title: Copper(I)-assisted mild and convenient synthesis of new Se--N heterocycles: access to a promising class of GPx mimics.
abstract: Benzisoselenazolines 15 and benzisoselenazines 21, designed as low molecular weight mimics of glutathione peroxidases, were synthesized for the first time. Starting from amines 13 and 14, a smooth introduction of selenium in nonactivated aryl bromides using KSeCN in the presence of CuI was developed. An equimolar quantity of CuI and the presence of Et(3)N as a base are necessary to achieve a complete conversion of the starting material. The reaction is feasible in various solvents such as DMF, acetonitrile, and THF. The desired new Se-N heterocycles 15 and 21 were isolated under optimized conditions in yields of 82 and 68%, respectively. Experiments have been conducted with various copper(I) and copper(II) salts, a chloroamine 17, an aryl bromide 18, and an N-acylated amine 19 to show the scope and the limitations of this method. The previously unknown sulfur analogues 20 and 22 have been synthesized in moderate yields using a slightly modified procedure. Finally, a mechanistic scheme has been proposed to discuss some interesting findings, which were obtained during the optimization process of this new introduction of selenium.
authors: OXIS International SA, 1 place Boieldieu, 75002 Paris, France. erdelmeier@aol.com
authors: I
authors: I
authors: Erdelmeier
authors: C
authors: C
authors: Tailhan-Lomont
authors: J C
authors: JC
authors: Yadan
mesh_terms: D003300:Copper / Q000737:chemistry*; D005979:Glutathione Peroxidase / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D018716:Molecular Mimicry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012643:Selenium
chemical_list: D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; D003300:Copper; D005979:Glutathione Peroxidase; D012643:Selenium