Copper(I) Enolate Complexes in α‐Arylation Reactions: Synthesis, Reactivity, and Mechanism

Huang, Zheng; Hartwig, John F.

doi:10.1002/anie.201106719

Cited by 78 publications

(46 citation statements)

References 29 publications

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“…1, the linear two-coordinated Cu1 atom and the four-coordinated Cu3 atom are located on sites with crystallographically imposed twofold symmetry, while the three-coordinated Cu2 atom is on a general position. The Cu3-N bond lengths are similar to values reported previously for four-coordinated Cu I complexes (Barclay et al, 2001;Chowdhury et al, 2003;Huang & Hartwig, 2012). Cu1 is twocoordinated by two triazole N atoms of two BTA À ligands [N4 and N4 i ; symmetry code: (i) Àx, y, Àz À 1 2 ].…”

Section: Synthesis and Crystallizationsupporting

confidence: 85%

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[μ₃-benzotriazolato-κ³N¹:N²:N³-copper(I)]

Liu

Xiong

et al. 2014

Acta Crystallogr C Struct Chem

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The title complex, [Cu(C6H4N3)]n, was synthesized by the reaction of cupric nitrate, 1H-benzotriazole (BTAH) and aqueous ammonia under hydrothermal conditions. The asymmetric unit contains three crystallographically independent Cu(I) cations and two 1H-benzotriazolate ligands. Two of the Cu(I) cations, one with a linear two-coordinated geometry and one with a four-coordinated tetrahedral geometry, are located on sites with crystallographically imposed twofold symmetry. The third Cu(I) cation, with a planar three-coordinated geometry, is on a general position. Two Cu(I) cations are doubly bridged by two BTA(-) ligands to afford a noncentrosymmetric planar [Cu2(BTA)2] subunit, and two [Cu2(BTA)2] subunits are arranged in an antiparallel manner to form a centrosymmetric [Cu2(BTA)2]2 secondary building unit (SBU). The SBUs are connected in a crosswise manner via the sharing of four-coordinated Cu(I) cations, Cu-N bonding and bridging by two-coordinate Cu(I) cations, resulting in a one-dimensional chain along the c axis. These one-dimensional chains are further linked by C-H···π and weak van der Waals interactions to form a three-dimensional supramolecular architecture.

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Section: Synthesis and Crystallizationsupporting

confidence: 85%

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[μ₃-benzotriazolato-κ³N¹:N²:N³-copper(I)]

Liu

Xiong

et al. 2014

Acta Crystallogr C Struct Chem

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“…17 The mechanisms of these transformations have long been debated, primarily due to the lack of identification of discrete reactive intermediates involved in the catalytic reactions and experimental studies on the structure, dynamics, and reactivity of these intermediates. Thus, our group synthesized and characterized a series of reactive intermediates containing phenanthrolines, bipyridines, and diamines, and less reactive intermediates lacking ancillary ligands.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the Ullmann Biaryl Ether Synthesis Catalyzed by Complexes of Anionic Ligands: Evidence for the Reaction of Iodoarenes with Ligated Anionic Cu^I Intermediates

et al. 2018

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A series of experimental studies, along with DFT calculations, are reported that provide a detailed view into the mechanism of Ullmann coupling of phenols with aryl halides in the presence of catalysts generated from Cu(I) and bidentate, anionic ligands. These studies encompass catalysts containing anionic ligands formed by deprotonation of 8-hydroxyquinoline, 2-pyridylmethyl tert-butyl ketone, and 2,2,6,6-tetramethylheptane-3,5-dione. Three-coordinate, heteroleptic species [Cu(LX)OAr]− were shown by experiment and DFT calculations to be the most stable complexes in catalytic systems containing 8-hydroxyquinoline or 2-pyridylmethyl tert-butyl ketone and to be generated reversibly in the system containing 2,2,6,6-tetramethylheptane-3,5-dione. These heteroleptic complexes were characterized by a combination of 19F NMR, 1H NMR, and UV–vis spectroscopy, as well as ESI-MS. The heteroleptic complexes generated in situ react with iodoarenes to form biaryl ethers in high yields without evidence for an aryl radical intermediate. Measurements of 13C/12C isotope effects showed that oxidative addition of the iodoarene occurs irreversibly. This information, in combination with the kinetic data, shows that oxidative addition occurs to the [Cu(LX)OAr]− complexes and is turnover-limiting. A Hammett analysis of the effect of phenoxide electronic properties on the rate of the reaction of [Cu(LX)OAr]− with iodotoluene also is consistent with oxidative addition of the iodoarene to an anionic phenoxide complex. Calculations by DFT suggest that this oxidative addition is followed by dissociation of I− and reductive elimination of the biaryl ether from the resulting neutral Cu(III) complex.

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“…CuI and CuCl exhibited similar catalytic activity as did Cu(II) chloride dihydrate (Table 2, entries 1–3). There is general agreement that Cu(I) is the catalytic species in copper-catalyzed arylation of C, N or O-nucleophiles, which can be generated from Cu(II) or Cu(0) precursors by an in situ reduction or oxidation, respectively [53–55]. On the other hand, OTf − or OAc − counter ions decrease catalytic activity in Cu(II) salts, in comparison to chloride ions (Table 2, entries 4 and 5).…”

Section: Resultsmentioning

confidence: 99%

Efficient Cu-catalyzed base-free C–S coupling under conventional and microwave heating. A simple access to S-heterocycles and sulfides

Soria‐Castro¹,

Peñéñory²

2013

Beilstein J. Org. Chem.

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Summary S-aryl thioacetates can be prepared by reaction of inexpensive potassium thioacetate with both electron-rich and electron-poor aryl iodides under a base-free copper/ligand catalytic system. CuI as copper source affords S-aryl thioacetates in good to excellent yields, by using 1,10-phenanthroline as a ligand in toluene at 100 °C after 24 h. Under microwave irradiation the time was drastically reduced to 2 h. Both procedures are simple and involve a low-cost catalytic system. This methodology was also applied to the “one-pot” synthesis of target heterocycles, such as 3H-benzo[c][1,2]dithiol-3-one and 2-methylbenzothiazole, alkyl aryl sulfides, diaryl disulfides and asymmetric diaryl sulfides in good yields.

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Copper(I) Enolate Complexes in α‐Arylation Reactions: Synthesis, Reactivity, and Mechanism

Cited by 78 publications

References 29 publications

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[μ₃-benzotriazolato-κ³N¹:N²:N³-copper(I)]

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[μ₃-benzotriazolato-κ³N¹:N²:N³-copper(I)]

Mechanism of the Ullmann Biaryl Ether Synthesis Catalyzed by Complexes of Anionic Ligands: Evidence for the Reaction of Iodoarenes with Ligated Anionic Cu^I Intermediates

Efficient Cu-catalyzed base-free C–S coupling under conventional and microwave heating. A simple access to S-heterocycles and sulfides

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Copper(I) Enolate Complexes in α‐Arylation Reactions: Synthesis, Reactivity, and Mechanism

Cited by 78 publications

References 29 publications

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[μ3-benzotriazolato-κ3N1:N2:N3-copper(I)]

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[μ3-benzotriazolato-κ3N1:N2:N3-copper(I)]

Mechanism of the Ullmann Biaryl Ether Synthesis Catalyzed by Complexes of Anionic Ligands: Evidence for the Reaction of Iodoarenes with Ligated Anionic CuI Intermediates

Efficient Cu-catalyzed base-free C–S coupling under conventional and microwave heating. A simple access to S-heterocycles and sulfides

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Product

Resources

About

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[μ₃-benzotriazolato-κ³N¹:N²:N³-copper(I)]

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[μ₃-benzotriazolato-κ³N¹:N²:N³-copper(I)]

Mechanism of the Ullmann Biaryl Ether Synthesis Catalyzed by Complexes of Anionic Ligands: Evidence for the Reaction of Iodoarenes with Ligated Anionic Cu^I Intermediates