Copper‐Mediated Cross‐Coupling Reactions

Penn, Liza; Gelman, Dmitri

doi:10.1002/9780470682531.pat0451

Cited by 2 publications

(3 citation statements)

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“…This work establishes the structure of mixed-valence organocopper complexes, and we expect that this class of compounds could provide new synthetic targets for the development of reagents and catalysts that might exhibit yet undiscovered reactivity. Moreover, they could serve as intermediates in reactions that were previously only partially explained by mononuclear copper complexes or binuclear complexes containing only Cu(I) or Cu(II). , …”

Section: Discussionmentioning

confidence: 99%

Aryl Group Transfer from Tetraarylborato Anions to an Electrophilic Dicopper(I) Center and Mixed-Valence μ-Aryl Dicopper(I,II) Complexes

et al. 2016

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The synthesis of discrete, cationic binuclear μ-aryl dicopper complexes [Cu2(μ-η(1):η(1)-Ar)DPFN]X (Ar = C6H5, 3,5-(CF3)2C6H3, and C6F5; DPFN = 2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine; X = BAr4(-) and NTf2(-); Tf = SO2CF3) was achieved by treatment of a dicopper complex [Cu2(μ-η(1):η(1)-NCCH3)DPFN]X2 (X = PF6(-) and NTf2(-)) with tetraarylborates. Structural characterization revealed symmetrically bridging aryl groups, and (1)H NMR spectroscopy evidenced the same structure in solution at 24 °C. Electrochemical investigation of the resulting arylcopper complexes uncovered reversible redox events that led to the synthesis and isolation of a rare mixed-valence organocopper complex [Cu2(μ-η(1):η(1)-Ph)DPFN](NTf2)2 in high yield. The solid-state structure of the mixed-valence μ-phenyl complex exhibits inequivalent copper centers, despite a short Cu···Cu distance. Electronic and variable-temperature electron paramagnetic resonance spectroscopy of the mixed-valence μ-phenyl complex suggest that the degree of spin localization is temperature-dependent, with a high degree of spin localization observed at lower temperatures. Electronic structure calculations agree with the experimental results and suggest that the spin is localized almost entirely on one metal center.

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Section: Discussionmentioning

confidence: 99%

Aryl Group Transfer from Tetraarylborato Anions to an Electrophilic Dicopper(I) Center and Mixed-Valence μ-Aryl Dicopper(I,II) Complexes

et al. 2016

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“…The discovery of mild and versatile methods for the formation of C aryl –N bonds can have an impact on fields ranging from biology to natural-product synthesis to materials science. , An array of powerful approaches have been developed, including Ullmann couplings , and Buchwald–Hartwig reactions …”

Section: Introductionmentioning

confidence: 99%

“…Because aromatic nitrogen heterocycles are a particularly common motif in bioactive compounds, developing effective methods for their elaboration remains an important objective. Carbon–nitrogen bond-forming processes between nucleophilic nitrogen heterocycles and aryl electrophiles provide an attractive, convergent strategy for synthesizing derivatives, and such reactions can be accomplished with good efficiency with the aid of catalysts based on copper, palladium, and other metals. ,,, The use of copper can be advantageous from the standpoints of cost and/or toxicity, although an elevated temperature is almost always required and a plethora of catalyst/ligand combinations have been described that are often specific to certain families of nucleophiles.…”

Section: Introductionmentioning

confidence: 99%

A Versatile Approach to Ullmann C–N Couplings at Room Temperature: New Families of Nucleophiles and Electrophiles for Photoinduced, Copper-Catalyzed Processes

et al. 2013

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II. Photoinduced, Copper-Catalyzed N-Arylations (Tables 1-5) General Procedure. The nitrogen heterocycle (1.00 mmol), LiOt-Bu (112 mg, 1.40 mmol), and CuI (19.0 mg, 0.10 mmol) were added to an oven-dried 10-mL quartz test tube that contained a stir bar. The test tube was fitted with a rubber septum, the joint was wrapped with electrical tape, and the test tube was evacuated and backfilled with nitrogen (three cycles). Then, CH 3 CN (4.0 mL) and the aryl iodide (1.40 mmol; if the aryl iodide is a solid, then it was added immediately after the addition of CuI) were added in turn via syringe. The test tube was detached from the nitrogen manifold, and the puncture holes in the septum were covered with vacuum grease. The resulting mixture was stirred for 5 min, and then the test tube was transferred to a Luzchem LZC-4V photoreactor, where it was irradiated at 254 nm for 24 h (adequate stirring is important). Next, the mixture was passed through a long plug of silica gel (monitored by TLC), the solvent was removed, and the residue was purified by column chromatography. Notes: (a) A Honeywell ultraviolet air treatment system (model #RUVLAMP1), available for ~$110 from retail outlets such as Amazon or The Home Depot, furnishes a comparable result: indole and iodobenzene couple in 63% yield (calibrated GC analysis) after 48 h. (b) Use of a borosilicate, rather than a quartz, test tube leads to a low yield of the C-N coupling product. N 1-Phenyl-1H-indole (Table 1, entry 1) [16096-33-6]. The title compound was synthesized according to the General Procedure from indole (117 mg, 1.00 mmol), LiOt-Bu (112 mg, 1.40 mmol), CuI (19.0 mg, 0.10 mmol), and iodobenzene (286 mg, 1.40 mmol). The reaction mixture was filtered through a plug of silica gel (10% EtOAc/hexanes) and purified by column chromatography (hexanes). Pale-yellow oil. First run: 142 mg (73% yield). Second run: 148 mg (77% yield). N Me 1-(p-Tolyl)-1H-indole (Table 1, entry 2) [167283-32-1]. The title compound was synthesized according to the General Procedure from indole (117 mg, 1.00 mmol), LiOt-Bu (112 mg, 1.40 mmol), CuI (19.0 mg, 0.10 mmol), and 4-iodotoluene (305 mg, 1.40 mmol). The reaction mixture was filtered through a plug of silica gel (10% EtOAc/hexanes) and purified by column chromatography on silica gel (hexanes→1% Et 2 O/hexanes). Colorless oil. First run: 140 mg (68%). Second run: 143 mg (69%).

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Copper‐Mediated Cross‐Coupling Reactions

Abstract: General Introduction Carbon–Heteroatom Bond‐Forming Reactions Carbon–Carbon Bond Forming Reactions

Cited by 2 publications

References 461 publications

Aryl Group Transfer from Tetraarylborato Anions to an Electrophilic Dicopper(I) Center and Mixed-Valence μ-Aryl Dicopper(I,II) Complexes

Aryl Group Transfer from Tetraarylborato Anions to an Electrophilic Dicopper(I) Center and Mixed-Valence μ-Aryl Dicopper(I,II) Complexes

A Versatile Approach to Ullmann C–N Couplings at Room Temperature: New Families of Nucleophiles and Electrophiles for Photoinduced, Copper-Catalyzed Processes

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