- AIBN initiated functionalization of the benzylic sp3 C[sbnd]H and C[sbnd]C bonds in the presence of dioxygen
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A sp3 C[sbnd]H bond functionalization and C[sbnd]C bond cleavage were realized by AIBN/O2 catalyst system, providing a series of benzophenones under mild reaction conditions. The mechanistic study shows that a peroxide intermediate is involved in this transformation, and in the case of diphenylmethanes, the sp3 C[sbnd]C bond is cleaved through the peroxide rearrangement, which might provides a new way to cleave relatively strong C[sbnd]C bond and be applied to more general C[sbnd]C bond activation.
- Hu, Yingying,Shao, Yu,Zhang, Shuwei,Yuan, Yuan,Sun, Zheng,Yuan, Yu,Jia, Xiaodong
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supporting information
(2021/02/01)
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- Palladium-Catalyzed Amide N-C Hiyama Cross-Coupling: Synthesis of Ketones
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N-Acylglutarimides and arylsiloxanes reacted in the presence of Pd(OAc)2/PCy3, Et3N·3HF, and LiOAc to provide the corresponding arylketones in good yields. Aryl-, vinyl-, and alkyl-substituted N-acylglutarimides showed good activity in the coupling reactions of arylsiloxanes. The reaction had a broad substrate scope and showed good functional group tolerance. N-Benzoylsuccinimide and N-protected N-phenylbenzamides showed good activities in coupling reactions with phenylsiloxane. The employment of CuF2 as an activor afforded the decarbonylative products at 160 °C.
- Idris, Muhammad Aliyu,Lee, Sunwoo
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supporting information
p. 9190 - 9195
(2020/11/18)
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- Photo-nickel dual catalytic benzoylation of aryl bromides
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The dual catalytic arylation of aromatic aldehydes by aryl bromides using UV-irradiation and a nickel catalyst is reported. The reaction product serves as a photocatalyst and a hydrogen atom transfer agent for this transformation.
- Schirmer, Tobias Emanuel,Wimmer, Alexander,Weinzierl, Florian Wolfgang Clemens,K?nig, Burkhard
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supporting information
p. 10796 - 10799
(2019/09/13)
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- A Dendralenic C-H Acid
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The design and synthesis of a strong, dendralenic C-H acid is described. Crystal structure analyses confirm the proposed structure. Despite the moderate stability of our motif, an application to Bronsted acid catalysis has been explored.
- H?fler, Denis,Goddard, Richard,N?thling, Nils,List, Benjamin
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supporting information
p. 433 - 436
(2019/02/26)
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- Pd-Catalyzed Suzuki–Miyaura Cross-Coupling of Arylboronic Acids and α-Iminonitriles through C–CN Bond Activation
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A Pd-catalyzed Suzuki–Miyaura cross-coupling reaction between arylboronic acids and α-iminonitriles has been developed. The reaction proceeds through selective activation of the C–CN bond, tolerates a wide range of substituents, and delivers the versatile ketone products in moderate to excellent yields.
- Liu, Kui,Tao, Shou-Wei,Qian, Chun,Zhu, Yong-Ming
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supporting information
p. 4769 - 4775
(2018/09/06)
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- A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation
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The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.
- Kinney, R. Garrison,Tjutrins, Jevgenijs,Torres, Gerardo M.,Liu, Nina Jiabao,Kulkarni, Omkar,Arndtsen, Bruce A.
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p. 193 - 199
(2018/02/06)
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- Transition metal-free Suzuki type cross-coupling reaction for the synthesis of dissymmetric ketones
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A simple, efficient and metal-free route for the synthesis of dissymmetric ketones through Suzuki type cross-coupling reaction has been established. This strategy signifies an attractive, cost-effective and operationally convenient tool for the synthesis of a wide range of dissymmetric ketones. Although conventional routes for the synthesis of ketones have been widely used, the potential challenge with these methods is functional group tolerance. The reported metal-free method represents a reaction with moderate functional group tolerance. The procedure is operationally convenient and shows broad substrate scope with good to excellent product yields.
- Jadhav, Sanjay,Rashinkar, Gajanan,Salunkhe, Rajashri,Kumbhar, Arjun
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supporting information
p. 3201 - 3204
(2017/07/27)
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- A Zwitterionic Palladium(II) Complex as a Precatalyst for Neat-Water-Mediated Cross-Coupling Reactions of Heteroaryl, Benzyl, and Aryl Acid Chlorides with Organoboron Reagents
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The Suzuki–Miyaura cross-coupling (SMC) reactions of several heteroaryl chlorides, benzyl chlorides, and aryl acid chlorides with (hetero)arylboron reagents have been investigated in the presence of [Pd(HL1)(PPh3)Cl2] (I) [HL1 = 3-[(2,6-diisopropylphenyl)-1-imidazolio]-2-quinoxalinide] as catalyst and K2CO3 as base in neat water. The synthesis of the heterocycle-containing biaryls required the addition of 2 mol-% of a phosphine ligand (PPh3 or X-Phos). A combination of more than 115 substrates were screened and it was found that I is a versatile catalyst that can produce heterocycle-containing biaryls, diarylmethanes, and benzophenones in moderate-to-excellent yields.
- Ramakrishna, Visannagari,Rani, Morla Jhansi,Reddy, Nareddula Dastagiri
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p. 7238 - 7255
(2018/01/01)
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- 1,1,3,3-Tetratriflylpropene (TTP): A Strong, Allylic C–H Acid for Br?nsted and Lewis Acid Catalysis
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Tetratrifylpropene (TTP) has been developed as a highly acidic, allylic C–H acid for Br?nsted and Lewis acid catalysis. It can readily be obtained in two steps and consistently shows exceptional catalytic activities for Mukaiyama aldol, Hosomi–Sakurai, an
- H?fler, Denis,van Gemmeren, Manuel,Wedemann, Petra,Kaupmees, Karl,Leito, Ivo,Leutzsch, Markus,Lingnau, Julia B.,List, Benjamin
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supporting information
p. 1411 - 1415
(2017/01/24)
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- Synthesis of a polar phosphinoferrocene amidosulfonate ligand and its application in pd-catalyzed cross-coupling reactions of aromatic boronic acids and acyl chlorides in an aqueous medium
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The reaction of [1′-(diphenylphosphino)ferrocenyl]methylamine (1), generated in situ from its hydrochloride and triethylamine, with 2-sulfobenzoic anhydride afforded an anionic phosphino-amide, which was isolated as a triethylammonium salt, Ph2PfcCH2NHCOC6H4SO3(HNEt3) (2; fc = ferrocene-1,1′-diyl). A similar reaction of 1 with phthalic anhydride only furnished the salt (Ph2PfcCH2NH3)[C6H4CO2H(CO2)]. When it was reacted with [PdCl2(MeCN)2] and [LNCPd(μ-Cl)]2 (LNC = 2-[(dimethylamino-κN)methyl]phenyl-κC1), compound 2 gave rise to the bis-phosphine complex [PdCl2(2-κP)2] and the bridge-cleavage product [LNCPdCl(2-κP)], respectively. An analogue of the latter complex containing 2′-amino-[1,1′-biphenyl]-2-yl-κ2N,C2 as the auxiliary chelating ligand, compound 8, was prepared in a similar manner from 2 and the respective Pd precursor. Finally, the reaction of 2 with [LNCPd(acac)] proceeded with the replacement of the acetylacetonate ligand (acac), affording a dipalladium complex featuring two phosphinosulfonate anions as the O,P-bridges, [LNCPd(μ(P,O)-Ph2PfcCH2NHCOC6H4SO3)]2, which was structurally characterized by single-crystal X-ray diffraction analysis. All of these Pd(II) complexes, especially compound 8, formed active catalysts for Pd-mediated cross-coupling of aromatic boronic acids with benzoyl chlorides to produce substituted benzophenones in toluene (benzene)-water biphasic mixtures. This particular coupling reaction was employed during the preparation of 4′-chloro-4-hydroxybenzophenone, which was in turn converted to fenofibrate, a generic drug widely used to reduce cholesterol levels in blood.
- ?koch, Karel,Císa?ová, Ivana,?těpni?ka, Petr
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p. 3378 - 3387
(2016/10/21)
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- Transition-metal-free, ambient-pressure carbonylative cross-coupling reactions of aryl halides with potassium aryltrifluoroborates
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We disclose an unprecedented transition-metal-free carbonylative cross coupling of aryl halides with potassium aryl trifluoroborates even at atmospheric pressure of carbon monoxide. This protocol is efficient, operationally simple, and shows wide scope with regard to both aryl halides and potassium aryl trifluoroborates containing a series of active functional groups.
- Jin, Fengli,Han, Wei
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supporting information
p. 9133 - 9136
(2015/06/08)
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- AIBN-catalyzed oxidative cleavage of gem -disubstituted alkenes with O 2 as an oxidant
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A 2,2-azobis(isobutyronitrile) (AIBN) catalyzed oxidative cleavage of gem-disubstituted alkenes with molecular oxygen as the oxidant has been described. Carbonyl compounds were obtained as the desired products in high yield under mild conditions. Based on previous documents and current experimental results, a relatively reasonable mechanism is proposed.
- Wang, Guang-Zu,Li, Xing-Long,Dai, Jian-Jun,Xu, Hua-Jian
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p. 7220 - 7225
(2014/08/18)
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- Reversed-polarity synthesis of diaryl ketones through palladium-catalyzed direct arylation of 2-Aryl-1,3-dithianes
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An umpolung approach to the synthesis of diaryl ketones has been developed based on in situ generation of acyl anion equivalents and their catalytic arylation. This method entails the base-promoted, palladium-catalyzed direct C-H arylation of 2- aryl-1,3-dithianes with aryl bromides. Use of ( SiMe3)2 (M=Li, Na) base results in reversible deprotonation of the weakly acidic dithiane. In the presence of a Pd(NiXantphos)-based catalyst and aryl bromide, cross-coupling of the metallated 2-aryl- 1,3-dithiane takes place under mild conditions (2 h at rt) with yields as high as 96%. The resulting 2,2- diaryl-1,3-dithianes were converted into diaryl ketones by either molecular iodine, N-bromo succinimide (NBS) or Selectfluor in the presence of water. The dithiane arylation/hydrolysis can be performed in a one-pot procedure to yield a variety of diaryl ketones in good to excellent yields. This method is suitable for rapid and large-scale synthesis of diaryl ketones. A one-pot preparation of anti-cholesterol drug fenofibrate (TriCor) has been achieved on 10.0 mmol scale in 86% yield.
- Yucel, Baris,Walsh, Patrick J.
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p. 3659 - 3667
(2015/01/09)
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- Reversed-polarity synthesis of Diaryl Ketones through palladium-catalyzed direct Arylation of 2-Aryl-1,3-dithianes
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An umpolung approach to the synthesis of diaryl ketones has been developed based on in situ generation of acyl anion equivalents and their catalytic arylation. This method entails the base-promoted, palladium-catalyzed direct C-H arylation of 2- aryl-1,3-dithianes with aryl bromides. Use of MNACHTUNGTRENUNG( SiMe3)2 (M=Li, Na) base results in reversible deprotonation of the weakly acidic dithiane. In the presence of a Pd(NiXantphos)-based catalyst and aryl bromide, cross-coupling of the metallated 2-aryl- 1,3-dithiane takes place under mild conditions (2 h at rt) with yields as high as 96%. The resulting 2,2- diaryl-1,3-dithianes were converted into diaryl ketones by either molecular iodine, N-bromo succinimide (NBS) or Selectfluor in the presence of water. The dithiane arylation/hydrolysis can be performed in a one-pot procedure to yield a variety of diaryl ketones in good to excellent yields. This method is suitable for rapid and large-scale synthesis of diaryl ketones. A one-pot preparation of anti-cholesterol drug fenofibrate (TriCor) has been achieved on 10.0 mmol scale in 86% yield.
- Yucel, Baris,Walsh, Patrick J.
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supporting information
p. 3659 - 3667
(2015/01/09)
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- Tetraethylammonium iodide catalyzed synthesis of diaryl ketones via the merger of cleavage of C-C double bonds and recombination of aromatic groups
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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.
- Zeng, Xianghua,Xu, Daqian,Miao, Chengxia,Xia, Chungu,Sun, Wei
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p. 46494 - 46497
(2014/12/10)
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- Facile preparation of aromatic ketones from aromatic bromides and arenes with aldehydes
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Aromatic ketones were efficiently prepared in good yields by the reactions of aryl bromides with n-BuLi, followed by the reactions with aromatic aldehydes or aliphatic aldehydes and the subsequent treatment with molecular iodine and K2CO3, in a one-pot method. The same treatment of arenes, instead of aromatic bromides, also provided the corresponding aromatic ketones in good yields. Using these methods, various diaryl ketones and alkyl aryl ketones bearing electron-rich aromatics and electron-deficient aromatics could be prepared efficiently by a simple, transition-metal-free, and therefore environmentally benign experimental procedure.
- Ushijima, Sousuke,Dohi, Souya,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 1436 - 1442
(2012/03/09)
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- Practical one-pot preparation of ketones from aryl and alkyl bromides with aldehydes and DIH via Grignard reagents
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Various diaryl ketones, alkyl aryl ketones, and dialkyl ketones were efficiently prepared in good yields by the reactions of the Grignard reagents derived from aryl or alkyl bromides, followed by the reactions with aromatic or aliphatic aldehydes and the subsequent treatment with 1,3-diiodo-5,5- dimethylhydantoin and K2CO3, in a one-pot method. The same treatment of aromatic bromides bearing electron-withdrawing groups, such as ester, nitrile, ketone, and nitro groups with i-PrMgCl·LiCl or PhMgCl instead of Mg, also provided the corresponding diaryl and alkyl aryl ketones in good yields. The above methods are simple and practical transition-metal-free methods for the preparation of various diaryl ketones and alkyl aryl ketones bearing electron-rich aromatic groups and electron-deficient aromatic groups, as well as dialkyl ketones.
- Dohi, Souya,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 6557 - 6564
(2012/08/27)
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- Nickel-catalyzed Suzuki-Miyaura reaction of aryl fluorides
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Two protocols for the nickel-catalyzed cross-coupling of aryl fluorides with aryl boronic esters have been developed. The first employs metal fluoride cocatalysts, such as ZrF4 and TiF4, which enable Suzuki-Miyaura reactions of aryl fluorides bearing electron-withdrawing (ketones, esters, and CF3), aryl and alkenyl groups as well as those comprising fused aromatic rings, such as fluoronaphthalenes and fluoroquinolines. The second protocol employs aryl fluorides bearing ortho-directing groups, which facilitate the difficult C-F bond activation process via cyclometalation. N-heterocycles, such as pyridines, quinolines, pyrazoles, and oxazolines, can successfully promote cross-coupling with an array of organoboronic esters. A study into the substituent effects with respect to both coupling components has provided fundamental insights into the mechanism of the nickel-catalyzed cross-coupling of aryl fluorides.
- Tobisu, Mamoru,Xu, Tian,Shimasaki, Toshiaki,Chatani, Naoto
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supporting information; experimental part
p. 19505 - 19511
(2012/01/31)
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- Ionically tagged benzimidazole palladium(II) complex: Preparation and catalytic application in cross-coupling reactions
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An imidazolium chloride tagged palladium(II) complex has been conveniently prepared and structurally analyzed. It is active toward cross-coupling of arylboronic acid with aryl halide and benzoyl chloride, giving moderate to high yield of the desired biaryls and aryl ketones, respectively. The present phosphine-free (N-N)Pd(II) complex could be efficiently recycled at least four times with minor decrease of activity in the aqueous Suzuki-Miyaura coupling reaction.
- Zhang, Li,Wu, Junliang,Shi, Lijun,Xia, Chungu,Li, Fuwei
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supporting information; experimental part
p. 3897 - 3901
(2011/08/09)
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- Synthesis of arylketones by ruthenium-catalyzed cross-coupling of aldehydes with arylboronic acids
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The first ruthenium-catalyzed cross-coupling of aldehydes with arylboronic acids is reported. Various aliphatic and aromatic aldehydes are transformed to the corresponding arylketones. A total of 31 examples with moderate to excellent yields are presented, together with the results of an initial mechanistic investigation.
- Li, Hong,Xu, Yuan,Shi, Erbo,Wei, Wei,Suo, Xiangqiang,Wan, Xiaobing
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supporting information; experimental part
p. 7880 - 7882
(2011/08/06)
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- Direct addition of functionalized organozinc reagents to carbon dioxide, ketones, and aldehydes in the presence of MgCl2
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A variety of functionalized organozinc reagents undergo smooth addition reactions at ambient temperature to carbon dioxide, ketones, and aldehydes in the presence of stoichiometric amounts of MgCl2. Several reactions were performed on a 20 mmol scale. Georg Thieme Verlag Stuttgart · New York.
- Bernhardt, Sebastian,Metzger, Albrecht,Knochel, Paul
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experimental part
p. 3802 - 3810
(2011/01/12)
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- Aryl ketone synthesis via tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation
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Tandem orthoplatinated triaryl phosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%.
- Liao, Yuan-Xi,Hu, Qiao-Sheng
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supporting information; experimental part
p. 6986 - 6989
(2010/11/17)
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- A novel Br?nsted acid catalyst for Friedel-Crafts acylation
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Bis(trifluoroalkylsulfonylimino)trifluoromethanesulfonic acid has demonstrated remarkable catalytic ability in the electrophilic acylation of aromatic substrates. Various perfluoroalkyl substituted aroyl chlorides are employed in Friedel-Crafts acylation typically using 1 mol % of catalyst. Crown Copyright
- Posternak, Anna G.,Garlyauskayte, Romute Yu.,Yagupolskii, Lev M.
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supporting information; body text
p. 446 - 447
(2009/05/27)
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- Preparation process of fluorine substituted aromatic compound
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A preparation process of a fluorine substituted aromatic compound comprising reacting an alkali metal or alkali earth metal salt of an aromatic compound having a hydroxy group with an organic fluorinating agent is disclosed. As a representative fluorinating agent, a bis-dialkylamino-difluoromethane compound, for example, 2,2′-difluoro-1,3-dimethylimidazolidine, is exemplified. According to the process, an industrially useful fluorinated aromatic compound, for example, a fluorobenzene, a fluorine substituted benzophenone, a fluorine substituted diarylsulfone can be prepared with ease in economy without specific equipment.
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- Unexpected side products in the tetramethylammonium fluoride-dimethylsulphoxide system
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Reactions of chloro- and nitro-aromatics with low water content solutions of TMAF in DMSO can lead to complex product mixtures resulting from activation of DMSO by fluoride and the formation of DMSO-derived products. Also, the system has been shown to give hydrolysis products in addition to the well-known ethers and phenols, with carboxylic acids and benzamides being formed from the attempted fluorodenitration of substituted benzonitriles.
- Adams, Dave J.,Clark, James H.,McFarland, Heather,Nightingale, David J.
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- Preparation of 4-fluorophenol and 4-fluorobenzoic acid by the Baeyer-Villiger reaction
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The possibility of preparing 4-fluorophenol or 4-fluorobenzoic acid via the Baeyer-Villiger reaction starting from unsymmetrical fluoroaryl ketones is disscussed.Several unsymmetrical 4-fluorobenzophenones having different substituents in the fluorine-free aryl group were prepared and converted to esters by treatment with peracetic acid.The electrophilicity of the substituents influenced the molecular structure of the ester formed as a result of a carbon-to-oxygen migration, and hence 4-fluorophenol or 4-fluorobenzoic acid formation.Electron-withdrawing substituents favoured the formation of 4-fluorophenol in good yields, while electron-donating substituents formed 4-fluorobenzoic acid preferentially.
- Conte, L.,Napoli, M.,Gambaretto, J. P.,Guerrato, A.,Carlini, F. M.
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- Amino terminated poly(aryl ether ketones)
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Described herein are novel amino-terminated poly(aryl ether ketone) oligomers and methods for their production. These amino-terminated poly(aryl ether ketone) oligomers are used as building blocks for a variety of polymers and copolymers.
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- Polymerisation and Related Reactions involving Nucleophilic Aromatic Substitution. Part 1. The Rates of Reaction of Substituted 4-Halogenobenzophenones with the Potassium Salts of Substituted 4-Hydroxybenzophenones
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The rate of displacement of fluorine from 4'-X,4-fluorobenzophenones by the potassium salts of 4'-X,4-hydroxybenzophenones (X = CF3, Cl, F, H, OPh, and OMe) has been studied at 175-225 deg C in diphenyl sulphone as solvent.Comparison with the corresponding rate of displacement of chlorine indicates that the reaction is a bimolecular nucleophilic aromatic substitution.The reaction obeys the Hammett equation using normal ? values for substitution in both the substrate (ρ 1.19) and the phenolate (ρ -0.53).There is also a marked salt effect on the reaction rate and this has been included with the substituent constants in a general equation for the calculation of rate coefficients.The effect of an O- substituent is more marked than would have been expected from the previous range of ? values ascribed to this substituent.
- Ridd, John H.,Yousaf, Taher I.,Rose, John B.
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p. 1729 - 1734
(2007/10/02)
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