- Rapid and Direct Photocatalytic C(sp3)?H Acylation and Arylation in Flow
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Herein, we report a photocatalytic procedure that enables the acylation/arylation of unfunctionalized alkyl derivatives in flow. The method exploits the ability of the decatungstate anion to act as a hydrogen atom abstractor and produce nucleophilic carbon-centered radicals that are intercepted by a nickel catalyst to ultimately forge C(sp3)?C(sp2) bonds. Owing to the intensified conditions in flow, the reaction time can be reduced from 12–48 hours to only 5–15 minutes. Finally, kinetic measurements highlight how the intensified conditions do not change the reaction mechanism but reliably speed up the overall process.
- Bovy, Lo?c,Broersma, Rémy,Mazzarella, Daniele,No?l, Timothy,Pulcinella, Antonio
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supporting information
p. 21277 - 21282
(2021/08/23)
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- Synergistic Activation of Amides and Hydrocarbons for Direct C(sp3)–H Acylation Enabled by Metallaphotoredox Catalysis
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The utilizations of omnipresent, thermodynamically stable amides and aliphatic C(sp3)?H bonds for various functionalizations are ongoing challenges in catalysis. In particular, the direct coupling between the two functional groups has not been realized. Here, we report the synergistic activation of the two challenging bonds, the amide C?N and unactivated aliphatic C(sp3)?H, via metallaphotoredox catalysis to directly acylate aliphatic C?H bonds utilizing amides as stable and readily accessible acyl surrogates. N-acylsuccinimides served as efficient acyl reagents for the streamlined synthesis of synthetically useful ketones from simple C(sp3)?H substrates. Detailed mechanistic investigations using both computational and experimental mechanistic studies were performed to construct a detailed and complete catalytic cycle. The origin of the superior reactivity of the N-acylsuccinimides over other more reactive acyl sources such as acyl chlorides was found to be an uncommon reaction pathway which commences with C?H activation prior to oxidative addition of the acyl substrate.
- Baik, Mu-Hyun,Choi, Seulhui,Hong, Soon Hyeok,Lee, Geun Seok,Won, Joonghee
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p. 16933 - 16942
(2020/08/03)
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- Vinyl Triflate–Aldehyde Reductive Coupling–Redox Isomerization Mediated by Formate: Rhodium-Catalyzed Ketone Synthesis in the Absence of Stoichiometric Metals
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Direct conversion of aldehydes to ketones is achieved via rhodium-catalyzed vinyl triflate-aldehyde reductive coupling-redox isomerization mediated by potassium formate. This method circumvents premetalated C-nucleophiles and discrete redox manipulations typically required to form ketones from aldehydes.
- Shuler, William G.,Swyka, Robert A.,Schempp, Tabitha T.,Spinello, Brian J.,Krische, Michael J.
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supporting information
p. 12517 - 12520
(2019/09/17)
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- Cobalt-catalyzed acylation-reactions of (hetero)arylzinc pivalates with thiopyridyl ester derivatives
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A cobalt-catalyzed acylation reaction of various primary, secondary and tertiary alkyl, benzyl and (hetero)aryl S-pyridyl thioesters with (hetero)arylzinc pivalates is reported. The thioesters were prepared directly from the corresponding carboxylic acids under mild conditions, thus tolerating sensitive functional groups. Acylations of α-chiral S-pyridyl esters proceeded with very high stereoretention leading to optically enriched α-chiral ketones.
- Lutter, Ferdinand H.,Grokenberger, Lucie,Hofmayer, Maximilian S.,Knochel, Paul
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p. 8241 - 8245
(2019/09/19)
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- Aryl containing nitrogen heterocyclic substituted 1-hydroxy cyclohexyl benzene ketone method for the preparation of
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The invention discloses a preparation method of 1-hydroxycyclohexylphenylketone having a nitrogen heterocyclic ring substituent on aryl. The 1-hydroxycyclohexylphenylketone has a structural formula shown in the formula 1. The preparation method creatively
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Paragraph 0038-0040
(2017/02/24)
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- Iron-Catalyzed Acylation of Polyfunctionalized Aryl- and Benzylzinc Halides with Acid Chlorides
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FeCl2 (5 mol %) catalyzes a smooth and convenient acylation of functionalized arylzinc halides at 50 °C (2-4 h) and benzylic zinc chlorides at 25 °C (0.5-4 h) with a variety of acid chlorides leading to polyfunctionalized diaryl and aryl heteroaryl ketones.
- Benischke, Andreas D.,Leroux, Marcel,Knoll, Irina,Knochel, Paul
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supporting information
p. 3626 - 3629
(2016/08/16)
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- A ketone the synthetic method of the compound of (by machine translation)
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The invention discloses a method for the synthesis of ketone compound, the aldehyde compound and cyclanes mixed or dissolved in organic solvent, in the microwave radiation and presence of radical initiator under the condition of the 140 [...] 180 °C reaction to obtain the target product ketone compound, in the synthesis method of the reaction equation: , Wherein R 1 is phenyl or substituted phenyl, substituted phenyl benzene ring substituted the base is the fluorine, chloro, bromo, methyl, methoxy, trifluoromethyl or hydroxy in one or more of, the position of the substituent on the benzene ring is ortho, meta or para position, as n the 1 [...] 4 integer between the, free-radical initiator is benzoyl peroxide, di-tert-butyl peroxide, or cumyl peroxide, organic solvent as the alkane or benzene. The invention discloses method for the synthesis of the raw material is cheap and easy to obtain, good atom economy, wide range of the application of substrates, and the like, is suitable for industrial production. (by machine translation)
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Paragraph 0036-0038
(2017/01/05)
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- Synthesis of Ketones through Microwave Irradiation Promoted Metal-Free Alkylation of Aldehydes by Activation of C(sp3)-H Bond
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In this paper, a novel methodology for the synthesis of ketones via microwave irradiation promoted direct alkylation of aldehydes by activation of the inert C(sp3)-H bond has been developed. Notably, the reactions were accomplished under metal-free conditions and used commercially available aldehydes and cycloalkanes as substrates without prefunctionalization. By using this novel method, an alternative synthetic approach toward the key intermediates for the preparation of the pharmaceutically valuable oxaspiroketone derivatives was successfully established.
- Zhang, Xinying,Wang, Zhangxin,Fan, Xuesen,Wang, Jianji
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p. 10660 - 10667
(2015/11/18)
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- Fe-catalyzed regiodivergent [1,2]-shift of α-aryl aldehydes
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An Fe-catalyzed conversion of aldehydes to ketones via [1,2]-shift has been developed. This skeletal rearrangement shows a wide substrate scope and chemoselectivity profile while exhibiting an excellent [1,2]-aryl or [1,2]-alkyl shift selectivity that is easily switched by electronic effects.
- Gutierrez-Bonet, Alvaro,Flores-Gaspar, Areli,Martin, Ruben
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p. 12576 - 12579
(2013/09/23)
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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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- Ketone substituted benzimidazole compounds
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Disclosed are ketone substituted benzimidazole compounds of formula(I): wherein R1, R2, R3, R4 and Xa are defined herein. The compounds of the invention inhibit Itk kinase and are therefore useful for
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Page/Page column 12
(2010/02/13)
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- Ruthenium-catalyzed coupling of aldimines with arylboronates: New synthetic method for aromatic ketones
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Using the chelation strategy, the reaction of aldimines bearing the 3-picolin-2-yl group with various arylboronates in the presence of a ruthenium catalyst furnished the corresponding ketimines in high yields for a short reaction time; the resulting ketimines were readily converted to ketones by hydrolysis. The Royal Society of Chemistry 2005.
- Park, Young Jun,Jo, Eun-Ae,Jun, Chul-Ho
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p. 1185 - 1187
(2007/10/03)
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