title: Synthesis of the Strychnos Alkaloid (-)-Strychnopivotine and Confirmation of its Absolute Configuration.
abstract: The first enantioselective synthesis of (-)-strychnopivotine from a known and inexpensive phenol has been achieved in 15 steps. The strategy is based on a new diastereoselective aza-Michael-enol-ether cascade desymmetrization of a dienone, guided by a removable lactic acid-derived chiral auxiliary. Synthesis involves a phenol dearomatization, a conjugated silicon addition, a stereoselective double reductive amination, and two Heck-type carbopalladations as key steps. The absolute configuration of the natural compound, which, to date, has been uncertain, was confirmed by using circular dichroism (CD) spectroscopy and X-ray analyses.
authors.affiliation: Laboratoire de Méthodologie et Synthèse de, Produit Naturels, Université du Québec à Montréal, C.P.8888, Succ. Centre-Ville, Montréal, H3C 3P8, Québec, Canada.
authors.forename: Gaëtan
authors.initials: G
authors.lastname: Maertens
authors.affiliation: Laboratoire de Méthodologie et Synthèse de, Produit Naturels, Université du Québec à Montréal, C.P.8888, Succ. Centre-Ville, Montréal, H3C 3P8, Québec, Canada. canesi.sylvain@uqam.ca.
authors.forename: Sylvain
authors.initials: S
authors.lastname: Canesi
mesh_terms: D018360:Crystallography, X-Ray; D008958:Models, Molecular; D008968:Molecular Conformation; D010636:Phenols / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism; D013331:Strychnine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D031451:Strychnos / Q000737:chemistry*
chemical_list: D010636:Phenols; D013331:Strychnine
keywords: alkaloid; chiral auxiliary; desymmetrization; hypervalent iodine; total synthesis