title: Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates.
abstract: Huisgen's 1,3-dipolar cycloadditions become nonconcerted when copper(I) acetylides react with azides and nitrile oxides, providing ready access to 1,4-disubstituted 1,2,3-triazoles and 3,4-disubstituted isoxazoles, respectively. The process is highly reliable and exhibits an unusually wide scope with respect to both components. Computational studies revealed a stepwise mechanism involving unprecedented metallacycle intermediates, which appear to be common for a variety of dipoles.
authors.affiliation: Department of Molecular Biology, The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
authors.forename: Fahmi
authors.initials: F
authors.lastname: Himo
authors.forename: Timothy
authors.initials: T
authors.lastname: Lovell
authors.forename: Robert
authors.initials: R
authors.lastname: Hilgraf
authors.forename: Vsevolod V
authors.initials: VV
authors.lastname: Rostovtsev
authors.forename: Louis
authors.initials: L
authors.lastname: Noodleman
authors.forename: K Barry
authors.initials: KB
authors.lastname: Sharpless
authors.forename: Valery V
authors.initials: VV
authors.lastname: Fokin
mesh_terms: D002384:Catalysis; D002414:Cations, Monovalent; D003300:Copper / Q000737:chemistry*; D007555:Isoxazoles / Q000138:chemical synthesis*; D008958:Models, Molecular; D009570:Nitriles / Q000737:chemistry; D013816:Thermodynamics; D014230:Triazoles / Q000138:chemical synthesis*
chemical_list: D002414:Cations, Monovalent; D007555:Isoxazoles; D009570:Nitriles; D014230:Triazoles; D003300:Copper