title: Bridgehead enolate or bridgehead organolithium? DFT calculations provide insights into a difficult bridgehead substitution reaction in the synthesis of the polycyclic polyprenylated acylphloroglucinol (PPAP) nemorosone.
abstract: A computational study (B3LYP), of the metallation of a bridged ketone, an important step in the synthesis of a polycyclic polyprenylated acylphloroglucinol (PPAP), nemorosone, shows three energetically distinct structural possibilities for the lithiated intermediate. These findings, along with observations of the reactivity of the intermediates in bridgehead substitutions, suggest that different intermediates may be formed depending upon the type of process used for lithiation.
authors.affiliation: School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK. chris.hayes@nottingham.ac.uk.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Hayes
authors.forename: Nigel S
authors.initials: NS
authors.lastname: Simpkins
mesh_terms: D000215:Acylation; D001577:Benzophenones / Q000138:chemical synthesis* / Q000737:chemistry; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D008094:Lithium / Q000737:chemistry*; D008958:Models, Molecular; D010696:Phloroglucinol / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D001577:Benzophenones; D001952:Bridged-Ring Compounds; C437463:nemorosone; D008094:Lithium; D010696:Phloroglucinol