Enantioselective total synthesis of pyrinodemin A
Annie Pouilhès1, Anel Florès Amado, Anne Vidal
1Laboratoire de Chimie des Procédés et Substances Naturelles, Institut de Chimie Moléculaire et des Matériaux dOrsay UMR CNRS no 8182, Bâtiment 410, Univ. Paris-Sud 11, F-91405 Orsay, France.
Abstract:
Pyrinodemin A 1, a cytotoxic marine alkaloid, was synthesized in a convergent and enantioselective fashion. The key steps are an asymmetric intramolecular dipolar cycloaddition of an oxazoline N-oxide to introduce the bicyclic ring system of the molecule, a cuprate coupling for the extension of the saturated chain and a B-alkyl Suzuki coupling for the introduction of a 3-pyridyl moiety. Reductive amination allowed the coupling of the second side-chain onto the nitrogen atom to give 1. Additionally, attempts to prepare 1 from a trienic precursor by a double B-alkyl Suzuki reaction are described.
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