- 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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- A general approach to C-Acyl glycosides via palladium/copper Co-catalyzed coupling reaction of glycosyl carbothioates and arylboronic acids
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A general and efficient approach to the synthesis of various C-acyl glycosides has been developed via Pd2(dba)3/CuTC co-catalyzed cross-coupling reaction of glycosyl carbothioates with arylboronic acids. The reaction showed a broad s
- Wang, Li-Na,Niu, You-Hong,Cai, Qing-Hui,Li, Qin,Ye, Xin-Shan
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supporting information
(2021/02/03)
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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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- 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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- 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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- Synthesis of Spirobicyclic Pyrazoles by Intramolecular Dipolar Cycloadditions/[1s, 5s] Sigmatropic Rearrangements
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The formation of fused pyrazoles via intramolecular 1,3-dipolar cycloadditions of diazo intermediates with pendant alkynes is described. A subsequent thermal [1s, 5s] sigmatropic shift of these pyrazole systems resulted in a ring contraction, forming spirocyclic pyrazoles. The limitations of this rearrangement were explored by changing the substituents on the nonmigrating aromatic ring and by using substrates lacking an aromatic linkage to the propargyl group.
- Dimirjian, Christine A.,Casti?eira Reis, Marta,Balmond, Edward I.,Turman, Nolan C.,Rodriguez, Elys P.,Di Maso, Michael J.,Fettinger, James C.,Tantillo, Dean J.,Shaw, Jared T.
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p. 7209 - 7212
(2019/10/02)
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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 0031; 0032
(2019/04/11)
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- Integrating Metal-Catalyzed C-H and C-O Functionalization to Achieve Sterically Controlled Regioselectivity in Arene Acylation
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One major goal of organometallic chemists is the direct functionalization of the bonds most recurrent in organic molecules: C-H, C-C, C-O, and C-N. An even grander challenge is C-C bond formation when both precursors are of this category. Parallel to this is the synthetic goal of achieving reaction selectivity that contrasts with conventional methods. Electrophilic aromatic substitution (EAS) via Friedel-Crafts acylation is the most renowned method for the synthesis of aryl ketones, a common structural motif of many pharmaceuticals, agrochemicals, fragrances, dyes, and other commodity chemicals. However, an EAS synthetic strategy is only effective if the desired site for acylation is in accordance with the electronic-controlled regioselectivity of the reaction. Herein we report steric-controlled regioselective arene acylation with salicylate esters via iridium catalysis to access distinctly substituted benzophenones. Experimental and computational data indicate a unique reaction mechanism that integrates C-O activation and C-H activation with a single iridium catalyst without an exogenous oxidant or base. We disclose an extensive exploration of the synthetic scope of both the arene and the ester components, culminating in the concise synthesis of the potent anticancer agent hydroxyphenstatin.
- Serratore, Nicholas A.,Anderson, Constance B.,Frost, Grant B.,Hoang, Truong-Giang,Underwood, Steven J.,Gemmel, Philipp M.,Hardy, Melissa A.,Douglas, Christopher J.
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supporting information
p. 10025 - 10033
(2018/07/21)
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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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- An efficient and practical preparation of a potent low-affinity na+-dependent glucose cotransporter (SGLT2) inhibitor, sergliflozin etabonate
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The development of an efficient and practical process for the preparation of Sergliflozin etabonate (1), a prodrug of a novel selective low-affinity Na+-dependent glucose cotransporter (SGLT2) inhibitor, Sergliflozin (2), is described. Its development required a suitable process for large-scale manufacturing. We established a chromatography-free approach for 2-[(4-methoxyphenyl)methyl]phenol (5), the efficient O-glycosylation of 5 with penta-O-acetyl-β-D-glucopyranose (7) without using a trichloroacetimidate intermediate (9), and efficient reaction conditions to introduce an ethoxycarbonyl group onto the primary alcohol of 2 with high selectivity. This process provided 1 with a 45% overall yield from anisole (10).
- Kobayashi, Masahiro,Isawa, Hidetoshi,Sonehara, Junichi,Kubota, Minoru
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p. 1599 - 1613
(2016/10/12)
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- A Domino Oxidation/Arylation/Protodecarboxylation Reaction of Salicylaldehydes: Expanded Access to meta-Arylphenols
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A method that allows salicylaldehydes to be efficiently transformed into meta-arylated phenol derivatives through a cascade oxidation/arylation/protodecarboxylation sequence is presented. We demonstrate that the aldehyde functional group can be used as a convenient removable directing group to control site selectivity in C-H activation. Aldehydes are easily introduced into the starting materials and the group is readily cleaved after the C-H functionalization event.
- Luo, Junfei,Preciado, Sara,Araromi, Solomon Olatokunbo,Larrosa, Igor
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supporting information
p. 347 - 350
(2016/05/19)
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- First direct access to 2-hydroxybenzophenones via nickel-catalyzed cross-coupling of 2-hydroxybenzaldehydes with aryl iodides
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An efficient, inexpensive and reusable NiCl2·6H2O/n-Bu4NBr catalytic system is described for the direct C-H arylation of 2-hydroxybenzaldehydes with aryl iodides for the first time.
- Nowrouzi,Zarei,Roozbin
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p. 102448 - 102453
(2015/12/11)
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- Palladium-catalyzed direct ortho aroylation of 2-phenoxypyridines with aldehydes and catalytic mechanism investigation
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A direct ortho aroylation of 2-phenoxypyridines with aldehydes leading to aryl ketones by the use of palladium(II) acetate, tert-butyl hydroperoxide, and chlorobenzene as the catalyst, oxidant, and solvent, respectively, is presented. Intra- and intermolecular kinetic isotope effects, radical trapping, and controlled experiments were carried out to support the proposed catalytic mechanism for the reaction. Syntheses of (2-hydroxyphenyl)(phenyl)methanones and 1-hydroxy-9H-fluoren-9-ones directed from ortho-aroylated 2-phenoxypyridines were demonstrated.
- Chu, Jean-Ho,Chen, Shih-Tien,Chiang, Meng-Fan,Wu, Ming-Jung
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p. 953 - 966
(2015/03/18)
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- Palladium catalyzed addition of arylboronic acid or indole to nitriles: Synthesis of aryl ketones
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Aryl ketones can be synthesized conveniently by a palladium catalyzed addition of arylboronic acid to nitriles in aqueous triflic acid. This catalytic system was extended to the addition of unprotected indoles to nitriles under a slightly modified condition to produce 3-acyl indoles in good yields.
- Das, Tuluma,Chakraborty, Amarnath,Sarkar, Amitabha
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supporting information
p. 7198 - 7202
(2015/01/09)
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- Cytotoxicity and DNA binding property of triphenylethylene-coumarin hybrids with two amino side chains
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Novel triphenylethylene-coumarin hybrids containing two amino side chains were designed and synthesized. Some of these 3,4-diphenyl coumarins, 7b-c (the double chains at 4-position on 3-,4-phenyl, respectively), and 13b-f (the double chains at 4-position on 3-phenyl and 7-position, respectively), showed a broad-spectrum and good anti-proliferative activity against five tumor cells and low cytotoxicity in osteoblast. UV-vis, fluorescence, and circular dichroism (CD) spectroscopies and thermal denaturation exhibited that compounds 7b (R = piperidinyl), 7e (R = NEt2), and 7f (R = 4-methylpiperazinyl) had significant interactions with Ct-DNA by the intercalative mode of binding. Structure activity relationships (SARs) analysis suggested that the location of the two amino alkyl chains would play an important role both in the compounds against tumor cells proliferation and their interactions with DNA.
- Zhao, Lian,Yao, Yuchao,Li, Shuai,Lv, Mengjiao,Chen, Hua,Li, Xiaoliu
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p. 900 - 904
(2014/02/14)
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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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- FAMILY OF ARYL, HETEROARYL, O-ARYL AND O-HETEROARYL CARBASUGARS
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The present invention relates to a compound of the following formula (I): as well as its process of preparation, pharmaceutical and cosmetics composition comprising it and use thereof, notably as an inhibitor of the sodium-dependent glucose co-transporter, such as SGLTl, SGLT2 and SGLT3, in particular in the treatment or prevention of diabetes, and more particularly type-II diabetes, diabetes-related complications, such as arthritis of the lower extremities, cardiac infarction, renal insufficiency, neuropathy or blindness, hyperglycemia, hyperinsulinemia, obesity, hypertriglyceridemia, X syndrome and arteriosclerosis, as well as for its use as an anticancer, anti-infective, anti-viral, anti-thrombotic or anti- inflammatory drug, or for lightening, bleaching, depigmenting the skin, removing blemishes from the skin, particularly age spots and freckles, or preventing pigmentation of the skin.
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- An improved synthesis of hydroxy aryl ketones by fries rearrangement with methanesulfonic acid/methanesulfonic anhydride
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Methanesulfonic acid treated with methanesulfonic anhydride effectively mediates the Fries rearrangement of aryl esters to give hydroxy aryl ketones with high yields. Georg Thieme Verlag Stuttgart · New York.
- Jeon, Ingyu,Mangion, Ian K.
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experimental part
p. 1927 - 1930
(2012/10/08)
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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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- Rh(1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) (COD) tetrafluoroborate, an unsymmetrical Rh-homoazallylcarbene: Synthesis, X-ray structure and reactivity in carbonyl arylation and hydrosilylation reactions
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The synthesis of novel Rh(1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6- tetrahydropyrimidin-2-ylidene)(COD) tetrafluoroborate (1, COD = η4-1,5-cyclooctadiene) is described. The N-heterocyclic carbene acts as a bidentate ligand with the carbene coordinating to the Rh(I) center and an arene group acting as a homoazallyl ligand. 1 was used in various carbonyl arylation and hydrosilylation reactions allowing the formation of the desired products with unprecedented selectivity and efficiency. Thus, turn-over numbers (TONs) up to 2000 were achieved.
- Imlinger, Nicolas,Wurst, Klaus,Buchmeiser, Michael R.
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p. 4433 - 4440
(2007/10/03)
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- Solvent-free catalytic Friedel - Crafts acylation of aromatic compounds with carboxylic acids by using a novel heterogeneous catalyst system: p-Toluenesulfonic acid/graphite
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TsOH/graphite was found to be an effective catalyst system for the Friedel-Crafts acylation of aromatic compounds with carboxylic acids. Both aliphatic and aromatic carboxylic acids reacted smoothly under TsOH/graphite catalysis to afford the corresponding aromatic ketones in high yields. The graphite was easily recovered by simple extraction and could be reused without decrease of activity in the presence of fresh TsOH.
- Sarvari, Mona Hosseini,Sharghi, Hashem
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p. 2282 - 2287
(2007/10/03)
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- Arylation of carbonyl compounds catalyzed by rhodium and iridium 1,3-R 2-tetrahydropyrimidin-2-ylidenes: Structure-reactivity correlations
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Six different well-defined rhodium and iridium N-heterocyclic carbene complexes, i.e., RhCl-(1,3-dimesityltetrahydropyrimidin-2-ylidene)(COD) (1), RhBr(1,3-dimesityltetrahydropyrimidin-2-ylidene)-(COD) (2), RhCl[1,3-di(2- propyl)tetrahydropyrimidin-2-ylidene](COD) (3), IrCl(1,3- dimesityltetrahydropyrimidin-2-ylidene)(COD) (4), Rh(CF3COO) (1,3-dimesityltetrahydropyrimidin-2-ylidene)(COD) (5), and IrBr[1,3-di(2-propyl) tetrahydropyrimidin-2-ylidene](COD) (6) (COD = 1,5-cyclooctadiene, mesityl = 2,4,6-trimethylphenyl) have been used as catalysts for the arylation of aldehydes and α,β-unsaturated ketones using different arylboronic acids. Compounds 1-4 and 6 were prepared by reaction of [RhCl(COD)]2 and [IrCl(COD)]2, respectively, with a base and the corresponding 1,3-R2-tetrahydropyrimidinium salt. Compound 5 was prepared by reaction of 1.0 equivalents of CF3COOAg with 1. The use of an excess of CF3COOAg resulted in the replacement of Rh(I) by Ag(I) and yielded Ag(1,3-dimesityltetrahydropyrimidin-2-ylidene)+Rh 2(CF3COO)3(COD)- (8). Compounds 4 and 8 were characterized by X-ray analysis. The activity of the rhodium complexes increased in the order 5 > 3 > 1 > 2, indicating the necessity of strongly electron-withdrawing groups at the metal centers, thus increasing their nucleophilicity. In due consequence, the softer iridium complexes 4 and 6 exhibited significantly reduced catalytic activity albeit with enhanced selectivity. The syntheses of the metal complexes as well as a detailed study on their reactivity in the arylation of carbonyl compounds using equimolar amounts of arylboronic acid and carbonyl compound in the presence of 0.08-1 mol % catalyst are presented.
- Imlinger, Nicolas,Mayr, Monika,Wang, Dongren,Wurst, Klaus,Buchmeiser, Michael R.
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p. 1836 - 1843
(2007/10/03)
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- Simple and improved procedure for the regioselective acylation of aromatic ethers with carboxylic acids on the surface of graphite in the presence of methanesulfonic acid
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Friedel-Crafts acylation of aromatic compounds such as anisole has been successfully carried out using the combination of graphite with MeSO 3H. Both aromatic and aliphatic carboxylic acids reacted smoothly under the conditions to afford the corresponding aromatic ketones in high yield.
- Sarvari, Mona Hosseini,Sharghi, Hashem
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p. 2165 - 2168
(2007/10/03)
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- A concise approach to the preparation of 2-hydroxydiarylketones by an intramolecular acyl radical ipso substitution
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Substituted 2-hydroxydiarylketones have been simply prepared using an intramolecular acyl radical [1,6] ipso substitution reaction. (C) 2000 Elsevier Science Ltd.
- Motherwell,Vazquez
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p. 9667 - 9671
(2007/10/03)
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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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- Hypervalent iodine in synthesis 59: Application of polymeric diaryliodonium salts as aryl transfer reagents in SPOS
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Polymeric diaryliodonium salts were employed as aryl transfer reagents in the Pd(II) catalyzed cross-coupling reaction with salicylaldehydes, and could be regenerated and recycled for the same reactions.
- Chen,Chen
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p. 1175 - 1177
(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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- A Complex Induced Proximity Effect in the Anionic Fries Rearrangement of o-Iodophenyl Benzoates: Synthesis of Dihydro-O-methylsterigmatocystin and Other Xanthones
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The success of an anionic Fries rearrangement, used to synthesise dihydro-O-methylsterigmatocystin and other xanthones, is dependent on the presence of a remote methoxyl substituent.
- Horne, Stephen,Rodrigo, Russell
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p. 4520 - 4522
(2007/10/02)
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