- Monodisperse CuPd alloy nanoparticles as efficient and reusable catalyst for the C (sp2)–H bond activation
-
Metal-catalyzed selective activation of C–H bonds is very important for the construction of a variety of biologically active molecules. Supported alloy nanoparticles are of great interest in various catalytic applications due to the synergistic effects between different metals. Here, well-dispersed CuPd alloy nanoparticles supported on reduced graphene oxide (rGO) were synthesized and found to be highly efficient and recyclable catalyst for the chelation-assisted C (sp2)–H bond activation. Aromatic ketones or esters were synthesized via the cross-dehydrogenative coupling (CDC) reaction between 2-arylpyridines and alcohols or acids. Moreover, the catalyst was recovered and used for five times without significantly losing activity.
- Huang, Fei,Wang, Feifan,Hu, Qiyan,Tang, Lin,Xu, Dongping,Fang, Yang,Zhang, Wu
-
-
- Acylation of Arenes with Aldehydes through Dual C-H Activations by Merging Photocatalysis and Palladium Catalysis
-
An acylation of arenes with aldehydes through dual C-H activations at room temperature is reported. The acylation was initiated by phenanthraquinone-catalyzed hydrogen atom transfer from aldehyde under visible light irradiation. The aldehyde-derived acyl
- Wang, Haiyang,Li, Tao,Hu, Dongyan,Tong, Xiaogang,Zheng, Liyan,Xia, Chengfeng
-
supporting information
p. 3772 - 3776
(2021/05/10)
-
- A Strategy for Amide C-N Bond Activation with Ruthenium Catalyst: Selective Aromatic Acylation
-
A strategy for amide C-N bond activation with ruthenium catalyst is described for the first time. The in situ formed bis-cycloruthenated complexes were demonstrated to be the key active species with superior oxidative addition ability to an inert amide C-N bond. The direct C-H bond activation of 2-arylpyridines followed by the amide C-N bond activation took place in the presence of a ruthenium precatalyst to produce monoacylation products in moderate to good yields. Synthetically useful functional groups, such as halogen atoms (F and Cl), ester, acetyl, and vinyl, remained intact during tandem C-H/C-N bond activation reactions.
- Li, Wenkuan,Zhang, Sheng,Feng, Xiujuan,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
-
supporting information
p. 2521 - 2526
(2021/04/05)
-
- Preparation method of nitrogen-containing heterocyclic diarylketone compound
-
The invention belongs to the technical field of pharmaceutical and chemical intermediates and related chemistry, and provides a preparation method of a nitrogen-containing heterocyclic diarylketone compound. According to the method, N,N-phenyl p-toluenesulfonyl benzamide and derivatives thereof are used as acylation reagents and are subjected to a C-H acylation reaction with a 2-phenylpyridine compound in an anhydrous organic solvent under the action of a metal catalyst, a ligand, carboxylic acid and an alkali to be converted into the nitrogen-containing heterocyclic diarylketone compound. According to the preparation method of the nitrogen-containing heterocyclic diarylketone compound, reaction steps are few, amide widely existing in the nature is used as an acyl source, and the nitrogen-containing heterocyclic diarylketone compound is environmentally friendly, low in price, mild in reaction condition and convenient to operate; and the target product is obtained with high yield and high selectivity, and the method has good industrial production value and practical application value. The diarylketone compound synthesized by the method can be subjected to further functionalization reaction, and can be widely applied to the fields of synthesis of medicines, pesticides, bioactive molecules, functional material molecules and the like.
- -
-
Paragraph 0059-0062
(2021/02/10)
-
- Silver catalyzed pyridine-directed acceptorless dehydrogenation of secondary alcohols
-
A silver catalyzed pyridine-directed acceptorless dehydrogenation of secondary benzyl alcohols was developed. This general procedure delivers ketones with high atom-economy and hydrogen was the sole byproduct. This dehydrogenation reaction has a good functional group tolerance and high efficiency (up to 90% yield and 10,000/1 substrates-to-catalyst ratio).
- Zhuang, Xin,Tao, Jing,Luo, Zhen,Hong, Chuan-Ming,Liu, Zheng-Qiang,Li, Qing-Hua,Ren, Li-Qing,Luo, Qun-Li,Liu, Tang-Lin
-
p. 245 - 249
(2021/02/03)
-
- Dual photoredox/palladium-catalyzed C-H acylation of 2-arylpyridines with oxime esters
-
An unprecedented dual photoredox/palladium-catalyzed iminyl-radical-mediated C-C bond cleavage and directed ortho C-H acylation of 2-arylpyridines by using oxime esters is described. Oxime esters can serve as efficient acyl sources through formation of the corresponding acyl radicals by photoredox-catalyzed iminyl-radical-mediated C-C bond cleavage. This redox-neutral protocol features excellent regioselectivity, a broad substrate scope, and good functional-group tolerance with respect to both components, giving a broad range of aryl ketones with generally good yields.
- He, Bin-Qing,Gao, Yuan,Wang, Peng-Zi,Wu, Hong,Zhou, Hong-Bin,Liu, Xiao-Peng,Chen, Jia-Rong
-
p. 373 - 377
(2020/09/11)
-
- Ruthenium-Catalyzed Carbonylative Coupling of Anilines with Organoboranes by the Cleavage of Neutral Aryl C-N Bond
-
Herein, we report the first ruthenium-catalyzed Suzuki-type carbonylative reaction of electronically neutral anilines via C(aryl)-N bond cleavage. Without any ligand and base, diaryl ketones can be obtained in moderate to high yields by using Ru3/su
- Xu, Jian-Xing,Zhao, Fengqian,Yuan, Yang,Wu, Xiao-Feng
-
p. 2756 - 2760
(2020/03/30)
-
- Ag1Pd1-rGO nanocomposite as recyclable catalyst for CDC reactions of 2-arylpyridines with aldehydes
-
Ag1Pd1 nanoparticle-reduced graphene oxide (Ag1Pd1-rGO) nanocomposite was used as an efficient catalyst for the synthesis of aromatic ketones via cross dehydrogenative coupling (CDC) reactions of 2-arylpyridines
- Hu, Qiyan,Liu, Xiaowang,Huang, Fei,Wang, Feifan,Li, Qian,Zhang, Wu
-
-
- Use of Cyclopropane as C1 Synthetic Unit by Directed Retro-Cyclopropanation with Ethylene Release
-
Cyclopropanation of alkenes is a well-established textbook reaction for the synthesis of cyclopropanes, where a "high-energy" carbene species is exploited to drive the reaction forward. However, little attention has been focused toward molecular transformations involving the reverse reaction, retro-cyclopropanation (RC). This is because of difficulties associated with both cleaving the two geminal C-C single bonds and exploiting the generated carbenes for further transformations in an efficient and selective manner. Here, we report that a molybdenum-based catalytic system overcomes the above challenges and effects the RC of cyclopropanes bearing a pyridyl group with the release of ethylene (alkene) and the subsequent intramolecular cyclization leading to pyrido[2,1-a]isoindoles. The reaction allows for the uncommon use of cyclopropanes as C1 synthetic units in contrast to most conventional reactions in which cyclopropanes are used as C3 synthetic units. We anticipate that this new strategy will pave the way for C1 cyclopropane chemistry.
- Asako, Sobi,Kobashi, Takaaki,Takai, Kazuhiko
-
supporting information
p. 15425 - 15429
(2018/11/23)
-
- Palladium-catalyzed decarboxylative, decarbonylative and dehydrogenative C(sp2)-H acylation at room temperature
-
Over the past few decades, an impressive array of C-H activation methodology has been developed for organic synthesis. However, due to the inherent inertness of the C-H bonds (e.g. ~110 kcal mol-1 for the cleavage of C(aryl)-H bonds) harsh reaction conditions have been realized to overcome high energetic transition states resulting in a limited substrate scope and functional group tolerance. Therefore, the development of mild C-H functionalization protocols is in high demand to exploit the full potential of the C-H activation strategy in the synthesis of a complex molecular framework. Although, electron-rich substrates undergo electrophilic metalation under relatively mild conditions, electron-deficient substrates proceed through a rate-limiting C-H insertion under forcing conditions at high temperature. In addition, a stoichiometric amount of toxic silver salt is frequently used in palladium catalysis to facilitate the C-H activation process which is not acceptable from the environmental and industrial standpoint. We report herein, a Pd(ii)-catalyzed decarboxylative C-H acylation of 2-arylpyridines with α-ketocarboxylic acids under mild conditions. The present protocol does not require stoichiometric silver(i) salts as additives and proceeds smoothly at ambient temperature. A novel decarbonylative C-H acylation reaction has also been accomplished using aryl glyoxals as acyl surrogates. Finally, a practical C-H acylation via a dehydrogenative pathway has been demonstrated using commercially available benzaldehydes and aqueous hydroperoxides. We also disclose that acetonitrile solvent is optimal for the acylation reaction at room temperature and has a prominent role in the reaction outcome. Control experiments suggest that the acylation reaction via decarboxylative, decarbonylative and dehydrogenative proceeds through a radical pathway. Thus we disclose a practical protocol for the sp2 C-H acylation reaction.
- Hossian, Asik,Manna, Manash Kumar,Manna, Kartic,Jana, Ranjan
-
supporting information
p. 6592 - 6603
(2017/08/16)
-
- Preparation method of 2-(2-benzoyl)phenyl pyridines compound
-
The invention relates to a preparation method of a 2-(2-benzoyl)phenyl pyridines compound. The preparation method comprises the following steps: adding 5 mol percent of a catalyst PdCl2, 10 mol percent of a phosphine ligand XPhos, 0.3mmol of a reactant I,
- -
-
Paragraph 0018; 0019; 0020; 0021
(2017/02/17)
-
- Palladium catalyzed ortho-C-H-acylation of 2-arylpyridines using phenylacetylenes and styrene epoxide
-
A palladium-catalyzed ortho-C-H-acylation of 2-arylpyridine using phenylacetylenes and styrene epoxide as the acylated reagents was developed. With the employment of tert-butyl hydroperoxide (TBHP) as the oxidant and a phosphorous ligand, the protocol generates corresponding aryl ketones in moderated to good yields with high regioselectivity and good functional group compatibility.
- Zhang, Qian,Wang, Yang,Yang, Tingting,Li, Li,Li, Dong
-
-
- Replacing Pd(OAc)2 with supported palladium nanoparticles in ortho-directed CDC reactions of alkylbenzenes
-
Supported palladium nanoparticles are used as efficient catalysts for the synthesis of aromatic ketones via cross dehydrogenative coupling reactions of 2-arylpyridines with alkylbenzenes. The catalyst can be reused for five cycles without significantly losing activity. Mechanism research showed that alkylbenzenes were oxidized to their corresponding aldehydes and subsequently coupled with 2-arylpyridines to generate aryl ketones through a Pd0/PdII/PdIV catalytic cycle.
- Bao, Yong-Sheng,Zhang, Dongling,Jia, Meilin,Zhaorigetu, Bao
-
supporting information
p. 2072 - 2077
(2016/04/19)
-
- Decarboxylative acylation of arenes with mandelic acid derivatives via palladium-catalyzed oxidative sp2 C-H activation
-
An efficient palladium catalyzed decarboxylative acylation of arenes with mandelic acid derivatives via oxidative sp2 C-H activation in the presence of tert-butyl hydroperoxide has been developed. The acylation reaction is assisted by a pyridine directing group. The starting materials are inexpensive and readily available. This method provides an economical and convenient way to synthesize aryl ketones.
- Liu, Xia,Yi, Ze,Wang, Jianhui,Liu, Guiyan
-
p. 10641 - 10646
(2015/02/05)
-
- Palladium-Catalyzed Oxidative Direct ortho-C-H Acylation of Arenes with Aldehydes under Aqueous Conditions
-
Palladium-catalyzed ortho-acylation of arenes with aldehydes in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant under aqueous conditions has been demonstrated. The acylation reaction exhibits excellent regioselectivity and wide functional g
- Xiao, Fuhong,Chen, Shuqing,Huang, Huawen,Deng, Guo-Jun
-
supporting information
p. 7919 - 7925
(2015/12/24)
-
- Manganese-Catalyzed Direct Nucleophilic C(sp2)-H Addition to Aldehydes and Nitriles
-
Herein, a manganese-catalyzed nucleophilic addition of inert C(sp2)-H bonds to aldehydes and nitriles is disclosed by virtue of a dual activation strategy. The reactions feature mild reaction conditions, excellent regio- and stereoselectivity, and a wide substrate scope, which includes both aromatic and olefinic C-H bonds, as well as a large variety of aldehydes and nitriles. Moreover, mechanistic studies shed light on possible catalytic cycles.
- Zhou, Bingwei,Hu, Yuanyuan,Wang, Congyang
-
supporting information
p. 13659 - 13663
(2015/11/16)
-
- Palladium(II)-Catalyzed C-H Acylation with Arylglycine Derivatives
-
A novel palladium(II)-catalyzed ortho acylation of arenes with arylglycines in the presence of Cu(OAc)2 and K2S2O8 to afford the benzophenones was developed. This direct C-H acylation is suitable for a broad range of substrates. The control experiments suggested a possible oxidative addition mechanism.
- Fan, Weizheng,Su, Jiapeng,Feng, Bainian
-
p. 2033 - 2036
(2015/09/01)
-
- Benzyl bromides as aroyl surrogates in substrate directed Pd catalysed o-aroylation
-
An oxidative cross-coupling between directing substrates and benzyl bromides via the combined effect of oxidants TBHP and NMO, catalysed by Pd(ii) has been investigated. Benzyl bromides served as efficient aroyl surrogates in this substrate directed C-H f
- Behera, Ahalya,Ali, Wajid,Guin, Srimanta,Khatun, Nilufa,Mohanta, Prakash R.,Patel, Bhisma K.
-
p. 33334 - 33338
(2015/04/27)
-
- Arylmethyl chlorides: New bifunctional reagents for palladium-catalyzed ortho -chlorination and acylation of 2-arylpyridines
-
A chemoselective, palladium-catalyzed, ligand-directed ortho-C-H chlorination and acylation process has been developed, exhibiting high regioselectivity for 2-arylpyridines bearing a meta-substituent. Worthy of note is the fact that arylmethyl chlorides a
- Zhang, Guodong,Sun, Suyan,Yang, Fan,Zhang, Qian,Kang, Jianxun,Wu, Yusheng,Wu, Yangjie
-
p. 443 - 450
(2015/02/19)
-
- Palladium-catalyzed oxidative synthesis of aromatic ketones using olefins as acyl equivalents through selective ortho aromatic C-H bond activation
-
An efficient catalytic system has been developed for selective ortho-acylation of arenes by oxidative C-H bond activation using a palladium catalyst. Olefins were oxidized to the corresponding aldehydes/benzoyl radicals, which, on coupling with 2-phenylpy
- Khemnar, Ashok B.,Bhanage, Bhalchandra M.
-
p. 6746 - 6752
(2016/02/18)
-
- Pd(ii)-catalysed o-aroylation of directing arenes using terminal aryl alkenes and alkynes
-
A substrate-directed Pd-catalysed o-aroylation strategy has been demonstrated using new aroyl surrogates viz. terminal aryl alkenes and alkynes in the presence of TBHP. By a subtle change in catalyst from Cu to Pd, a differential selectivity is observed.
- Khatun, Nilufa,Banerjee, Arghya,Santra, Sourav K.,Behera, Ahalya,Patel, Bhisma K.
-
p. 54532 - 54538
(2015/01/16)
-
- Pd/Mg-La mixed oxide catalyzed oxidative sp2 CH bond acylation with alcohols
-
Pd/Mg-La mixed oxide is used as an efficient catalyst for the oxidative direct acylation of arene sp2 CH bonds with alcohols. TBHP was used for in situ oxidation of the alcohols to aldehydes which after coupling with 2-aryl pyridines forms aryl ketones. The catalyst is recovered and used for four cycles.
- Kishore,Kantam, M. Lakshmi,Yadav,Sudhakar,Laha,Venugopal
-
p. 213 - 218
(2013/10/08)
-
- Ruthenium-catalyzed carbonylative C-C coupling in water by directed C-H bond activation
-
First things first: The title reaction of arenes bearing ortho-directing groups (DG) in the presence of a ruthenium catalyst and aryl iodide is presented. The reaction is general for variously substituted aryl iodides to give ketones in moderate to good yields, and water serves as the solvent. The system is highly selective towards the mono-carbonylative arylation by ortho C-H functionalization. cod=cyclo-1,5-octadiene. Copyright
- Tlili, Anis,Schranck, Johannes,Pospech, Jola,Neumann, Helfried,Beller, Matthias
-
supporting information
p. 6293 - 6297
(2013/07/05)
-
- Palladium-catalyzed synthesis of aromatic ketones and isoindolobenzimidazoles via selective aromatic C-H bond acylation
-
A convenient and efficient palladium-catalyzed synthesis of aromatic ketones and isoindolobenzimidazoles has been developed via selective aromatic C-H bond acylation. The protocol uses palladium acetate as the catalyst, readily available carboxylic acids as the acylating reagents, trifluoroacetic anhydride as the activated agent of the acids, and the corresponding aromatic ketones and isoindolobenzimidazoles were obtained in good to excellent yields. This finding should provide a new and useful strategy for synthesis of aromatic ketones and isoindolobenzimidazoles.
- Lu, Juyou,Zhang, Hao,Chen, Xiaowu,Liu, Hongxia,Jiang, Yuyang,Fu, Hua
-
p. 529 - 536
(2013/05/08)
-
- Palladium catalyzed direct ortho C-H acylation of 2-arylpyridines using toluene derivatives as acylation reagents
-
A facile ortho-acylation of 2-arylpyridines by a Pd-catalyzed oxidative C-H activation was developed, in which no prefunctionalized toluene derivatives were used as acylation reagents in a tandem reaction to form 2-pyridyldiaryl ketones with moderate yiel
- Xu, Zhipeng,Xiang, Biao,Sun, Peipei
-
p. 1679 - 1682
(2013/03/13)
-
- Direct carbo-acylation reactions of 2-arylpyridines with α-diketones via Pd-catalyzed C-H activation and selective C(sp2)-C(sp2) cleavage
-
An efficient carbo-acylation reaction of 2-arylpyridines with α-diketones via Pd-catalyzed C-H bond activation and C-C bond cleavage in the presence of TBHP was developed that generated aryl ketones in good yields. The highly selective formation of aryl ketones was observed when 2-arylpyridines reacted with aromatic/aliphatic α-diketones.
- Zhou, Wei,Li, Hongji,Wang, Lei
-
p. 4594 - 4597
(2012/10/29)
-
- Four tandem C-H activations: A sequential C-C and C-O bond making via a Pd-catalyzed cross dehydrogenative coupling (CDC) approach
-
An unprecedented aroylation at the ortho C-H bond with respect to a directing group has been accomplished via a Pd(II)-catalyzed cross dehydrogenative coupling approach using alkylbenzene as the synthetic equivalent of an aroyl moiety. The reaction proceeds through sequential C-C and C-O bond making at the expense of four consecutive C-H bond cleavages (three sp 3 benzylic C-H's and one sp2 arene C-H) to selectively install an aroyl functionality at the proximal site of substrates containing various directing groups.
- Guin, Srimanta,Rout, Saroj Kumar,Banerjee, Arghya,Nandi, Shyamapada,Patel, Bhisma K.
-
p. 5294 - 5297,4
(2020/09/02)
-
- Palladium-catalyzed oxidative sp2 C-H bond acylation with alcohols
-
An efficient method was developed for the direct acylation of arene sp 2 C-H bonds with alcohols using palladium chloride as a catalyst and peroxide as the oxidant. The alcohols were oxidized to their corresponding aldehydes in situ and efficiently coupled with 2-arylpyridines to give aryl ketones in chlorobenzene.
- Xiao, Fuhong,Shuai, Qi,Zhao, Feng,Basle, Olivier,Deng, Guojun,Li, Chao-Jun
-
supporting information; experimental part
p. 1614 - 1617
(2011/05/04)
-
- Decarboxylative acylation of arenes with α-oxocarboxylic acids via palladium-catalyzed C-H activation
-
(Equation Presented). An efficient palladium-catalyzed decarboxylative acylation of unactivated arenes with α-oxocarboxylic acids is reported. This method provides a novel access to aryl ketones.
- Li, Mingzong,Ge, Haibo
-
supporting information; experimental part
p. 3464 - 3467
(2010/10/01)
-
- Palladium-catalyzed acylation of sp2 C-H bond: Direct access to ketones from aldehydes
-
A palladium-catalyzed direct access to ketones from aldehydes via C-H cleavage of arenes is described. The procedure utilizes air as a clean and free terminal oxidant.
- Jia, Xiaofei,Zhang, Shouhui,Wang, Wenhui,Luo, Fang,Cheng, Jiang
-
supporting information; experimental part
p. 3120 - 3123
(2009/12/06)
-