- Copper-catalyzed radical ring-opening halogenation with HX
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An efficient copper-catalyzed radical ring-opening halogenation with HX (aq) is described. This protocol features redox-neutral conditions, green halogen sources, and a broad substrate scope, providing practical access to distally chlorinated, brominated and iodinated alkyl ketones and alkyl nitriles with moderate to good yields. This journal is
- Bai, Ming,Duan, Xin-Hua,Guo, Li-Na,Liu, Shuai,Sun, Qing-Xin,Xu, Peng-Fei
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supporting information
p. 8652 - 8655
(2021/09/04)
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- In-situ-generation of alkylsilyl peroxides from alkyl hydroperoxides and their subsequent copper-catalyzed functionalization with organosilicon compounds
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Alkylsilyl peroxides were generated in situ from the corresponding alkyl hydroperoxides using organosilicon compounds of the type Me3SiX (X = CN, N3, and halogens) and an amine base. Subsequent in situ copper-catalyzed homolytic cleavage of the alkylsilyl peroxides afforded alkyl radicals, which were then trapped with X (X = CN, N3, and halogens) to furnish products with new carbon-carbon, carbon-nitrogen, or carbon-halogen bonds in good to high yields.
- Xu, Weiping,Zhong, Wenfeng,Yang, Qin,Kato, Terumasa,Liu, Yan,Maruoka, Keiji
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supporting information
(2021/06/16)
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- Far-end halogenated alkyl ketone taking HX as halogen source and synthesis method of far-end halogenated alkyl ketone
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The invention relates to a far-end halogenated alkyl ketone taking HX as a halogen source and a synthesis method of the far-end halogenated alkyl ketone. The method comprises the following steps that: cycloalkyl peroxy alcohol and a copper acetate catalyst are added in a nitrogen atmosphere, then HCl, HBr and an HI solution are added as halogens, and stirring is carried out at normal temperature; after a reaction is finished, sufficient water is added to extract a reaction solvent N-methyl pyrrolidone, performing washing with saturated saline solution, an organic phase is dried with anhydrous sodium sulfate, the organic phase is concentrated under reduced pressure, so that the solvent can be removed; and column chromatography is performed on the organic phase to obtain a target product. According to the far-end halogenated alkyl ketone taking the HX as the halogen source and the synthesis method of the far-end halogenated alkyl ketoneinvention, industrial bulk raw materials HCl, HBr and an HI solution are used as the halogen source, free radical halogenation of C-C bond cracking is realized, and the far-end halogenated alkyl alkyl ketone compound is obtained with high yield; the byproduct of the reaction is water, so that the environmental pollution is reduced, and the industrial production benefit is greatly improved.
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Paragraph 0032
(2021/08/21)
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- Mn-Enabled Radical-Based Alkyl-Alkyl Cross-Coupling Reaction from 4-Alkyl-1,4-dihydropyridines
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Highly efficient alkylation of β-chloro ketones and their derivatives was achieved by means of domino dehydrochlorination/Mn-enabled radical-based alkyl-alkyl cross-coupling reaction. In situ-generated α,β-unsaturated ketones and their analogues were identified as the reaction intermediates. Known bioactive compounds, such as melperone and azaperone, could be easily prepared from β-chloropropiophenone in two steps.
- Wang, Jie,Pang, Yu-Bo,Tao, Na,Zeng, Run-Sheng,Zhao, Yingsheng
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p. 15315 - 15322
(2019/11/19)
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- Regioselective Synthesis of Carbonyl-Containing Alkyl Chlorides via Silver-Catalyzed Ring-Opening Chlorination of Cycloalkanols
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A novel and regioselective approach to carbonyl-containing alkyl chlorides via silver-catalyzed ring-opening chlorination of cycloalkanols is reported. Concurrent C(sp3)-C(sp3) bond cleavage and C(sp3)-Cl bond formation efficiently occur with good yields under mild conditions, and the chlorinated products are readily transformed into other useful synthetic intermediates and drugs. The reaction features complete regioselectivity, high efficiency, and excellent practicality. (Chemical Equation Presented).
- Huang, Feng-Qing,Xie, Jian,Sun, Jian-Guo,Wang, Yue-Wei,Dong, Xin,Qi, Lian-Wen,Zhang, Bo
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supporting information
p. 684 - 687
(2016/03/01)
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- Synthesis of alkyl aryl ketones by Pd/light induced carbonylative cross-coupling of alkyl iodides and arylboronic acids
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Alkyl aryl ketones were synthesized by the carbonylative cross-coupling reaction of alkyl iodides and arylboronic acids under combined Pd/light conditions. In this reaction, it is likely that an acylpalladium species would be formed via carbonylation of t
- Sumino, Shuhei,Ui, Takahito,Ryu, Ilhyong
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supporting information
p. 3142 - 3145
(2013/07/26)
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- Polymethylene derivatives of nucleic bases bearing ω-functional groups. VIII.1 ω-oxo-ω-phenylalkylpyrimidines and - Purines
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Novel polymethylene derivatives of nucleic bases containing a phenylketo functional group at the ω-position were synthesized by the alkylation of uracil, thymine, cytosine, hypoxanthine, adenine, and N-isobutyrylguanine with ω-chloro-l-phenylalkan-1-ones and their physicochemical properties were studied. Pleiades Publishing, Ltd., 2010.
- Komissarov,Kritzyn
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experimental part
p. 477 - 487
(2011/06/19)
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- Cross-coupling of organic compounds using cuprous iodide
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Cross-coupling or addition reactions of organic compounds, including acid halides, allylic halides, and α,β-unsaturated carbonyl containing compounds, with organozinc compounds may be readily and safely carried out in the presence of cuprous iodide. The use of this catalyst in the coupling reaction provides for the preparation of commercially useful products in the pharmaceutical, agrochemical and other industries.
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- Preparation and Chemistry of the Active Copper Species Derived from CuI*PBu3, CuI*PPh3, and CuCN*nLiX Complexes
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The preparation of highly reactive copper by the reduction of CuI*PBu3, CuI*PPh3, and CuCN*nLiX copper(I) complexes with the preformed lithium naphthalenide is described.It was found, for all three Cu(I) complexes, that the reduction temperature proved crucial to reactivity of the zerovalent copper species as measured by the ability of the active copper to undergo oxidative addition to carbon-halogen bonds.The lower the reduction temperature the more reactive the zerovalent copper species becomes.The low-temperature reduction allows for the formation of highly reactive copper from CuCN*nLiX complexes.This active copper species undergoes oxidative addition to alkyl and aryl bromides in high yield to form the corresponding organocopper reagent directly without the need for other organometallic precursors.Moreover, the alkyl and aryl bromides can obtain a wide range of functional groups as they are not affected in the oxidative addition step.The functionalized organocopper reagents derived from CuCN*nLiX based active copper are the reagent of choice in the cross-coupling of acid chlorides to produce ketones as well as the 1,4-addition reaction with enones.The lack of phosphines associated with organocopper reagents stemming from CuCN-based active copper makes product isolation more facile.While the functionalized organocopper reagents derived from CuCN*nLiX complexes provide higher isolated yields in the formentioned reactions, they are not nucleophilic enough to undergo inter- or intramolecular epoxide openings.The use of both CuI*PBu3 and CuI*PPh3 Cu(I) complexes in the intramolecular epoxide openings of aryl bromoepoxides is presented.The regiochemistry, endo vs. exo, was shown to be affected by the Cu(I) complex used to generate the active copper species, the solvent, and the pattern of substitution around the epoxide moiety.The active copper species as well as the resulting organocopper reagents derived from both CuI*PBu3 and CuCN*nLiX were investigated using both 31P and 13C NMR.The data from 31P NMR investigation held some evidence for a highly reduced copper(0)-phosphine complex while the 13C studies of the CuCN*nLiX complexes indicated that these species have limited solubility in THF.
- Rieke, Reuben D.,Stack, Douglas E.,Dawson, Bryan T.,Wu, Tse-Chong
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p. 2483 - 2491
(2007/10/02)
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- Direct Formation and Reaction of Thienyl-Based Organocopper Reagents
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The preparation of a highly reactive zerovalent copper complex by the direct reduction of lithium (2-thienylcyano)cuprate with preformed lithium naphthalenide is described.This active copper species oxidatively adds to carbon-halogen bonds to form organocopper reagents.The ability to directly form the organocopper reagent from organic halides and active copper allows for the incorporation of a wide variety of functionalities to be present in the organic halides and the organocopper reagents.Significantly, this formulation of active copper was able to oxidatively add to allyl chlorides and acetates at low temperatures to allow the direct formation of allylic organocopper reagents without Wurtz-type homocoupling.These functionalized organocopper compounds are able to undergo a variety of reactions, such as cross-coupling with acid chlorides, 1,4-conjugate addition with α,β-unsaturated carbonyl compounds, and intermolecular and intramolecular epoxide-opening reactions.Subsequently, this copper species avoids the use of phosphine ligands affording the product isolation much more convenient than with phosphine-based organocopper reagents.
- Rieke, Reuben D.,Klein, Walter R.,Wu, Tse-Chong
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p. 2492 - 2500
(2007/10/02)
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- The Direct Formation of Functionalized Alkyl(aryl)zinc Halides by Oxidative Addition of Highly Reactive Zinc with Organic Halides and Their Reactions with Acid Chlorides, α,β-Unsaturated Ketones, and Allylic, Aryl, and Vinyl Halides
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Highly reactive zinc, prepared by the lithium naphthalenide reduction of ZnCl2, readily undergoes oxidative addition to alkyl, aryl, and vinyl halides under mild conditions to generate the corresponding organozinc compounds in excellent yields.Significantly, the reaction will tolerate a spectrum of functional groups on the organic halides.Accordingly, this approach can now be used to prepare a wide variety of highly functionalized organozinc compounds.In the presence of Cu(I) salts, the organozinc compounds cross-couple with acid chlorides, conjugatively add to α,β-unsaturated ketones, and regioselectively undergo SN2' substitution reactions with allylic halides.They also cross-couple with aryl or vinyl halides with Pd(0) catalysts.
- Zhu, Lishan,Wehmeyer, Richard M.,Rieke, Reuben D.
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p. 1445 - 1453
(2007/10/02)
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- NEW ORGANOCOPPER REAGENTS PREPARED UTILIZING HIGHLY REACTIVE COPPER
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Highly reactive copper solutions have been prepared by the lithium naphthalide reduction of copper(I) iodide/trialkylphosphine complexes.These activated copper solutions will react with organic halides under very mild conditions to form stable organocopper reagents.Significantly, the organocopper reagents can contain considerable functionalities such as ester, nitrile, chloride, epoxide, and ketone groups.These functionalized organocopper species undergo many reactions typical of other organocopper species.Intermolecular 1,4-additions, epoxide-opening reactions, and ketone formation with acid chlorides have been successfully achieved.In addition, this methodology has been applied to an intramolecular epoxide-cleavage reaction.The influence of the connecting chain length, substitution pattern, reaction solvent, and CuI/phosphine complex upon the regioselectivity of the intramolecular cyclization is described.
- Rieke, Reuben D.,Wehmeyer, Richard M.,Wu, Tse-Chong,Ebert, Greg W.
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p. 443 - 454
(2007/10/02)
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- DIRECT FORMATION OF FUNCTIONALIZED KETONES VIA THE COUPLING OF FUNCTIONALIZED ORGANOCOPPER REAGENTS WITH ACID CHLORIDES
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Highly reactive copper solutions have been prepared by the lithium naphtalide reduction of copper(I) iodide/triphenyl-phosphine complex.These copper solutions react rapidly with functionalized alkyl halides to give organocopper reagents wich have been effectively trapped with acid chlorides giving functionalized ketones in good yields.Ester, nitrile, chloride, remote epoxide, and, to some degree, ketone groups can be tolerated by this approach.
- Wehmeyer, Richard M.,Rieke, Reuben D
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p. 4513 - 4516
(2007/10/02)
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- La reaction d'ω-azidocetones avec la triphenylphosphine: une voie d'acces generale aux imines cycliques
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The ω-azidoketones RC(=O)-CH(R')-(CH2)n-CH(R'')-N3 react with triphenylphosphine in anhydrous media to give 5, 6 and 7 membered cyclic imines via an intramolecular aza-Wittig reaction with good yields.A general synthesis of ω-haloketones which are the precursors of the azidoketones was also devised.
- Vaultier, M.,Lambert, P. H.,Carrie, R.
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