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Synthèse de pyrrolizidines naturelles par cycloaddition [2+2] :
la (+)-rétronécine et la (+)-hyacinthacine A1

Abstract : The enantioselective total synthesis of two natural pyrrolizidines, (+)-retronecine and (+)-hyacinthacine A1, has been achieved based on a [2+2] cycloaddition of dichloroketene with a sterically hindered chiral enol ether. The syntheses involve a high-yield sequence to afford a common chiral lactam, which is easily converted into the pyrrolizidine skeleton.
The synthesis of (+)-retronecine features an allylic oxidation of the terminal double bond of the lactam and a Pd-catalyzed methoxycarbonylation reaction to introduce a hydroxymethyl equivalent. For (+)-hyacinthacine A1, a masked hydroxymethyl group is introduced by addition of a phenyldimethylsilylmethyl cuprate to an intermediate imminium ion derived from the common lactam. This group is then converted into the hydroxymethyl at the end of the synthesis by a Tamao-Fleming oxidation.
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https://tel.archives-ouvertes.fr/tel-00124795
Contributor : Amaël Veyron <>
Submitted on : Tuesday, January 16, 2007 - 11:02:23 AM
Last modification on : Friday, November 6, 2020 - 4:03:46 AM
Long-term archiving on: : Tuesday, April 6, 2010 - 8:59:04 PM

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Amaël Veyron. Synthèse de pyrrolizidines naturelles par cycloaddition [2+2] :
la (+)-rétronécine et la (+)-hyacinthacine A1. Autre. Université Joseph-Fourier - Grenoble I, 2006. Français. ⟨tel-00124795⟩

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