title: Generation of Benzyne Species from Diphenylphosphoryl Derivatives: Simultaneous Exchange of Three Functional Groups.
abstract: Interaction of (2-diphenylphosphoryl-3-iodo-4-methoxy-phenyl) methanol with NaH in DMF at ambient temperature results in the generation of benzyne intermediates that can be trapped by furan or DMF. Trapping with DMF forms 3-(dimethylaminomethyl)-2-hydroxy-6-methoxybenzaldehyde demonstrating the simultaneous exchange of three functionalities in a single step. The presence of the alkoxy substituent adjacent to iodine is critical for high regioselectivity addition of DMF. The corresponding bromide or triflate can be used in place of the iodide with equal efficiency. This methodology was used to synthesize the reported structure of gigasol and leading to a structural reassignment of this biscoumarin natural product.
authors.affiliation: Department of Chemistry, University of Calgary, Calgary, AB, T2N 1N4, Canada.
authors.forename: Evgueni
authors.initials: E
authors.lastname: Gorobets
authors.affiliation: Department of Chemistry, University of Calgary, Calgary, AB, T2N 1N4, Canada.
authors.forename: Masood
authors.initials: M
authors.lastname: Parvez
authors.affiliation: Department of Chemistry, University of Calgary, Calgary, AB, T2N 1N4, Canada.
authors.forename: Darren J
authors.initials: DJ
authors.lastname: Derksen
authors.affiliation: Department of Chemistry, University of Calgary, Calgary, AB, T2N 1N4, Canada. keay@ucalgary.ca.
authors.forename: Brian A
authors.initials: BA
authors.lastname: Keay
mesh_terms: D001555:Benzene Derivatives / Q000138:chemical synthesis / Q000737:chemistry*; D001578:Benzopyrans / Q000138:chemical synthesis / Q000737:chemistry; D002087:Butyrates / Q000138:chemical synthesis / Q000737:chemistry; D003374:Coumarins / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D061565:Cycloaddition Reaction; D004126:Dimethylformamide / Q000737:chemistry; D005663:Furans / Q000737:chemistry; D008968:Molecular Conformation; D017670:Sodium Compounds / Q000737:chemistry
chemical_list: D001555:Benzene Derivatives; D001578:Benzopyrans; D002087:Butyrates; D003374:Coumarins; D005663:Furans; D017670:Sodium Compounds; C524146:benzyne; C524957:sodium hydride; D004126:Dimethylformamide; C030123:coumarin; C101278:decursin; C039281:furan
keywords: benzynes; coumarin; decursinol; gigasol; peucedanol