Copper(I) phenoxide complexes in the etherification of aryl halides.
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ABSTRACT:
SUBMITTER: Tye JW
PROVIDER: S-EPMC3008396 | biostudies-literature | 2010 Mar
REPOSITORIES: biostudies-literature
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Copper(I) phenoxide complexes in the etherification of aryl halides.
Tye Jesse W JW Weng Zhiqiang Z Giri Ramesh R Hartwig John F JF
Angewandte Chemie (International ed. in English) 20100301 12
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Project description:The copper(I) thiophenolato complexes 1-3 containing 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (Me(2)phen) were isolated in excellent yields from reactions of [CuOtBu](4) with the dative ligands and subsequent addition of 1 equiv of arylthiol and characterized spectroscopically. X-ray structural analysis of a single crystal of [(phen)Cu(µ-SC(6)H(5))](2) (1) revealed that this complex adopts a neutral dimeric form with a weak Cu-Cu bonding interaction. These complexes were found to react with iodoarenes to form aryl sulfide products. The intermediacy of such complexes in copper-catalyzed thioetherification of aryl halides was demonstrated by the reactivity with p-tolyl iodide and o-tolyl iodide to form two aryl thioethers with selectivities similar to those of catalytic reactions conducted with the same two iodoarenes.
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Project description:Copper(I) imidate and amidate complexes of chelating N,N-donor ligands, which are proposed intermediates in copper-catalyzed amidations of aryl halides, have been synthesized and characterized by X-ray diffraction and detailed solution-phase methods. In some cases, the complexes adopt neutral, three-coordinate trigonal planar structures in the solid state, but in other cases they adopt an ionic form consisting of an L 2Cu (+) cation and a CuX 2 (-) anion. A tetraalkylammonium salt of the CuX 2 (-) anion in which X = phthalimidate was also isolated. Conductivity measurements and (1)H NMR spectra of mixtures of two complexes all indicate that the complexes exist predominantly in the ionic form in DMSO and DMF solutions. One complex was sufficiently soluble for conductance measurements in less polar solvents and was shown to adopt some degree of the ionic form in THF and predominantly the neutral form in benzene. The complexes containing dative nitrogen ligands reacted with iodoarenes and bromoarenes to form products from C-N coupling, but the ammonium salt of [Cu(phth) 2] (-) did not. Similar selectivities for stoichiometric and catalytic reactions with two different iodoarenes and faster rates for the stoichiometric reactions implied that the isolated amidate and imidate complexes are intermediates in the reactions of amides and imides with haloarenes catalyzed by copper complexes containing dative N,N ligands. These amidates and imidates reacted much more slowly with chloroarenes, including chloroarenes that possess more favorable reduction potentials than some bromoarenes and that are known to undergo fast dissociation of chloride from the chloroarene radical anion. The reaction of o-(allyloxy)iodobenzene with [(phen) 2Cu][Cu(pyrr) 2] results in formation of the C-N coupled product in high yield and no detectable amount of the 3-methyl-2,3-dihydrobenzofuran or 3-methylene-2,3-dihydrobenzofuran products that would be expected from a reaction that generated free radicals. These data and computed reaction barriers argue against mechanisms in which the haloarene reacts with a two-coordinate anionic copper species and mechanisms that start with electron transfer to generate a free iodoarene radical anion. Instead, these data are more consistent with mechanisms involving cleavage of the carbon-halogen bond within the coordination sphere of the metal.
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Project description:[18F]-labeled aryl fluorides are widely used as radiotracers for positron emission tomography (PET) imaging. Aryl halides (ArX) are particularly attractive precursors to these radiotracers, as they are readily available, inexpensive, and stable. However, to date, the direct preparation of [18F]-aryl fluorides from aryl halides remains limited to SNAr reactions between highly activated ArX substrates and K18F. This report describes an aryl halide radiofluorination reaction in which the C(sp2)-18F bond is formed via a copper-mediated pathway. Copper N-heterocyclic carbene complexes serve as mediators for this transformation, using aryl halide substrates with directing groups at the ortho position. This reaction is applied to the radiofluorination of electronically diverse aryl halide derivatives, including the bioactive molecules vismodegib and PH089.
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Project description:Detailed mechanistic studies on the coupling of aryl halides with thiols catalyzed by palladium complexes of the alkylbisphosphine ligand CyPF-(t)Bu (1-dicyclohexylphosphino-2-di-tert-butylphosphinoethylferrocene) are reported. The elementary steps that constitute the catalytic cycle, i.e. oxidative addition, transmetalation and reductive elimination, have been studied, and their relative rates are reported. Each of the steps of the catalytic process occurs at temperatures that are much lower than those required for the reactions catalyzed by a combination of palladium precursors and CyPF-(t)Bu. To explain these differences in rates between the catalytic and stoichiometric reactions, studies were conducted to identify the resting state of the catalyst of the reactions catalyzed by a combination of Pd(OAc)(2) and CyPF-(t)Bu, a combination of Pd(dba)(2) and CyPF-(t)Bu, or the likely intermediate Pd(CyPF-(t)Bu)(Ar)(Br). These data show that the major palladium complex in each case lies off of the catalytic cycle. The resting state of the reactions catalyzed by Pd(OAc)(2) and CyPF-(t)Bu was the palladium bis-thiolate complex [Pd(CyPF-(t)Bu)(SR)(2)] (R = alkyl or aryl). The resting state in reactions catalyzed by Pd(2)(dba)(3) and CyPF-(t)Bu was the binuclear complex [Pd(CyPF-(t)Bu)](2)(mu(2),eta(2)-dba) (9). The resting states of reactions of both aromatic and aliphatic thiols catalyzed by [Pd(CyPF-(t)Bu)(p-tolyl)(Br)] (3a) were the hydridopalladium thiolate complexes [Pd(CyPF-(t)Bu)(H)(SR)] (R= alkyl and aryl). All these palladium species have been prepared independently, and the mechanisms by which they enter the catalytic cycle have been examined in detail. These features of the reaction catalyzed by palladium and CyPF-(t)Bu have been compared with those of reactions catalyzed by the alkylbisphosphine DiPPF and Pd(OAc)(2) or Pd(dba)(2). Our data indicate that the resting states of these reactions are similar to each other and that our mechanistic conclusions about reactions catalyzed by palladium and CyPF-(t)Bu can be extrapolated to reactions catalyzed by complexes of other electron-rich bisphosphines.
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Project description:AbstractFour new copper complexes based on bidentate imino phenoxide ligands were synthesized and characterized by IR, UV-Vis spectroscopy, ESI mass spectrometry, single crystal X-ray diffraction, and electrochemistry. The crystal structures revealed that the copper(II) atoms are surrounded by phenolate oxygen and imine nitrogen atoms of two ligands in a distorted square-planar geometry. The existence of ligand-centered, as well as Cu(II)-centered quasi-reversible and reversible redox reactions are observed in the cyclic voltammetry experiments of all the complexes. All complexes are able to catalyze the ring-opening polymerization of rac-lactide yielding polymers with moderate molecular weights and moderately broad molecular weight distributions.Graphical abstract
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