946-01-0Relevant articles and documents
Copper-catalyzed radical ring-opening halogenation with HX
Bai, Ming,Duan, Xin-Hua,Guo, Li-Na,Liu, Shuai,Sun, Qing-Xin,Xu, Peng-Fei
, p. 8652 - 8655 (2021/09/04)
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
Far-end halogenated alkyl ketone taking HX as halogen source and synthesis method of far-end halogenated alkyl ketone
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Paragraph 0032, (2021/08/21)
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.
Visible-light-promoted site-specific and diverse functionalization of a c(sp3)-c(sp3) bond adjacent to an arene
Fang, Fang,Liu, Zhong-Quan,Sun, Minzhi,Wang, Nengyong,Wang, Yaxin,You, Huichao,Zhao, Jianyou
, p. 6603 - 6612 (2020/07/27)
We report here a strategy for inert C-C bond functionalization. Site-specific cleavage and functionalization of a saturated C(sp3)-C(sp3) bond via a visible-light-induced radical process have been achieved. The general features of this reaction are as follows. (1) Both linear and cyclic C(sp3)-C(sp3) bonds with a vicinal arene can be specifically functionalized. (2) One carbon is converted into a ketone, and another can be tunably converted into nitrile, peroxide, or halide. (3) The typical conditions include 1.0 mol % of Ru(bpy)3Cl2, 1.0 or 5.0 equiv of Zhdankin reagent, white CFL (24 W), open flask, and room temperature. These reactions offer powerful tools to modify carbon skeletons that are intractable by conventional methods. Good selectivity and functional group tolerance, together with mild and open air conditions, make these transformations valuable and attractive.
Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols
Verheyen, Thomas,Van Turnhout, Lars,Vandavasi, Jaya Kishore,Isbrandt, Eric S.,De Borggraeve, Wim M.,Newman, Stephen G.
supporting information, (2019/05/08)
An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.
Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols
Verheyen, Thomas,Van Turnhout, Lars,Vandavasi, Jaya Kishore,Isbrandt, Eric S.,De Borggraeve, Wim M.,Newman, Stephen G.
supporting information, p. 6869 - 6874 (2019/05/10)
An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.
Photocatalytic decarboxylative alkylations mediated by triphenylphosphine and sodium iodide
Fu, Ming-Chen,Shang, Rui,Zhao, Bin,Wang, Bing,Fu, Yao
, p. 1429 - 1434 (2019/04/30)
Most photoredox catalysts in current use are precious metal complexes or synthetically elaborate organic dyes, the cost of which can impede their application for large-scale industrial processes. We found that a combination of triphenylphosphine and sodium iodide under 456-nanometer irradiation by blue light–emitting diodes can catalyze the alkylation of silyl enol ethers by decarboxylative coupling with redox-active esters in the absence of transition metals. Deaminative alkylation using Katritzky’s N-alkylpyridinium salts and trifluoromethylation using Togni’s reagent are also demonstrated. Moreover, the phosphine/iodide-based photoredox system catalyzes Minisci-type alkylation of N-heterocycles and can operate in tandem with chiral phosphoric acids to achieve high enantioselectivity in this reaction.
The synthesis of ω-(2-aryl-1,3-dioxolan-2-yl)alkyl purine derivatives and their activity towards HIV reverse transcriptase
Komissarov,Valuev-Elliston,Ivanova,Kochetkov,Kritzyn
, p. 37 - 45 (2015/02/05)
Novel derivatives of 6-substituted purines were synthesized by alkylation of 6-substituted purines with various 2-(chloroalkyl)-2-aryl-1,3-dioxolanes and related compounds. Their inhibitory properties toward HIV reverse transcriptase were studied. The structure-activity relationship within the synthesized compounds was found.
Synthesis of nitrogenated heterocycles by asymmetric transfer hydrogenation of N-(tert-butylsulfinyl)haloimines
Pablo, Oscar,Guijarro, David,Yus, Miguel
, p. 9181 - 9189 (2013/10/08)
Highly optically enriched, protected, nitrogenated heterocycles with different ring sizes have been synthesized by a very efficient methodology consisting of the asymmetric transfer hydrogenation of N-(tert-butylsulfinyl) haloimines followed by treatment with a base to promote an intramolecular nucleophilic substitution process. N-Protected aziridines, pyrrolidines, piperidines, and azepanes bearing aromatic, heteroaromatic, and aliphatic substituents have been obtained in very high yields and diastereomeric ratios up to >99:1. The free heterocycles can be easily obtained by a simple and mild desulfinylation procedure. Both enantiomers of the free heterocycles can be prepared with the same good results by changing the absolute configuration of the sulfur atom of the sulfinyl group.
Efficient synthesis of functionalized organozinc compounds by the direct insertion of zinc into organic iodides and bromides
Krasovskiy, Arkady,Malakhov, Vladimir,Gavryushin, Andrei,Knochel, Paul
, p. 6040 - 6044 (2007/10/03)
(Chemical Equation Presented) Insider dealing: A wide range of poly-functional (hetero)aromatic and aliphatic zinc reagents can be easily prepared in THF. The compounds are formed by a Zn insertion reaction mediated by the addition of LiCl (see scheme; All = allyl).
Design and synthesis of orally active benzamide derivatives as potent serotonin 4 receptor agonist
Sonda, Shuji,Kawahara, Toshio,Murozono, Takahiro,Sato, Noriko,Asano, Kiyoshi,Haga, Keiichiro
, p. 4225 - 4234 (2007/10/03)
A series of 4-amino-5-chloro-2-methoxy-N-(piperidin-4-ylmethyl)benzamide derivatives bearing an aralkylamino, alkylamino, benzoyl or phenylsulfonyl group at its side chain part at the 1-position on the piperidine ring was synthesized. They were evaluated
