title: The daphniphyllum alkaloids: total synthesis of (-)-calyciphylline N.
abstract: Presented here is a full account on the development of a strategy culminating in the first total synthesis of the architecturally complex daphniphyllum alkaloid, (-)-calyciphylline N. Highlights of the approach include a highly diastereoselective, intramolecular Diels-Alder reaction of a silicon-tethered acrylate; an efficient Stille carbonylation of a sterically encumbered vinyl triflate; a one-pot Nazarov cyclization/proto-desilylation sequence; and the chemoselective hydrogenation of a fully substituted diene ester.
authors.affiliation: Department of Chemistry, Laboratory for Research on the Structure of Matter, and Monell Chemical Senses Center, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Artem
authors.initials: A
authors.lastname: Shvartsbart
authors.affiliation: Department of Chemistry, Laboratory for Research on the Structure of Matter, and Monell Chemical Senses Center, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Amos B
authors.initials: AB
authors.lastname: Smith
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry; D060326:Chemistry Techniques, Synthetic; D003517:Cyclopentanes / Q000737:chemistry; D004852:Epoxy Compounds / Q000737:chemistry; D004952:Esters; D006865:Hydrogenation; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000470:Alkaloids; D002264:Carboxylic Acids; D003517:Cyclopentanes; D004852:Epoxy Compounds; D004952:Esters; D011083:Polycyclic Compounds; C535098:calyciphylline N; C013905:cyclopentenone