Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates.
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.
Himo
Fahmi
F
Department of Molecular Biology, The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Lovell
Timothy
T
Hilgraf
Robert
R
Rostovtsev
Vsevolod V
VV
Noodleman
Louis
L
Sharpless
K Barry
KB
Fokin
Valery V
VV
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*
D002414:Cations, Monovalent; D007555:Isoxazoles; D009570:Nitriles; D014230:Triazoles; D003300:Copper