.
Abstract:
[reaction: see text] The radical cyclization approach to the morphine alkaloids has been applied in an asymmetric synthesis of (-)-dihydrocodeinone. A chiral cyclohexenol (R-32), from the CBS reduction of the enone, is the source of chirality. The first key step, tandem closure in which stereochemistry is controlled by geometric constraints, (-)-15b --> (+)-16, was followed by an unprecedented reductive hydroamination, completing the synthesis of (-)-dihydroisocodeine ((-)-17) in 13 steps from commercially available materials.
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