- Water-Tolerant ortho-Acylation of Phenols
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A metal-free, water-tolerant, and one-pot process for ortho-acylation of phenols promoted by the iodine source/hydrogen peroxide system has been developed. This transformation undergoes ether formation, iodocyclization, C-C bond cleavage, and oxidative hydrolysis in a one-step manner, which is supported by control experiments.
- Dong, Shuang-Feng,Gao, Zhi-Yuan,He, Yu,Liu, Xu,Loh, Teck-Peng,Tian, Jie-Sheng,Wu, Peng
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p. 6594 - 6598
(2021/09/02)
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- Cu/Ag mediated peroxide-free synthesis of benzoylated naphthol derivatives
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A peroxide-free methodology was developed for the synthesis of benzoylated naphthol/phenol derivatives through oxidative deamination reaction performed under aerobic reaction conditions. A synergistic combination of Cu(OTf)2 and Ag2O was used to convert the aminonaphthols and aminophenols to the corresponding benzoylated derivatives. The definite role of atmospheric oxygen to assist the reaction was proved by performing the reaction in the argon atmosphere.
- Prasanna Kumari, Subramaniyan,Suresh, Pavithira,Muthukumar, Vijayashree,Selva Ganesan, Subramaniapillai
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supporting information
(2020/10/13)
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- Asymmetric Transfer Hydrogenation of o-Hydroxyphenyl Ketones: Utilizing Directing Effects That Optimize the Asymmetric Synthesis of Challenging Alcohols
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A systematic range of o-hydroxyphenyl ketones were reduced under asymmetric transfer hydrogenation conditions using the C3-tethered catalyst 2. Two directing effects, i.e., an o-hydroxyphenyl coupled to a bulky aromatic on the opposite side of the ketone substrate, combine in a matched manner to deliver reduction products with very high enantiomeric excess.
- Clarkson, Guy J.,Wills, Martin,Zheng, Ye
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supporting information
(2020/05/05)
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- Efficient visible-light photocatalytic aerobic oxidation of cyclic sulfamides to imines
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A highly efficient photocatalytic aerobic oxidation of cyclic sulfamides to synthesize cyclic N-sulfonyl imines with Ir(ppy)2(dtbpy)PF6 as photocatalyst is reported. These environmentally friendly transformations exihibit good to excellent isolated yields and good generality with respect to both five-membered and six-membered cyclic sulfamides.
- Ming, Zong-Yao,Li, Kang-Rui,Meng, Fan-Jie,Shi, Lei,Jiang, Wen-Feng
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supporting information
(2020/06/17)
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- Ruthenium-Catalyzed Direct Asymmetric Reductive Amination of Diaryl and Sterically Hindered Ketones with Ammonium Salts and H2
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A Ru-catalyzed direct asymmetric reductive amination of ortho-OH-substituted diaryl and sterically hindered ketones with ammonium salts is reported. This method represents a straightforward route toward the synthesis of synthetically useful chiral primary diarylmethylamines and sterically hindered benzylamines (up to 97 % yield, 93–>99 % ee). Elaborations of the chiral amine products into bioactive compounds and a chiral ligand were demonstrated through manipulation of the removable and convertible -OH group.
- Hu, Le' an,Zhang, Yao,Zhang, Qing-Wen,Yin, Qin,Zhang, Xumu
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p. 5321 - 5325
(2020/02/28)
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- Deoxygenative Arylation of Carboxylic Acids by Aryl Migration
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An unprecedented deoxygenative arylation of aromatic carboxylic acids has been achieved, allowing the construction of an enhanced library of unsymmetrical diaryl ketones. The synergistic photoredox catalysis and phosphoranyl radical chemistry allows for precise cleavage of a stronger C?O bond and formation of a weaker C?C bond by 1,5-aryl migration under mild reaction conditions. This new protocol is independent of substrate redox-potential, electronic, and substituent effects. It affords a general and promising access to 60 examples of synthetically versatile o-amino and o-hydroxy diaryl ketones under redox-neutral conditions. Furthermore, it also brings one concise route to the total synthesis of quinolone alkaloid, (±)-yaequinolone A2, and a viridicatin derivative in satisfying yields.
- Ruzi, Rehanguli,Ma, Junyang,Yuan, Xiang-Ai,Wang, Wenliang,Wang, Shanshan,Zhang, Muliang,Dai, Jie,Xie, Jin,Zhu, Chengjian
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p. 12724 - 12729
(2019/11/05)
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- Efficient catalytic synthesis method of 2-hydroxybenzophenone compound
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The invention discloses a 2-hydroxybenzophenone compound and a green catalytic synthesis method thereof. According to the method, under the conditions of using coumaranone and coumaranone derivativesas raw materials, using nickel chloride as a catalyst, using methylbenzene as a solvent, using di-tert-butyl peroxide as an oxidizing agent, and using sodium carbonate as alkali, the 2-hydroxybenzophenone compound is obtained at high yield. The method has the advantages that the cost is low; the yield is high; the operation is simple and convenient; no pollution is caused and the like. The potential industrial application prospects are realized. The method provides a cheap and green path for the preparation of the 2-hydroxybenzophenone compound.
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Paragraph 0035; 0036
(2019/04/11)
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- Rhodium-Catalyzed Directing-Group-Assisted Aldehydic C–H Arylations with Aryl Halides
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A rhodium-catalyzed general protocol for the directing-group-assisted arylation of aromatic aldehydic C–H bonds was developed. This method involves either hydroxy- or amino-group-directed aldehyde C–H arylation with various aryl halides. A broad synthetic scope for the preparation of 2-hydroxybenzophenones was established with electronically variant salicylaldehydes and aryl halides with chemo- and regioselective possibilities. The developed protocol was also applied in the synthesis of medicinally important 3-salicyloylpyridines in high yields.
- Rao, Maddali L. N.,Ramakrishna, Boddu S.
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p. 5080 - 5093
(2017/09/20)
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- Acylation of Csp2-H bond with acyl sources derived from alkynes: Rh-Cu bimetallic catalyzed CC bond cleavage
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A Rh-Cu bimetallic catalyzed o-acylation of acyloxacetamide with alkynes has been described. This transformation provides a novel, concise way to synthesize ortho-acylphenols using functionalized alkynes as acylating reagents. Mechanistic studies revealed a Rh-Cu relay process, in which O2 plays a critical role for the formation of carbonyl compounds.
- Xie, Ying
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p. 12372 - 12375
(2016/10/22)
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- Iridium- and rhodium-catalyzed C-H activation and formyl arylation of benzaldehydes under chelation-assistance
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Mild and efficient synthesis of benzophenones via Ir(iii)- and Rh(iii)-catalyzed, directing group-assisted formyl C-H arylation of benzaldehydes has been achieved using diaryliodonium salts, in which Rh(iii) and Ir(iii) catalysts exhibited a complementary
- Yang, Xifa,Wang, He,Zhou, Xukai,Li, Xingwei
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supporting information
p. 5233 - 5237
(2016/07/06)
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- Rh(III)-catalyzed aldehyde C-H bond functionalization of salicylaldehydes with arylboronic acids
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A Rh(III)-catalyzed aldehyde C-H bond functionalization of salicylaldehydes with arylboronic acids has been developed, with features of mild reaction condition and high efficiency. Furthermore, the functionalized 2-hydroxybenzophenone could be subject to divergent synthesis of heterocycles.
- Wang, Dahai,Cui, Sunliang
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p. 8511 - 8516
(2016/01/25)
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- Palladium-catalyzed synthesis of benzofurans via C-H activation/oxidation tandem reaction and its application to the synthesis of decursivine and serotobenine
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A new palladium-catalyzed method for the synthesis of benzofurans by reaction of 2-hydroxystyrenes and iodobenzenes via a C-H activation/oxidation tandem reaction has been unprecedentedly discovered. By using this strategy, the overall synthetic efficienc
- Guo, Lei,Zhang, Fengying,Hu, Weimin,Li, Lei,Jia, Yanxing
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supporting information
p. 3299 - 3302
(2014/03/21)
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- Broadening the catalyst and reaction scope of regio- and chemoselective C-H oxygenation: A convenient and scalable approach to 2-acylphenols by intriguing Rh(ii) and Ru(ii) catalysis
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A unique Rh(ii) and Ru(ii) catalyzed C-H oxygenation of aryl ketones and other arenes has been developed for the facile synthesis of diverse functionalized phenols. The reaction demonstrates excellent reactivity, regio- and chemoselectivity, good functional group compatibility and high yields. The practicality of this method has been proved by gram-scale synthesis of a few different 2-acylphenols. Its utility has been well exemplified in further applications in heterocycle synthesis and direct modifications of drug Fenofibrate.
- Shan, Gang,Han, Xuesong,Lin, Yun,Yu, Shanyou,Rao, Yu
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supporting information
p. 2318 - 2322
(2013/04/10)
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- Pd-catalyzed sp2 C-H hydroxylation with TFA/TFAA via weak coordinations
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An efficient sp2 C-H hydroxylation has been developed for the synthesis of a wide range of functionalized phenols with aryl ketones, benzoates, benzamides, acetanilides and sulfonamides through palladium(II) catalysis. A trifluoroacetic acid (TFA)/trifluoroacetic anhydride (TFAA) co-solvent system serves as the oxygen source and is the critical factor for weak coordination promoted C-H activation. Georg Thieme Verlag Stuttgart New York.
- Rao, Yu
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p. 2472 - 2476
(2013/12/04)
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- Palladium-catalyzed ortho-CH-bond oxygenation of aromatic ketones
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A palladium-catalyzed C(sp2)-H bond oxygenation reaction is described. This protocol represents the first example of a C-H bond cleavage/C-O bond formation sequence, by employing a ketone moiety as the directing group. With this new catalytic method, a variety of ortho-acylphenols can be easily accessed from arylketones.
- Choy, Pui Ying,Kwong, Fuk Yee
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supporting information
p. 270 - 273
(2013/03/13)
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- Synthesis of ortho-hydroxybenzophenones catalyzed by magnetically retrievable Fe3O4 nanoparticles under ligand-free conditions
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ortho-Benzoylation of phenols with aryl aldehydes to afford the substituted 2-hydroxybenzophenones can be catalyzed efficiently by Fe3O 4 nanoparticles under ligand-free conditions. This method is useful for the preparation of xanthones in good yields. The catalyst can be magnetically removed and recycled easily over four cycles without a significant decrease in activity. The applicability of magnetically retrievable Fe 3O4 nanoparticles in the oxidative coupling of aryl aldehydes with phenols under ligand free conditions is demonstrated.
- Ramani, Thekkathu,Umadevi, Paspulati,Prasanth, K. Leon,Sreedhar, Bojja
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supporting information
p. 6021 - 6026
(2013/09/24)
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- Pd-catalyzed C-H oxygenation with TFA/TFAA: Expedient access to oxygen-containing heterocycles and late-stage drug modification
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Functionalized phenols are valuable industrial chemicals related to pharmaceuticals, agrochemicals, and polymers. Therefore, the direct catalytic hydroxylation of arenes to produce phenols has attracted much attention. Although tremendous progress has been made in this field, there are still difficult substrates which remain unmet challenges for direct hydroxylation in terms of regio- and chemoselectivity, as well as the practicality of current methods (Scheme 1). For example, 2-hydroxy aromatic ketones are useful synthetic intermediates for the preparation of various oxygen-containing heterocycles such as benzofuranone, chromanone, benzoxazole, and dibenzooxazepine; they also serve as key building blocks for drugs such as celiprolol, acebutolol, and propafenone. Traditional strategies for accessing 2-hydroxy aromatic ketones have mainly involved the oxidation of benzylic alcohols, the hydrolysis of aromatic halides, Fries rearrangement of esters or the demethylation of methyl phenyl ether. These methods generally suffer from one limitation or another, such as tedious reaction procedures, harsh reaction conditions, low yields, or the formation of side products. Hence, direct transformation of readily available aromatic ketones into valuable 2-hydroxylated products by transition metal-catalyzed C-H functionalization is arguably a highly efficient and atom-economic method to access these compounds. Moreover, developing a more general strategy for the regio- and chemoselective C-H oxygenation of a variety of challenging arenes would be especially desirable for phenol synthesis (Scheme 1).
- Shan, Gang,Yang, Xinglin,Ma, Linlin,Rao, Yu
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supporting information
p. 13070 - 13074
(2013/02/26)
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- Benzofurans from benzophenones and dimethylacetamide: Copper-promoted cascade formation of furan O1-C2 and C2-C3 bonds under oxidative conditions
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DMA donates: Copper(II) acetate and 8-hydroxyquinoline promote the formation of a benzofuran core through a cascade of copper-catalyzed processes wherein the key carbon atom comes from the dimethylacetamide (DMA) solvent. Strong evidence for the participation of a Wacker cyclization catalyzed solely by copper is provided, not only in the title reaction from benzophenones but also from 2-hydroxy-α-arylstyrene derivatives. Copyright
- Moure, Maria J.,Sanmartin, Raul,Dominguez, Esther
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supporting information; experimental part
p. 3220 - 3224
(2012/05/05)
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- Rearrangement of 2-aryloxybenzaldehydes to 2-hydroxybenzophenones by rhodium-catalyzed cleavage of aryloxy C-O bonds
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Lost in the shuffle: An unprecedented rearrangement of the title compounds proceeds by the simultaneous rhodium-catalyzed cleavage of aryloxy C-O and aldehyde C-H bonds (see scheme). The reaction tolerates the presence of various catalytically reactive substituents such as aryl halides, nitrile, and esters.
- Rao, Honghua,Li, Chao-Jun
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supporting information; experimental part
p. 8936 - 8939
(2011/11/07)
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- Direct C-H bond arylation of 2-hydroxybenzaldehydes with arylboronic acids via ligand-free palladium catalysis
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A mild and efficient ligand-free palladium-catalyzed direct C-H bond arylation reaction was developed to afford 2-hydroxybenzophenones in good to excellent yields from easily available 2-hydroxybenzaldehydes and arylboronic acids. The given reaction provided one of the easiest pathways for accessing 2-hydroxybenzophenones, and a variety of functional groups could be tolerated in this process.
- Weng, Fei,Wang, Chengming,Xu, Bin
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supporting information; experimental part
p. 2593 - 2596
(2010/07/04)
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- Hypervalent iodine in synthesis XXXIV: Palladium-catalyzed coupling reaction of o-hydroxyarylaldehydes with hypervalent iodonium salts via cleavage of the aldehyde C-H bond
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A novel way of preparation for o-hydroxyarylketones with mild conditions and good yields by palladium-catalyzed coupling reaction of o- hydroxyarylaldehydes with hypervalent iodonium salts via the cleavage of the aldehyde C-H bond has been reported.
- Xia, Min,Chen, ZhenChu
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p. 531 - 536
(2007/10/03)
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- Palladium-catalyzed coupling reaction of salicylaldehydes with aryl iodides via cleavage of the aldehyde C-H bond
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It has been found that the cross-coupling reaction of salicylaldehydes with aryl iodides smoothly proceeds by using a catalyst system of PdCl2/LiCl in the presence of Na2CO3 as base to give the corresponding 2-aroylphenols in good yields, which appears to involve cleavage of the aldehyde C-H bond.
- Satoh, Tetsuya,Itaya, Tomoaki,Miura, Masahiro,Nomura, Masakatsu
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p. 823 - 824
(2007/10/03)
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- Antianaphylactic Benzophenones and Related Compounds
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The synthesis and biological properties of 85 benzophenones and related compounds are described.The majority of the compounds inhibit the release of leukotrienes (LT) C4 and D4 in vitro from sensitized guinea pig chopped lung.In addition, some of the compounds inhibited the release of LTs from passively sensitized human chopped lung and protected guinea pigs from the effects of anaphylaxis in a modified Herxheimer test.
- Evans, Delme,Cracknell, Mark E.,Saunders, John C.,Smith, Christine E.,Williamson, W. R. Nigel,et al.
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p. 1321 - 1327
(2007/10/02)
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- Method of treating inflammation
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A method of treating inflammation and inhibiting prostaglandin synthesis employing 2-hydroxybenzophenone and substituted 2-hydroxybenzophenones.
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