Preparation of thermally stable and soluble mesitylcopper(I) and its application in organic synthesis

Tsuda, Tetsuo; Yazawa, Tetsuo; Watanabe, Katsuhiko; Fujii, Tomoyuki; Saegusa, Takeo

doi:10.1021/jo00314a048

Cited by 132 publications

(59 citation statements)

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“…Acetonitrile (CH 3 CN) was dried over CaH 2 and distilled under nitrogen prior to use. [Cu 4 Mes 4 ] (Mes = mesityl),14 and the protonated forms of 4 9 and 5 10 were prepared according to published procedures. All metal complexes were prepared and stored in a Vacuum Atmospheres inert atmosphere glovebox under a dry nitrogen atmosphere or were manipulated using standard inert atmosphere vacuum and Schlenk techniques.…”

Section: Methodsmentioning

confidence: 99%

Effects of Electron-Deficient β-Diketiminate and Formazan Supporting Ligands on Copper(I)-Mediated Dioxygen Activation

et al. 2009

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Copper(I) complexes of a diketiminate featuring CF 3 groups on the backbone and dimethylphenyl substituents (4) and a nitroformazan (5) were synthesized and shown by spectroscopy, X-ray crystallography, cyclic voltammetry, and theory to contain Cu(I) sites electron deficient relative to those supported by previously studied diketiminate complexes comprising alkyl or aryl backbone substituents. Despite their electron poor nature, oxygenation of LCu(CH 3 CN) (L = 4 or 5) at room temperature yielded bis(hydroxo)dicopper(II) compounds and at − 80 °C yielded bis(μ-oxo)dicopper complexes that were identified on the basis of UV-vis and resonance Raman spectroscopy, spectrophotometric titration results (2:1 Cu/O 2 ratio), EPR silence, and DFT calculations. The bis (μ-oxo)dicopper complex supported by 5 exhibited unusual spectroscopic properties and decayed via a novel intermediate proposed to be a metallaverdazyl radical complex, findings which highlight the potential for the formazan ligand to exhibit 'non-innocent' behavior.

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Section: Methodsmentioning

confidence: 99%

Effects of Electron-Deficient β-Diketiminate and Formazan Supporting Ligands on Copper(I)-Mediated Dioxygen Activation

et al. 2009

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“…{CuA C H T U N G T R E N N U N G (mes)} n was synthesized by following a literature procedure. [38] All other reagents were obtained from commercial sources and used without any further purification. 19 F NMR spectra were referenced to internal CFCl 3 .…”

Section: A C H T U N G T R E N N U N G (C 6 H 5 )A C H T U N G T R E mentioning

confidence: 99%

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Lum

Tahsini

Golen

et al. 2013

Chemistry A European J

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Seven E[Cu(OR)2] copper(I) complexes (E = K(+), {K(18C6)}(+) (18C6 = [18]crown-6), or Ph4P(+); R = C4F9, CPhMe(F)2, and CMeMe(F)2) have been prepared and their reactivity with O2 studied. The K[Cu(OR)2] species react with O2 in a copper-concentration-dependent manner such that 2:1 and 3:1 Cu/O2 adducts are observed manometrically at -78 °C. Analogous reactivity with O2 is not observed with the {K(18C6)}(+) or Ph4P(+) derivatives. Solution conductivity data demonstrate that these K[Cu(OR)2] complexes do not behave as 1:1 electrolytes in solution. The K(+) ions induce aggregation of multiple [Cu(OR)2](-) units through K⋅⋅⋅F/O interactions and thereby effect irreversible O2 reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K(+) ions. Intramolecular hydroxylation of ligand aryl and alkyl C-H bonds is observed. Nucleophilic reactivity with CO2 is observed for the oxygenated Cu complexes and a Cu(II) carbonate has been isolated and characterized.

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“…An alternative preparative route employing CuMes as a copper metalation reagent (Route B, Scheme ) was used to prepare copper(I) piperidide ([Cu(NC 5 H 10 )] n ; 4 ), and copper(I) benzylamide ([Cu(N(H)CH 2 Ph)] n ; 5 ) 41. 42, 49 This synthetic route avoided the formation of halide salt byproducts and allowed preparation of the copper(I) amides in high purity. It is interesting to note that the success of Route B was very dependent upon the parent amine used, and despite several attempts it was not possible to prepare complexes 1 and 2 via this route.…”

Section: Resultsmentioning

confidence: 99%

Aplysiasecosterol A: A 9,11‐Secosteroid with an Unprecedented Tricyclic γ‐Diketone Structure from the Sea Hare Aplysia kurodai

2015

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A new 9,11‐secosteroid having an unprecedented tricyclic γ‐diketone structure, aplysiasecosterol A (1), was isolated from the sea hare Aplysia kurodai. The structure was determined by one‐ and two‐dimensional NMR spectroscopic analysis, molecular modeling studies, a comparison of experimental and calculated ECD spectra, and a modified Mosher′s method. Aplysiasecosterol A (1) exhibited cytotoxicity against human myelocytic leukemia HL‐60 cells. A biosynthetic pathway for 1 from a known cholesterol was proposed and includes twice α‐ketol rearrangements and an intramolecular acetalization.

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Preparation of thermally stable and soluble mesitylcopper(I) and its application in organic synthesis

Abstract: combined, washed one time with saturated Na2S203, dried (MgS04), and evaporated to give 0.12 g (87%) of 4-hydroxy-3methyl-4-phenyl-2-butanone (8) as a nearly colorless oil: IR (thin

Cited by 132 publications

References 0 publications

Effects of Electron-Deficient β-Diketiminate and Formazan Supporting Ligands on Copper(I)-Mediated Dioxygen Activation

Effects of Electron-Deficient β-Diketiminate and Formazan Supporting Ligands on Copper(I)-Mediated Dioxygen Activation

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Aplysiasecosterol A: A 9,11‐Secosteroid with an Unprecedented Tricyclic γ‐Diketone Structure from the Sea Hare Aplysia kurodai

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