title: Investigation of transannular cycloaddition reactions involving furanoxonium ions using DFT calculations. Implications for the origin of plumarellide and rameswaralide and related polycyclic metabolites isolated from corals.
abstract: DFT calculations probing potential (4 + 2) and (4 + 3) cycloaddition pathways leading to the polycyclic ring systems found in the coral secondary metabolites plumarellide, mandapamate and rameswaralide are described. Formation of plumarellide and mandapamate via stepwise intramolecular cycloaddition of a furanoxonium ion onto a 1,3-diene is shown to be viable. The calculations also predict the outcome of related cyclisations involving model systems.
authors.affiliation: School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
authors.forename: B
authors.initials: B
authors.lastname: Lygo
authors.forename: M J
authors.initials: MJ
authors.lastname: Palframan
authors.forename: G
authors.initials: G
authors.lastname: Pattenden
mesh_terms: D000818:Animals; D037421:Anthozoa / Q000737:chemistry* / Q000378:metabolism; D061565:Cycloaddition Reaction; D005663:Furans / Q000737:chemistry* / Q000378:metabolism; D006576:Heterocyclic Compounds, 4 or More Rings / Q000737:chemistry / Q000302:isolation & purification* / Q000378:metabolism; D007477:Ions / Q000737:chemistry / Q000378:metabolism; D008968:Molecular Conformation; D009861:Onium Compounds / Q000737:chemistry* / Q000378:metabolism; D011083:Polycyclic Compounds / Q000737:chemistry / Q000302:isolation & purification* / Q000378:metabolism; D011789:Quantum Theory
chemical_list: D005663:Furans; D006576:Heterocyclic Compounds, 4 or More Rings; D007477:Ions; D009861:Onium Compounds; D011083:Polycyclic Compounds