title: Phosphorylated cyclopropanes in the synthesis of α-alkylidene-γ-butyrolactones: total synthesis of (±)-savinin, (±)-gadain and (±)-peperomin E.
abstract: Phosphorylated cyclopropanes, generated via the Rh(ii)-catalysed intramolecular cyclopropanation of α-(diethoxyphosphoryl)acetates, have been found to be useful precursors in the synthesis of α-alkylidene-γ-butyrolactones. These cyclopropyl intermediates undergo regioselective reductive ring-opening and subsequent Horner-Wadsworth-Emmons olefination to complete the synthesis. Total syntheses of (±)-savinin and (±)-gadain, as well as the first total synthesis of (±)-peperomin E, are all described using this method.
authors.affiliation: Department of Chemistry, University of York, Heslington, York YO10 5DD, UK. richard.taylor@york.ac.uk william.unsworth@york.ac.uk.
authors.forename: Matthew G
authors.initials: MG
authors.lastname: Lloyd
authors.affiliation: Department of Chemistry, University of York, Heslington, York YO10 5DD, UK. richard.taylor@york.ac.uk william.unsworth@york.ac.uk.
authors.forename: Richard J K
authors.initials: RJ
authors.lastname: Taylor
authors.affiliation: Department of Chemistry, University of York, Heslington, York YO10 5DD, UK. richard.taylor@york.ac.uk william.unsworth@york.ac.uk.
authors.forename: William P
authors.initials: WP
authors.lastname: Unsworth
mesh_terms: D015107:4-Butyrolactone / Q000138:chemical synthesis* / Q000737:chemistry; D052117:Benzodioxoles / Q000138:chemical synthesis* / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D003521:Cyclopropanes / Q000138:chemical synthesis / Q000737:chemistry*; D017705:Lignans / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D010766:Phosphorylation; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D052117:Benzodioxoles; D001688:Biological Products; D003521:Cyclopropanes; D017705:Lignans; C000626211:gadain; C545363:peperomin E; C425325:savinin; D012238:Rhodium; D015107:4-Butyrolactone