Copper-catalyzed reaction of aryl iodides with active methylene compounds

Okuro, Kazumi; Furuune, Makoto; Miura, Masahiro; Nomura, Masakatsu

doi:10.1021/jo00078a053

Cited by 142 publications

(76 citation statements)

References 2 publications

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“…Compound 11 e was obtained with 79 % selectivity and was isolated in decent yield (62 %, entry 9). This yield is noteworthy compared with the 55 % reported by Miura [59] for the same coupling performed at 120 8C without additional ligand, and with the 42-61 % yields obtained using stoichiometric amounts of copper salts.…”

Section: Introductionsupporting

confidence: 62%

“…[44a] diethyl malonate, [8] and malononitrile [59] arylation. With regard to amides and carbamates, our catalytic systems were particularly efficient for condensations with oxazolidin-2-one and pyridin-2-one.…”

Section: Resultsmentioning

confidence: 99%

“…[13] Extension of the method to aryl halides lacking substituents capable of coordinating to the active Cu species is hampered by numerous restrictions, including modest yields, the requirement of at least stoichiometric amounts of copper, [56a, 57] limited substrate scope, [58] or a high reaction temperature (120 8C), at which malonate esters tend to decompose. [59] Only recently was a variant of this transformation performed under mild conditions, in the presence of simultaneously catalytic copper and a weak base, allowing high functional-group tolerance. Buchwald et al employed CuI as a precatalyst and 2-phenylphenol as ligand to mediate the C-arylation of diethyl malonate with aryl iodides in the presence of cesium carbonate at 70 8C.…”

Section: Introductionmentioning

confidence: 99%

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Highly Efficient and Mild Copper‐Catalyzed N‐ and C‐Arylations with Aryl Bromides and Iodides

Cristau

Cellier

Spindler³

et al. 2004

Chemistry A European J

576

239

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Mild, efficient, copper-catalyzed N-arylation procedures for nitrogen heterocycles, amides, carbamates, and C-arylation procedures for malonic acid derivatives have been developed that afford high yields of arylated products with excellent selectivity. The N-arylation of imidazole with aryl bromides or iodides was found to be greatly accelerated by inexpensive, air-stable catalyst systems, combining catalytic copper salts or oxides with a set of structurally simple chelating ligands. The reaction was shown to be compatible with a broad range of aryl halides, encompassing sterically hindered, electron-poor, and electron-rich ones, providing the arylated products under particularly mild conditions (50-82 degrees C). The lower limit in ligand and catalyst loading and the scope of Ullmann-type condensations catalyzed by complexes bearing those ligands with respect to the nucleophile class have also been investigated. Chelating Schiff base Chxn-Py-Al (1c) generates a remarkably general copper catalyst for N-arylation of pyrrole, indole, 1,2,4-triazole, amides, and carbamates; and C-arylation of diethyl malonate, ethyl cyanoacetate, and malononitrile with aryl iodides under mild conditions (50-82 degrees C). The new method reported here is the most successful to date with regard to Ullmann-type arylation of some of these nucleophiles.

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Section: Introductionsupporting

confidence: 62%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Highly Efficient and Mild Copper‐Catalyzed N‐ and C‐Arylations with Aryl Bromides and Iodides

Cristau

Cellier

Spindler³

et al. 2004

Chemistry A European J

576

239

View full text Add to dashboard Cite

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“…For the synthesis of these substituted 1,3-diketonep recursors, arylation of activatedm ethylene compounds mediated by coppers altsu sing iodoarenes is aw ell-established process [9] and usually requires as toichiometric [9,10] or catalytic [11] amount of copper salt. This approachw as used to prepare3 -(4-benzyloxyphenyl)-2,4-pentanodione, ac ompound similart oo ur target, in moderatey ield (54 %).…”

Section: Synthesismentioning

confidence: 99%

Supramolecular Columnar Liquid Crystals with Tapered‐Shape Simple Pyrazoles Obtained by Efficient Henry/Michael Reactions

Blanco

Iguarbe

Barberá

et al. 2016

Chemistry A European J

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A straightforward synthesis of mesogenic pyrazoles starting from benzaldehydes by a combination of efficient Henry and Michael reactions led to novel supramolecular liquid crystals. The mesogens are fluorescent 3,5-dimethyl-4-(di or trialkoxyphenyl)pyrazoles and, in spite of the tapered shape of these molecules and their structural simplicity (only one phenyl ring), columnar liquid-crystal phases were formed that are stable at room temperature. The self-assembled structure was studied by XRD and the columnar cross section contains two molecules on average with an antiparallel arrangement of pyrazoles interacting through hydrogen bonds. In contrast, the single-crystal structure of a trimethoxy analog did not show hydrogen-bonded pyrazoles but chains of head-to-tail arranged molecules.

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“…Copper-catalyzed arylation of malonates [205] and other activated methylene compounds (malononitrile, ethyl cyanoacetate) [206] has been also reported. It is likely that the catalytically active species is a Cu(I) enolate.…”

Section: Formation Of Cc-bonds In the Palladium-catalyzed A-arylatiomentioning

confidence: 99%

Mechanistic Aspects of Metal‐Catalyzed C—C and C—X Bond‐Forming Reactions

Echavarren

Cárdenas

2005

ChemInform

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Cross-coupling reactions, such as the Stille reaction of organostannanes [1][2][3] and the Suzuki (or Suzuki-Miyaura) cross-coupling of organoboron compounds [4] have settled amongst the more general and selective palladium-catalyzed cross-coupling reactions [5] (Scheme 1-1). These reactions are closely related to other cross-couplings based on transmetallations of a variety of hard or soft organometallic nucleophiles [6] such as the Hiyama [7,8], Sonogashira [9], Kumada (or Kumada-Corriu), and other related couplings [10][11][12].Coupling reactions are somewhat related to the Heck alkenylation of organic electrophiles [13, 14], which is often referred to in the literature as a coupling process. However, although the first steps in both processes are identical, in the Heck reaction there is no transmetallation step. In the alkenylation reaction, the C-C bond is formed by an insertion process, which is followed by a b-hydride elimination to form the substituted alkene product. Cross-coupling (transmetallationbased) processes are a family of closely related catalytic processes that share most mechanistic aspects, although some differences exist on the activation of the organometallic nucleophile. So far, most of the detailed mechanistic studies have cen-

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Copper-catalyzed reaction of aryl iodides with active methylene compounds

Cited by 142 publications

References 2 publications

Highly Efficient and Mild Copper‐Catalyzed N‐ and C‐Arylations with Aryl Bromides and Iodides

Highly Efficient and Mild Copper‐Catalyzed N‐ and C‐Arylations with Aryl Bromides and Iodides

Supramolecular Columnar Liquid Crystals with Tapered‐Shape Simple Pyrazoles Obtained by Efficient Henry/Michael Reactions

Mechanistic Aspects of Metal‐Catalyzed C—C and C—X Bond‐Forming Reactions

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