19811-05-3Relevant articles and documents
Asymmetric Transfer Hydrogenation of Diaryl Ketones with Ethanol Catalyzed by Chiral NCP Pincer Iridium Complexes
Huang, Zheng,Liu, Guixia,Qian, Lu,Tang, Xixia,Wang, Yulei
supporting information, (2022/02/23)
The use of a chiral (NCP)Ir complex as the precatalyst allowed for the discovery of asymmetric transfer hydrogenation of diaryl ketones with ethanol as the hydrogen source and solvent. This reaction was applicable to various ortho-substituted diaryl keontes, affording benzhydrols in good yields and enantioselectivities. This protocol could be carried out in a gram scale under mild reaction conditions. The utility of the catalytic system was highlighted by the synthesis of the key precursor of (S)-neobenodine.
Synthesis, structure, and characterization of picolyl- and benzyl-linked biphenyl palladium N-heterocyclic carbene complexes and their catalytic activity in acylative cross-coupling reactions
Muniyappan, Nalluchamy,Sabiah, Shahulhameed
, (2020/01/28)
N-heterocyclic carbene ligands with picolyl (L1H2Br2, L3H2Br2) and benzyl (L2H2Br2, L4H2Br2) linked biphenyl backbone were synthesized and characterized. Their palladium(II) complexes [PdL1]Br2 (1), [PdL2Br2] (2), [PdL3]Br2 (3), and [PdL4Br2] (4) were synthesized by direct method using Pd(OAc)2. All complexes (1–4) were characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and single-crystal X-ray diffraction. Molecular structures confirm the distorted square planar geometry around the Pd(II) center. All of them showed good catalytic activity in acylative Suzuki cross coupling of phenyl boronic acid with benzoyl chloride to afford benzophenone in good yields.
Decarboxylation with Carbon Monoxide: The Direct Conversion of Carboxylic Acids into Potent Acid Triflate Electrophiles
Kinney, R. Garrison,Arndtsen, Bruce A.
, p. 5085 - 5089 (2019/04/01)
We report a new strategy for the conversion of carboxylic acids into potent acid triflate electrophiles. The reaction involves oxidative carbonylation of carboxylic acids with I2 in the presence of AgOTf, and is postulated to proceed via acyl hypoiodites that react with CO to form acid triflates. Coupling this chemistry with subsequent trapping with arenes offers a mild, room temperature approach to generate ketones directly from broadly available carboxylic acids without the use of corrosive and reactive Lewis or Bronsted acid additives, and instead from compounds that are readily available, stable, and functional group compatible.
MeZnOMe-mediated reaction of aldehydes with Grignard reagents: A glance into nucleophilic addition/Oppenauer oxidation pathway
Fu, Ying,Ma, Xian-Zhen,Shi, Chun-Zhao,Shen, Tong,Du, Zhengyin
, (2018/07/31)
A novel organozincate of RMgX ?MeZnOMe ?LiCl type, formed in situ via transmetalation of Grignard reagent RMgBr ?LiCl with MeZnOMe, is shown to be an excellent organometallic species in the nucleophilic addition/Oppenauer oxidation of aldehydes to generate aromatic ketones in high yield. This transformation allows quick access to structurally diverse aryl, heteroaryl, benzyl and alkyl ketones with broad substrate scope and excellent functional group tolerance.
Synthesis of structurally diverse diarylketones through the diarylmethyl sp3 C-H oxidation
He, Chao,Zhang, Xiaohui,Huang, Ruofeng,Pan, Jing,Li, Jiaqiang,Ling, Xuege,Xiong, Yan,Zhu, Xiangming
, p. 4458 - 4462 (2014/08/05)
Under open-flask conditions, an efficient method to assemble a series of diversely functionalized diarylketones in the presence of commercially available NBS has been developed. Yields of up to 99% have been achieved employing diarylmethanes as starting material. Based on 18O-labeled experiment, the addition of stoichiometric water eventually leads to excellent yields in all carbonylation cases.
Tetraethylammonium iodide catalyzed synthesis of diaryl ketones via the merger of cleavage of C-C double bonds and recombination of aromatic groups
Zeng, Xianghua,Xu, Daqian,Miao, Chengxia,Xia, Chungu,Sun, Wei
, p. 46494 - 46497 (2014/12/10)
An efficient method for synthesizing diaryl ketones via merging of oxidative cleavage of C-C double bonds and recombination of aromatic groups is developed with Et4NI (2.5 mol%) as the catalyst and NaIO4 as the oxidant. The control experiments provide valuable mechanistic insights into the formation of diaryl ketones, and suggest that NaIO4 serves as an epoxidation and nucleophilic deformylation reagent.
Tandem nucleophilic addition-Oppenauer oxidation of aromatic aldehydes to aryl ketones with triorganoaluminium reagents
Fu, Ying,Yang, Yanshou,Hügel, Helmut M.,Du, Zhengyin,Wang, Kehu,Huang, Danfeng,Hu, Yulai
supporting information, p. 4429 - 4432 (2013/08/23)
In the presence of pinacolone, the in situ prepared triorganoaluminium reagents reacted with aromatic aldehydes to give ketones in moderate to high yield. We propose that the products are formed via a tandem organoaluminium reagents addition-Oppenauer oxidation sequence. The Royal Society of Chemistry 2013.
AROMATIC KETONE SYNTHESIS WITH AMIDE REAGENTS AND RELATED REACTIONS
-
Paragraph 0037, (2013/10/22)
A method of preparing an aryl carbonyl or aryl thiocarbonyl compound, comprises reacting an N-(nitroaryl)-amide or N-(nitroaryl)-thioamide with an aromatic ring, with a superacid catalyst, to produce the aryl carbonyl or aryl thiocarbonyl compound. The superacid is present in an amount of at most 8 equivalents in proportion to the N-(nitroaryl)-amide or N-(nitroaryl)-thioamide. A method of preparing aryl amide or aryl thioamide, comprises reacting an N-(nitroaryl)-carbamide or N-(nitroaryl)-thiocarbamide with an aromatic ring, with a superacid catalyst, to produce the aryl amide or aryl thioamide.
Friedel-crafts acylation with amides
Raja, Erum K.,Deschepper, Daniel J.,Nilsson Lill, Sten O.,Klumpp, Douglas A.
experimental part, p. 5788 - 5793 (2012/07/30)
Friedel-Crafts acylation has been known since the 1870s, and it is an important organic synthetic reaction leading to aromatic ketone products. Friedel-Crafts acylation is usually performed with carboxylic acid chlorides or anhydrides, while amides are generally not useful substrates in these reactions. Despite being the least reactive carboxylic acid derivative, we have found a series of amides capable of providing aromatic ketones in good yields (55-96%, 17 examples). We propose a mechanism involving diminished C-N resonance through superelectrophilic activation and subsequent cleavage to acyl cations.
Easy-to-execute carbonylative arylation of aryl halides using molybdenum hexacarbonyl: Efficient synthesis of unsymmetrical diaryl ketones
Jafarpour, Farnaz,Rashidi-Ranjbar, Parviz.,Kashani, Asieh Otaredi
experimental part, p. 2128 - 2132 (2011/05/09)
A versatile procedure for the synthesis of unsymmetrical diaryl ketones through a palladium-catalyzed carbonylative arylation of iodoarenes through easy-to-handle molybdenum hexacarbonyl as a condensed source of carbon monoxide is described. This method provides an efficient route to a wide variety of substituted diaryl ketones without direct use of high-pressure carbon monoxide. Copyright
