- Palladium-Catalyzed Synthesis of α-Methyl Ketones from Allylic Alcohols and Methanol
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One-pot synthesis of α-methyl ketones starting from 1,3-diaryl propenols or 1-aryl propenols and methanol as a C1 source is demonstrated. This one-pot isomerization-methylation is catalyzed by commercially available Pd(OAc)2 with H2O as the only by-product. Mechanistic studies and deuterium labelling experiments indicate the involvement of isomerization of allyl alcohol followed by methylation through a hydrogen-borrowing pathway in these isomerization-methylation reactions.
- Biswal, Priyabrata,Samser, Shaikh,Meher, Sushanta Kumar,Chandrasekhar, Vadapalli,Venkatasubbaiah, Krishnan
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p. 413 - 419
(2021/11/01)
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- Iron-Catalyzed Cleavage Reaction of Keto Acids with Aliphatic Aldehydes for the Synthesis of Ketones and Ketone Esters
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The radical–radical coupling reaction is an important synthetic strategy. In this study, the iron-catalyzed radical–radical cross-coupling reaction based on the decarboxylation of keto acids and decarbonylation of aliphatic aldehydes to obtain valuable aryl ketones is reported for the first time. Remarkably, when tertiary aldehydes were used as carbonyl sources, ketone esters were selectively obtained instead of ketones. The gram-scale preparation of aryl ketone through this strategy was easily achieved by using only 3 mol % of the iron catalyst. As a proof-of-concept, the bioactive molecule flurprimidol was synthesized in two steps by using this strategy.
- Zhou, Fangyuan,Li, Lesong,Lin, Kao,Zhang, Feng,Deng, Guo-Jun,Gong, Hang
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supporting information
p. 4246 - 4250
(2020/03/11)
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- Method for preparing aryl ketone based on iron-catalyzed free radical-free radical coupling reaction such as ketonic acid decarboxylation and fatty aldehyde de-carbonylation
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The invention discloses a method for preparing an aryl ketone derivative based on a free radical-free radical cross-coupling reaction such as ketonic acid decarboxylation and fatty aldehyde de-carbonylation. The method comprises the following steps: reacting aryl-substituted ketonic acid with fatty aldehyde under the catalytic action of ferric triacetylacetonate to generate an aryl ketone derivative; the gram-grade reaction can be realized by the method only by using 3mol% of an iron catalyst; and the method has the advantages of no need of consumption of a large amount of a Lewis acid catalyst or a stoichiometric organic metal reagent, mild reaction conditions, one-step reaction, few by-products, wide substrate application range and scalable reaction, and overcomes the defects of large catalyst consumption, insufficient functional group tolerance, many by-products and the like in the prior art.
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Paragraph 0051-0052
(2020/05/05)
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- Catalytic C1 Alkylation with Methanol and Isotope-Labeled Methanol
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A metal-catalyzed methylation process has been developed. By employing an air- and moisture-stable manganese catalyst together with isotopically labeled methanol, a series of D-, CD3-, and 13C-labeled products were obtained in good yields under mild reaction conditions with water as the only byproduct.
- Sklyaruk, Jan,Borghs, Jannik C.,El-Sepelgy, Osama,Rueping, Magnus
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supporting information
p. 775 - 779
(2019/01/04)
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- Process for preparing photoinitiator 185
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The invention provides a process for preparing a photoinitiator 185 and belongs to the field of photoinitiator preparation processes. The process includes a high temperature ketone preparing process:liquefy and mixing tert-butylbenzoic acid and iso-butyric acid and then obtaining a reaction mixed liquid, preheating the reaction mixed liquid and causing the reaction mixed liquid to come into contact with a metal salt catalyst, removing carbon dioxide through dehydration at a high temperature (300-500 DEG C) to manufacture ketone, and obtaining 2-methyl-1-[4-(tert-butyl)phenyl]-1-acetone; a one-pot method chlorination alkaline hydrolysis process: taking 2-methyl-1-[4-(tert-butyl)phenyl]-1-acetone, taking carbon tetrachloride and sodium hydroxide as reagents, taking tetrabutylammonium bromide as a phase transfer catalyst, and performing one-pot method chlorination and alkaline hydrolysis to obtain 2-hydroxyl-2-methyl-1-[4-(tert-butyl)phenyl]-1-acetone. According to the process, the use of hazardous chemicals such as phosphorus trichloride, aluminum trichloride and flammable carcinogenic raw material benzene in the prior art is eliminated, and the safety and environmental protection pressure of the whole process is effectively improved, and the treatment cost of three wastes is greatly reduced.
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Paragraph 0035; 0037; 0039; 0041; 0043; 0045
(2019/01/16)
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- Palladium-Catalyzed Carbonylative Coupling of Aryl Iodides with Alkyl Bromides: Efficient Synthesis of Alkyl Aryl Ketones
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Alkyl aryl ketones are important structures with applications in many areas of chemistry. Hence, efficient procedures for their production are particularly attractive. In this communication, a general and efficient carbonylative cross-coupling of aryl iodides and unactivated alkyl bromides is presented. By using a simple palladium catalyst, a series of alkyl aryl ketones were synthesized in moderate to excellent yields from readily available alkyl and aryl halides in an In-Ex tube with formic acid as the CO source. In this study both primary and secondary alkyl bromides/iodides were suitable coupling partners. Additionally, this method can also be employed for the late-stage functionalization of complex natural products and polyfunctionalized molecules. (Figure presented.).
- Peng, Jin-Bao,Chen, Bo,Qi, Xinxin,Ying, Jun,Wu, Xiao-Feng
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supporting information
p. 4153 - 4160
(2018/09/21)
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- Alkyl-aryl ketone synthesis via nickel-catalyzed reductive coupling of alkyl halides with aryl acids and anhydrides
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The present work disclosed a considerably improved method for the construction of alkyl-aryl ketones by the direct coupling of unactivated alkyl bromides with 1.5 equiv. of acids. In addition, the synthesis of aroyl C-glycosides was first achieved by the
- Jia, Xiao,Zhang, Xinghua,Qian, Qun,Gong, Hegui
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supporting information
p. 10302 - 10305
(2015/06/25)
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- Gram-scale ketone synthesis by direct reductive coupling of alkyl iodides with acid chlorides
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Alkyl aryl ketones were prepared on a gram scale by the nickel-catalyzed reductive coupling of alkyl iodides with aroyl chlorides. When scaled up 30-fold, this reaction shows a comparable coupling efficiency to the previously reported reaction performed under small-scale conditions. The mild and convenient reaction conditions show excellent tolerance to a range of functional groups and provide the ketones in good to excellent yields. Georg Thieme Verlag Stuttgart. New York.
- Lu, Wenbin,Liang, Zhuye,Zhang, Yuwei,Wu, Fan,Qian, Qun,Gong, Hegui
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p. 2234 - 2240
(2013/09/02)
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- Mild ketone formation via Ni-catalyzed reductive coupling of unactivated alkyl halides with acid anhydrides
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Ni-catalyzed ketone formation through mild reductive coupling of a diverse set of unactivated alkyl bromides and iodides with particularly aryl acid anhydrides was successfully developed using zinc as the terminal reductant. These conditions also allow direct coupling of alkyl iodides with aryl acids in the presence of Boc2O and MgCl2. The Royal Society of Chemistry 2012.
- Yin, Hongyu,Zhao, Chenglong,You, Hengzhi,Lin, Kunhua,Gong, Hegui
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supporting information; experimental part
p. 7034 - 7036
(2012/08/14)
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- Ketone formation via mild Nickel-catalyzed reductive coupling of alkyl halides with aryl acid chlorides
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The present work highlights unprecedented Ni-catalyzed reductive coupling of unactivated alkyl iodides with aryl acid chlorides to efficiently generate alkyl aryl ketones under mild conditions.
- Wu, Fan,Lu, Wenbin,Qian, Qun,Ren, Qinghua,Gong, Hegui
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p. 3044 - 3047
(2012/08/07)
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- Mechanisms of Elimination Reactions. 39. Steric and Electronic Effects on Stereochemistry in Eliminations from Primary Alkyltrimethylammonium Salts
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Percentages of syn elimination have been determined by high-field NMR on the products of elimination from R1R2CHCHDX.The results for X=OTs with t-BuO(-)/t-BuOH at 60 deg C were the following (R1, R2, percent syn): p-MeOC6H4, C6H5, 3.7; p-ClC6H4, C6H5, 29; p-ClC6H4, C6H5, 0 in EtO(-)/EtOH.For X=NMe3(+) with OH(-) in 50 molpercent Me2SO-50 molpercentH2O at 60 deg C, the results were as follows (R1, R2, percent syn): p-MeOC6H4, C6H5, 60; p-ClC6H4, C6H5, 72.For Ar(i-Pr)CHCHDNMe3(+) with OH(-) in 50 molpercent Me2SO-50 molpercent H2O at 80 deg C, the results were as follows (Ar, percent syn): m-ClC6H4, 78.6; p-ClC6H4, 69.5; C6H5, 59.6; p-EtC6H4, 58.3; p-t-BuC6H4, 60.5.Overall rates in this series were dissected into syn and anti rates, which fitted the Hammett equation to give ρsyn=3.69 +/- 0.20 and ρanti=3.02 +/- 0.22.This result supports the conclusion that syn elimination has a more carbanionic transition state than anti.The lower percent syn with X=OTs than with X=NMe3(+) is ascribed to the lesser steric requirements of OTs.
- Dohner, Brent R.,Saunders, William H. Jr.
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p. 245 - 247
(2007/10/02)
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- The Allopolarization Principle and its Applications, IV. Substituent Effects in the Methylation of Enolate Anions
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The ratio of O- and C-methylated products in the reaction of the sodium salts of acetophenones 1, propiophenones 3, phenylacetones 5, β-dicarbonyl compounds 12, α-cyanocarbonyl compounds 13, acetaldehyde, propionaldehyde, and diethylketone with dimethyl sulfate, methyl iodide, and trimethyl phosphate in HMPTA has been determined with regard to the effect of substituents.In some cases the influence of solvents, concentration and temperature has also been studied.
- Gompper, Rudolf,Vogt, Hans-Hubert
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p. 2866 - 2883
(2007/10/02)
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- P-tert-butyl-diphenylalkane insecticides
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1,1-Diphenylalkanes having a p-tert-butyl and a p'-alkoxy group substituted thereon are a novel class of compounds having a broad range of insecticidal activity.
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