- 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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supporting information
p. 6594 - 6598
(2021/09/02)
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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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- Structural studies of a novel bioactive benzophenone derivative: (4-Chloro-2-hydroxy-phenyl)-phenyl-methanone
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The title compound (4-Chloro-2-hydroxy-phenyl)-phenyl-methanone was synthesized and the product obtained was characterized by spectroscopic techniques, and finally the structure was confirmed by X-ray diffraction studies. The compound crystallizes in the orthorhombic crystal system with the space group Pbca with unit cell parameters, a = 14.0359(5) ?, b = 6.8084(3) ?, c = 23.1097(8) ?, and Z = 4. The structure exhibits an intramolecular hydrogen bond which closes an S(6) ring. No directional interactions beyond the van der Waals packing contacts were identified in the crystal structure.
- Zabiulla,Naveen,Begum, A. Bushra,Khanum, Shaukath Ara,Lokanath
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p. 233 - 237
(2016/03/05)
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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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- Chlorinated coumarins from the polypore mushroom fomitopsis officinalis and their activity against mycobacterium tuberculosis
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An EtOH extract of the polypore mushroom Fomitopsis officinalis afforded two new naturally occurring chlorinated coumarins, which were identified as the previously synthesized compounds 6-chloro-4-phenyl-2H-chromen-2-one (1) and ethyl 6-chloro-2-oxo-4-phe
- Hwang, Chang Hwa,Jaki, Birgit U.,Klein, Larry L.,Lankin, David C.,McAlpine, James B.,Napolitano, Jose G.,Fryling, Nicole A.,Franzblau, Scott G.,Cho, Sang Hyun,Stamets, Paul E.,Wang, Yuehong,Pauli, Guido F.
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p. 1916 - 1922
(2013/11/19)
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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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- The synthesis and electronic absorption spectra of 3-phenyl-3(4- pyrrolidino-2-substituted phenyl)-3H-naphtho[2,1-b]pyrans: Further exploration of the ortho substituent effect
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Introduction of a substituent into a sterically demanding 2-position of a 3-(4-pyrrolidinophenyl) ring of a 3,3-diaryl-3H-naphtho[2,1-b]pyran results in the generation of an additional short wavelength absorption band leading to organic photochromes that
- Gabbutt, Christopher D.,Heron, B. Mark,Instone, Alicia C.
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p. 737 - 745
(2007/10/03)
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- 2-AROYLBENZOIC ACIDS-VIII. THE SYNTHESIS AND SOME REACTIONS OF 2-AROYLBENZOIC ACIDS FROM m-CHLOROPHENOL
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The syntheses of the novel 2-(4'-chloro-2'-hydroxybenzoyl) benzoic acid 1 and 2-(2'-chloro-4'-hydroxybenzoyl) benzoic acid 2 are described and some of their reactions are given.
- Gronowska, Janina,Mokhtar, Hassan M.
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p. 1657 - 1660
(2007/10/02)
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- The Fries Rearrangement as an Equilibrium Reaction
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The Fries rearrangement of arylbenzoates 1, in 1,2-dichloroethane in the presence of trifluoromethanesulfonic acid (TFMS) as catalyst, to ortho- and para-hydroxyaryl ketones (2 and 3, resp.) is reversible at 170 deg C; an equilibrium of the compounds 1, 2, and 3 is established.The equilibrium is achieved starting from the aryl esters 1 as well as from the hydroxyaryl ketones 2 and 3, respectively.The higher stability of the ortho-compounds 2 compared to the para-compounds 3 can be explained by greater resonance interaction between the carbonyl group and the aromatic ring in 2.The torsion angles Θ, which are good indicators of this interaction, can be determined from 13C NMR spectra.A dissociative mechanism is proposed for the acryl group migration.
- Effenberger, Franz,Gutmann, Rainer
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p. 1089 - 1102
(2007/10/02)
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