title: Generation of arynes via ate complexes of arylboronic esters with an ortho-leaving group.
abstract: An efficient method of generating aryne has been achieved by treating ortho-(trifluoromethanesulfonyloxy)arylboronic acid pinacol ester with tert- or sec-butyllithium. Monitoring the reaction by (11)B NMR has indicated that a boron-ate complex formed in situ is the eventual precursor that converts into aryne near room temperature. The prior formation of the ate complex at a low temperature has enabled us to use various arynophiles, including those bearing base-sensitive groups. The ready availability of the aryne precursors and mutual orthogonality in aryne generation with widely used ortho-silylaryl triflate have enhanced the utility of the method.
authors.affiliation: Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kanda-Surugadai, Tokyo 101-0062, Japan.
authors.forename: Yuto
authors.initials: Y
authors.lastname: Sumida
authors.forename: Tomoe
authors.initials: T
authors.lastname: Kato
authors.forename: Takamitsu
authors.initials: T
authors.lastname: Hosoya
mesh_terms: D001897:Boronic Acids / Q000737:chemistry*; D002074:Butanones / Q000737:chemistry*; D002384:Catalysis; D004952:Esters; D018020:Lithium Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D001897:Boronic Acids; D002074:Butanones; D004952:Esters; D018020:Lithium Compounds