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Half-sandwich ruthenium complex containing phenyl benzoxazole structure as well as preparation method and application of half-sandwich ruthenium complex
The invention relates to a half-sandwich ruthenium complex containing a phenyl benzoxazole structure as well as a preparation method and application of the half-sandwich ruthenium complex. The ruthenium complex has the following structure as shown in the specification. The preparation method comprises the steps of dissolving phenyl benzoxazole, [CymRuCl2] 2 and sodium acetate in methanol at room temperature, heating the system, and continuing to react; and after the reaction is finished, standing, filtering, carrying out reduced pressure pumping on the solvent, carrying out column chromatography separation on the obtained crude product to obtain the red half-sandwich ruthenium complex containing the phenyl benzoxazole structure, and applying the red half-sandwich ruthenium complex to catalysis of oxidation of alkyl pyridine compounds to prepare nitrogen heterocyclic ketone compounds. Compared with the prior art, the preparation method provided by the invention is simple and green, the catalytic oxidation reaction can be carried out under mild conditions, and the catalyst has high stability and is not sensitive to air and water.
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Paragraph 0049-0052

(2021/04/14)

Aromatization as an Impetus to Harness Ketones for Metallaphotoredox-Catalyzed Benzoylation/Benzylation of (Hetero)arenes
Herein we report ketones as feedstock materials in radical cross-coupling reactions under Ni/photoredox dual catalysis. In this approach, simple condensation first converts ketones into prearomatic intermediates that then act as activated radical sources for cross-coupling with aryl halides. Our strategy enables the direct benzylation/benzoylation of (hetero)arenes under mild reaction conditions with high functional group tolerance.
Chen, Ting-Wei,Cheng, Cheng-Ku,Chiu, Cheng-Chau,Huang, Pin-Gong,Lee, Shao-Chi,Lee, Yi-Hsin,Li, Li-Yun,Liao, Hsuan-Hung,Lin, Heng-Bo,Tsai, Zong-Nan,Tsao, Yong-Ting,Yang, Chung-Hsin
(2022/01/04)

Photo-induced oxidative cleavage of C-C double bonds for the synthesis of biaryl methanoneviaCeCl3catalysis
A Ce-catalyzed strategy is developed to produce biaryl methanonesviaphotooxidative cleavage of C-C double bonds at room temperature. This reaction is performed under air and demonstrates high activity as well as functional group tolerance. A synergistic Ce/ROH catalytic mechanism is also proposed based on the experimental observations. This protocol should be the first successful Ce-catalyzed photooxidation reaction of olefins with air as the oxidant, which would provide inspiration for the development of novel Ce-catalyzed photochemical synthesis processes.
Xie, Pan,Xue, Cheng,Du, Dongdong,Shi, SanShan
supporting information
p. 6781 - 6785
(2021/08/20)

Decatungstate-mediated solar photooxidative cleavage of CC bonds using air as an oxidant in water
With the increasing attention for green chemistry and sustainable development, there has been much interest in searching for greener methods and sources in organic synthesis. However, toxic additives or solvents are inevitably involved in most organic transformations. Herein, we first report the combination of direct utilization of solar energy, air as the oxidant and water as the solvent for the selective cleavage of CC double bonds in aryl olefins. Various α-methyl styrenes, diaryl alkenes as well as terminal styrenes are well tolerated in this green and sustainable strategy and furnished the desired carbonyl products in satisfactory yields. Like heterogeneous catalysis, this homogeneous catalytic system could also be reused and it retains good activity even after repeating three times. Mechanism investigations indicated that both O2- and 1O2 were involved in the reaction. Based on these results, two possible mechanisms, including the electron transfer pathway and the energy transfer pathway, were proposed.
Du, Dongdong,Luo, Junfei,Shi, Sanshan,Xie, Pan,Xue, Cheng
p. 5936 - 5943
(2021/08/23)

A Fast and General Route to Ketones from Amides and Organolithium Compounds under Aerobic Conditions: Synthetic and Mechanistic Aspects
We report that the nucleophilic acyl substitution reaction of aliphatic and (hetero)aromatic amides by organolithium reagents proceeds quickly (20 s reaction time), efficiently, and chemoselectively with a broad substrate scope in the environmentally responsible cyclopentyl methyl ether, at ambient temperature and under air, to provide ketones in up to 93 % yield with an effective suppression of the notorious over-addition reaction. Detailed DFT calculations and NMR investigations support the experimental results. The described methodology was proven to be amenable to scale-up and recyclability protocols. Contrasting classical procedures carried out under inert atmospheres, this work lays the foundation for a profound paradigm shift of the reactivity of carboxylic acid amides with organolithiums, with ketones being straightforwardly obtained by simply combining the reagents under aerobic conditions and with no need of using previously modified or pre-activated amides, as recommended.
Ghinato, Simone,Territo, Davide,Maranzana, Andrea,Capriati, Vito,Blangetti, Marco,Prandi, Cristina
p. 2868 - 2874
(2021/01/21)

Organotellurium-catalyzed oxidative deoximation reactions using visible-light as the precise driving energy
Irradiated by visible light, the recyclable (PhTe)2-catalyzed oxidative deoximation reaction could occur under mild conditions. In comparison with the thermo reaction, the method employed reduced catalyst loading (1 mol% vs. 2.5 mol%), but afforded elevated product yields with expanded substrate scope. This work demonstrated that for the organotellurium-catalyzed reactions, visible light might be an even more precise driving energy than heating because it could break the Te–Te bond accurately to generate the active free radical catalytic intermediates without damaging the fragile substituents (e.g., heterocycles) of substrates. The use of O2 instead of explosive H2O2 as oxidant affords safer reaction conditions from the large-scale application viewpoint.
Deng, Xin,Qian, Rongrong,Zhou, Hongwei,Yu, Lei
supporting information
p. 1029 - 1032
(2020/10/23)

Visible light-driven direct synthesis of ketones from aldehydes via C[sbnd]H bond activation using NiCu nanoparticles adorned on carbon nano onions
An efficient, straightforward and high yield synthetic approach is described for the direct synthesis of diaryl ketones via the C[sbnd]H bond activation of aldehydes using NiCu nanoparticles adorned on carbon nano onions as an efficient heterogeneous catalyst under the irradiation of a mercury-vapor lamp (400 w) via simple workup. This C[sbnd]H bond activation reaction appears simple and convenient with a wide substrate scope in view of its excellent synthesis prowess as illustrated in the preparation of new-approved anti-Alzheimer and anti-HIV medicinal compounds under greener and mild reaction conditions; catalyst could be recycled and reused five times without any loss of catalytic activity.
Heydari, Akbar,Khorsandi, Zahra,Metkazini, S. Fatemeh Mohammadi,Varma, Rajender S.
(2021/11/09)

Ruthenium-Catalyzed Dehydrogenation of Alcohols with Carbodiimide via a Hydrogen Transfer Mechanism
Ruthenium-catalyzed oxidative dehydrogenation of alcohols using carbodiimide as an efficient hydrogen acceptor has been developed. The protocol exhibits wide substrate scope with good to excellent yields. The results of the kinetic analysis indicated that the reaction mechanism includes the hydrogen transfer process and that the addition of carbodiimide is essential for the reaction system, and the resulting amidine also could react as a hydrogen acceptor.
Sueki, Shunsuke,Matsuyama, Mizuki,Watanabe, Azumi,Kanemaki, Arata,Katakawa, Kazuaki,Anada, Masahiro
p. 4878 - 4885
(2020/06/02)

Overcoming Electron-Withdrawing and Product-Inhibition Effects by Organocatalytic Aerobic Oxidation of Alkylpyridines and Related Alkylheteroarenes to Ketones
An organocatalyzed aerobic benzylic C-H oxidation of alkyl and aryl heterocycles has been developed. This transition metal-free method is able to overcome the electron-withdrawing effect as well as product-inhibition effects in heterobenzylic radical oxidation. A variety of ketones bearing N-heterocyclic groups could be prepared under relatively mild conditions with moderate to high yields.
Wang, Hua,Liu, Jie,Qu, Jian-Ping,Kang, Yan-Biao
p. 3942 - 3948
(2020/03/23)

Catalytic C-H aerobic and oxidant-induced oxidation of alkylbenzenes (including toluene derivatives) over VO2+immobilized on core-shell Fe3O4?SiO2at room temperature in water
Direct C-H bond oxidation of organic materials, and producing the necessary oxygenated compounds under mild conditions, has attracted increasing interest. The selective oxidation of various alkylbenzenes was carried out by means of a new catalyst containing VO2+ species supported on silica-coated Fe3O4 nanoparticles using t-butyl hydroperoxide as an oxidant at room temperature in H2O or solvent-free media. The chemical and structural characterization of the catalyst using several methods such as FTIR spectroscopy, XRD, FETEM, FESEM, SAED, EDX and XPS showed that VO2+ is covalently bonded to the silica surface. High selectivity and excellent conversion of various toluene derivatives, with less reactive aliphatic (sp3) C-H bonds, to related benzoic acids were quite noticeable. The aerobic oxygenation reaction of these alkylbenzenes was studied under the same conditions. All the results accompanied by sustainability of the inexpensive and simple magnetically separable heterogeneous catalyst proved the important criteria for commercial applications. This journal is
Mohammadpour, Pegah,Safaei, Elham
p. 23543 - 23553
(2020/07/14)

Compound, organic electroluminescent device and electronic device
The invention belongs to the technical field of OLED and provides a compound with a structure shown in the chemical formula 1, wherein L1 and L2 are respectively and independently selected from a single bond, C1-C20 alkylene, C3-C20 cycloalkylene, C6-C30 arylene and C3-C30 heteroarylene, Ar1 and Ar2 are each independently selected from C1-C20 alkyl, C-C20 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, and Si (R1R2R3), and R1, R2, and R3 are each independently selected from C1-C20 alkyl and C6-C30 aryl. The invention provides the compound taking a phenanthrene fused ring derivative as a parent nucleus. Compound molecules have very strong plane ductility. The strong planar ductility of compound molecules enhances the rigidity of the material and prolongs the service life of the material. Besides, the molecular parent nucleus and the aryl substituent are easy to form a large conjugated system, a plurality of nitrogen atom centers exist at the same time, the intramolecular electron cloud density is increased, so that the HOMO energy level can be further adjusted to a proper level, the electron mobility and the transition rate are further improved, and thus the organic electroluminescent device has high device efficiency. The invention further provides an organic electroluminescent device and an electronic device.
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Paragraph 0139-0141

(2020/04/17)

Compound, organic electroluminescent device and electronic device
The invention belongs to the technical field of OLEDs and provides a compound with a structure of a chemical formula 1, wherein X1, X2 and X3 are C or N, and at least one of X1, X2 and X3 is N; X4, X5and X6 are C or N, and only one N exists in X4, X5 and X6; L1 and L2 are each independently selected from the group consisting of a single bond, a C1-C20 alkylene group, a C6-C30 arylene group, a C3-C30 heteroarylene group, and a C3-C20 cycloalkylene group; Ar1 and Ar2 are each independently selected from the group consisting of a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C30 aryl group, a C3-C30 heteroaryl group, and Si(R1R2R3). According to the phenanthrene fused ring compound provided by the invention, compound molecules have strong planar ductility. The strong planar ductility of the compound molecules can enhance the rigidity of the material and prolong the service life of the material. Besides, the molecular parent nucleus and the aryl substituent group are prone to forming a large conjugated system, and a plurality of nitrogen atom centers exist at the same time, so that the intramolecular electron cloud density is increased, the electron mobility and the transition rate can be improved, and an organic light-emitting device has relatively high device efficiency. The invention further provides the organic light-emitting device and an electronic device.
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Paragraph 0149-0151

(2020/05/01)

Copper-Catalyzed Oxidative Fragmentation of Alkynes with NFSI Provides Aryl Ketones
A copper-catalyzed oxidative cleavage reaction of alkynes using NFSI and TBHP was described. Various terminal and internal alkyne substrates were employed to render quick access to aryl ketone products in moderate to good yields. NFSI not only functioned as N-centered radical precursors but also engaged in the aryl group migration. Mechanistic studies also suggested the important role of water in the title reactions.
Chen, Hanfei,Cheng, Hao,Huang, Yifan,Jin, Chaochao,Song, Weihan,Tan, Chen,Tan, Jiajing,Tang, Lin,Yang, Fang,Zhang, Shuaifei
supporting information

(2020/11/03)

Novel synthesis method for aromatic ketone compounds
The invention discloses a novel method for synthesizing target aromatic ketone compounds by taking alkyne and N-fluorobenzenesulfonamide as initial raw materials of a reaction through a mechanism of catalyzing single electron transfer of alkyne breakage by copper under the action of an oxidizing agent. The method provided by the invention is wide in substrate range, and can construct different substituted aromatic ketone compounds by using fat and aromatic alkyne as substrates. In addition, the method provided by the invention has the advantages of mild reaction conditions, simple operation, product diversity, and capability of realizing large-scale production.
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Paragraph 0048-0050

(2020/12/08)

Silylcarboxylic Acids as Bifunctional Reagents: Application in Palladium-Catalyzed External-CO-Free Carbonylative Cross-Coupling Reactions
A palladium-catalyzed external-CO-free carbonylative Hiyama-Denmark cross-coupling reaction is presented. The introduction of silylcarboxylic acids as bifunctional reagents (CO and nucleophile source) avoids the need for external gaseous CO and a silylarene coupling partner. The transformation features high functional group tolerance and it is successful with electron-rich, -neutral, and -poor aryl iodides. Stoichiometric studies and control experiments provide insight into the reaction mechanism and support the hypothesized dual role of silylcarboxylic acids. (Figure presented.).
Li, Xiong,Xu, Jie,Li, Yue,Kramer, S?ren,Skrydstrup, Troels,Lian, Zhong
supporting information
p. 4078 - 4083
(2020/07/30)

Photoenzymatic Hydrogenation of Heteroaromatic Olefins Using ‘Ene’-Reductases with Photoredox Catalysts
Flavin-dependent ‘ene’-reductases (EREDs) are highly selective catalysts for the asymmetric reduction of activated alkenes. This function is, however, limited to enones, enoates, and nitroalkenes using the native hydride transfer mechanism. Here we demonstrate that EREDs can reduce vinyl pyridines when irradiated with visible light in the presence of a photoredox catalyst. Experimental evidence suggests the reaction proceeds via a radical mechanism where the vinyl pyridine is reduced to the corresponding neutral benzylic radical in solution. DFT calculations reveal this radical to be “dynamically stable”, suggesting it is sufficiently long-lived to diffuse into the enzyme active site for stereoselective hydrogen atom transfer. This reduction mechanism is distinct from the native one, highlighting the opportunity to expand the synthetic capabilities of existing enzyme platforms by exploiting new mechanistic models.
Biegasiewicz, Kyle F.,Black, Michael J.,Chung, Megan M.,Hyster, Todd K.,Meichan, Andrew J.,Nakano, Yuji,Sandoval, Braddock A.,Zhu, Tianyu
supporting information
p. 10484 - 10488
(2020/04/29)

Synthesis of biaryl ketones by arylation of Weinreb amides with functionalized Grignard reagents under thermodynamic controlvs.kinetic control ofN,N-Boc2-amides
A highly efficient method for chemoselective synthesis of biaryl ketones by arylation of Weinreb amides (N-methoxy-N-methylamides) with functionalized Grignard reagents is reported. This protocol offers rapid entry to functionalized biaryl ketones after Mg/halide exchange with i-PrMgCl·LiCl under operationally-simple and practical reaction conditions. The scope of the method is highlighted in >40 examples, including bioactive compounds and pharmaceutical derivatives. Collectively, this transition-metal-free approach offers a major advantage over the recently established cross-coupling of amides by oxidative addition of N-C(O) bonds. Considering the utility of amide acylation reactions in modern synthesis, we expect that this method will be of broad interest.
Li, Guangchen,Szostak, Michal
supporting information
p. 3827 - 3831
(2020/06/03)

Kinetically Controlled, Highly Chemoselective Acylation of Functionalized Grignard Reagents with Amides by N?C Cleavage
The direct transition-metal-free acylation of amides with functionalized Grignard reagents by highly chemoselective N?C cleavage under kinetic control has been accomplished. The method offers rapid and convergent access to functionalized biaryl ketones through transient tetrahedral intermediates. The direct access to functionalized Grignard reagents by in situ halogen–magnesium exchange promoted by the versatile turbo-Grignard reagent (iPrMgCl?LiCl) permits excellent substrate scope with respect to both the amide and Grignard coupling partners. These reactions enable facile, operationally simple and chemoselective access to tetrahedral intermediates from amides under significantly milder conditions than chelation-controlled intermediates. This novel direct two-component coupling sets the stage for using amides as acylating reagents in an alternative paradigm to the metal-chelated approach, acyl metals and Weinreb amides.
Li, Guangchen,Szostak, Michal
supporting information
p. 611 - 615
(2020/01/02)

I-Pr2NMgCl·LiCl Enables the Synthesis of Ketones by Direct Addition of Grignard Reagents to Carboxylate Anions
The direct preparation of ketones from carboxylate anions is greatly limited by the required use of organolithium reagents or activated acyl sources that need to be independently prepared. Herein, a specific magnesium amide additive is used to activate and control the addition of more tolerant Grignard reagents to carboxylate anions. This strategy enables the modular synthesis of ketones from CO2 and the preparation of isotopically labeled pharmaceutical building blocks in a single operation.
Colas, Kilian,Dos Santos, A. Catarina V. D.,Mendoza, Abraham
supporting information

(2019/10/08)

Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
p. 11823 - 11838
(2019/10/02)

Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols
An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.
Verheyen, Thomas,Van Turnhout, Lars,Vandavasi, Jaya Kishore,Isbrandt, Eric S.,De Borggraeve, Wim M.,Newman, Stephen G.
supporting information

(2019/05/08)

Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols
An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.
Verheyen, Thomas,Van Turnhout, Lars,Vandavasi, Jaya Kishore,Isbrandt, Eric S.,De Borggraeve, Wim M.,Newman, Stephen G.
supporting information
p. 6869 - 6874
(2019/05/10)

Fukuyama Cross-Coupling Approach to Isoprekinamycin: Discovery of the Highly Active and Bench-Stable Palladium Precatalyst POxAP
An efficient and user-friendly palladium(II) precatalyst, POxAP (post-oxidative-addition precatalyst), was identified for use in Fukuyama cross-coupling reactions. Suitable for storage under air, the POxAP precatalyst allowed reaction between thioesters and organozinc reagents with turnover numbers of ～90000. A series of 23 ketones were obtained with yields ranging from 53 to 99%. As proof of efficacy, an alternative approach was developed for the synthesis of a key precursor of the natural product isoprekinamycin.
Tang, Shuang-Qi,Bricard, Jacques,Schmitt, Martine,Bihel, Frédéric
p. 844 - 848
(2019/01/30)

A convenient and practical heterogeneous palladium-catalyzed carbonylative Suzuki coupling of aryl iodides with formic acid as carbon monoxide source
A practical heterogeneous palladium-catalyzed carbonylative Suzuki coupling of aryl iodides with arylboronic acids under carbon monoxide gas-free conditions has been developed using a bidentate phosphino-functionalized magnetic nanoparticle-immobilized palladium(II) complex as catalyst. Formic acid was utilized as the carbon monoxide source with dicyclohexylcarbodiimide as the activator, and a wide variety of biaryl ketones were generated in moderate to high yields. The new heterogeneous palladium catalyst can be prepared via a simple procedure and can easily be separated from a reaction mixture by simply applying an external magnet and recycled up to 10 times without any loss of activity.
You, Shengyong,Yan, Chenyu,Zhang, Rongli,Cai, Mingzhong
(2019/01/04)

Preparation method of aromatic ketone
The invention discloses a preparation method of aromatic ketone. Under the effects of a palladium catalyst and a nitrogen-containing ligand, nitrile compounds and arylsulfonylhydrazide take desulfurization addition reaction in an organic solvent; after the reaction is completed, post treatment is performed to obtain aromatic ketone. The reaction is applicable to aromatic nitrile compounds, and isalso applicable to aliphatic nitrile compounds; the reaction realizes the wide substrate applicability and functional group tolerance; the potential application value is realized in the aspect of aryl-carbonyl building.
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Paragraph 0041; 0042; 0043; 0045

(2018/09/11)

Aerobic Oxygenation of Alkylarenes over Ultrafine Transition-Metal-Containing Manganese-Based Oxides
The oxygenation of alkylarenes to the corresponding aryl ketones is an important reaction, and the development of efficient heterogeneous catalysts that can utilize O2 as the sole oxidant is highly desired. In this study, we developed an efficient alkylarene oxygenation process catalyzed by ultrafine transition-metal-containing Mn-based oxides with spinel or spinel-like structures (M-MnOx, M=Fe, Co, Ni, Cu). These M-MnOx catalysts were prepared by a low-temperature reduction method in 2-propanol-based solutions using tetra-n-butyl ammonium permanganate (TBAMnO4) as the Mn source, and they exhibited high Brunauer–Emmett–Teller surface areas (typically >400 m2 g?1). Using fluorene as the model substrate, the catalytic activities of M-MnOx and Mn3O4 were compared. The catalytic activities of M-MnOx were significantly higher than that of Mn3O4, which demonstrates that the incorporation of transition metals in manganese oxide was critical. Among the series of M-MnOx catalysts examined, Ni-MnOx exhibited the highest catalytic activity for the oxygenation. In addition, the catalytic activity of Ni-MnOx was higher than that of a physical mixture of Mn3O4 and NiO. Furthermore, Ni-MnOx exhibited a broad substrate scope with respect to various types of structurally diverse (hetero)alkylarenes (16 examples). The observed catalysis was truly heterogeneous, and the Ni-MnOx catalyst was reusable for the oxygenation of fluorene at least three times and its high catalytic performance was preserved, for example, the reaction rate, final product yield, and product selectivity. The present Ni-MnOx-catalyzed oxygenation process is possibly initiated by a single-electron oxidation process, and herein a plausible oxygen-transfer mechanism is proposed based on several pieces of experimental evidence.
Nakai, Satoru,Uematsu, Tsubasa,Ogasawara, Yoshiyuki,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
p. 1096 - 1106
(2018/01/15)

MeZnOMe-mediated reaction of aldehydes with Grignard reagents: A glance into nucleophilic addition/Oppenauer oxidation pathway
A novel organozincate of RMgX ?MeZnOMe ?LiCl type, formed in situ via transmetalation of Grignard reagent RMgBr ?LiCl with MeZnOMe, is shown to be an excellent organometallic species in the nucleophilic addition/Oppenauer oxidation of aldehydes to generate aromatic ketones in high yield. This transformation allows quick access to structurally diverse aryl, heteroaryl, benzyl and alkyl ketones with broad substrate scope and excellent functional group tolerance.
Fu, Ying,Ma, Xian-Zhen,Shi, Chun-Zhao,Shen, Tong,Du, Zhengyin
(2018/07/31)

Pd(II)-Catalyzed Denitrogenative and Desulfinative Addition of Arylsulfonyl Hydrazides with Nitriles
A Pd(II)-catalyzed denitrogenative and desulfinative addition of arylsulfonyl hydrazides with nitriles has been successfully achieved under mild conditions. This transformation is a new method for the addition reaction to nitriles with arylsulfonyl hydrazides as arylating agent, thus providing an alternative synthesis of aryl ketones. The reported addition reaction is tolerant to many common functional groups, and works well in the presence of electron-donating and electron-withdrawing substituents. Notably, the reported denitrogenative and desulfinative addition was also appropriate for alkyl nitriles, making this newly developed transformation attractive.
Meng, Mengting,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
p. 3275 - 3284
(2018/03/25)

Palladium-catalyzed synthesis of diaryl ketones from aldehydes and (hetero)aryl halides via C-H bond activation
We developed a palladium-catalyzed C-H transformation that enabled the synthesis of ketones from aldehydes and (hetero)aryl halides. The use of picolinamide ligands was key to achieving the transformation. Heteroaryl ketones, as well as diaryl ketones, were synthesized in good to excellent yields, even in gram-scale, using this reaction. Results of density functional theory (DFT) calculations support the C-H bond activation pathway.
Wakaki, Takayuki,Togo, Takaya,Yoshidome, Daisuke,Kuninobu, Yoichiro,Kanai, Motomu
p. 3123 - 3128
(2018/04/14)

Co (II)-C12 alkyl carbon chain multi-functional ionic liquid immobilized on nano-SiO2 nano-SiO2@CoCl3-C12IL as an efficient cooperative catalyst for C–H activation by direct acylation of aryl halides with aldehydes
Nano-silica supported ionic liquids composed of alkyl carbon chain and transition metal chlorides anions have been prepared and successfully applied as a heterogeneous catalyst in the direct aldehyde C-H activation. Catalytic results indicated that nano-SiO2 supported ionic liquid consisting C12 alkyl carbon chain and CoCl3 anion nano-SiO2@CoCl3-C12IL showed excellent catalytic properties with good to excellent yields towards the desired aryl ketones. The excellent recyclability of the supported catalyst, mild reaction conditions, low catalyst loading, and operational simplicity are the important features of this methodology.
Hu, Yu Lin,Wu, Ya Pan,Lu, Ming
(2017/09/25)

Co/NHPI-mediated aerobic oxygenation of benzylic C-H bonds in pharmaceutically relevant molecules
A simple cobalt(ii)/N-hydroxyphthalimide catalyst system has been identified for selective conversion of benzylic methylene groups in pharmaceutically relevant (hetero)arenes to the corresponding (hetero)aryl ketones. The radical reaction pathway tolerates electronically diverse benzylic C-H bonds, contrasting recent oxygenation reactions that are initiated by deprotonation of a benzylic C-H bond. The reactions proceed under practical reaction conditions (1 M substrate in BuOAc or EtOAc solvent, 12 h, 90-100 °C), and they tolerate common heterocycles, such as pyridines and imidazoles. A cobalt-free, electrochemical, NHPI-catalyzed oxygenation method overcomes challenges encountered with chelating substrates that inhibit the chemical reaction. The utility of the aerobic oxidation method is showcased in the multigram synthesis of a key intermediate towards a drug candidate (AMG 579) under process-relevant reaction conditions.
Hruszkewycz, Damian P.,Miles, Kelsey C.,Thiel,Stahl, Shannon S.
p. 1282 - 1287
(2017/02/10)

General Method for the Suzuki-Miyaura Cross-Coupling of Primary Amide-Derived Electrophiles Enabled by [Pd(NHC)(cin)Cl] at Room Temperature
A general, highly selective method for the room temperature Suzuki-Miyaura cross-coupling of commonly encountered primary benzamides is reported. A combination of site-selective N,N-di-Boc-activation (tert-butoxycarbonyl activation) of the amide nitrogen with practical air- and moisture-stable, well-defined, and highly reactive [Pd(NHC)(cin)Cl] (NHC = N-heterocyclic carbene; cin = cinnamyl) provides a highly effective route to biaryl ketones from primary amides in high yields. For the first time, a TON of >1000 has been achieved in amide acyl cross-coupling.
Lei, Peng,Meng, Guangrong,Ling, Yun,An, Jie,Nolan, Steven P.,Szostak, Michal
supporting information
p. 6510 - 6513
(2017/12/26)

A Nickel-Catalyzed Carbonyl-Heck Reaction
The use of transition-metal catalysis to enable the coupling of readily available organic molecules has greatly enhanced the ability of chemists to access complex chemical structures. In this work, an intermolecular coupling reaction that unites organotriflates and aldehydes is presented. A unique catalyst system is identified to enable this reaction, featuring a Ni0 precatalyst, a tridentate Triphos ligand, and a bulky amine base. This transformation provides access to a variety of ketone-containing products without the selectivity- and reactivity-related challenges associated with more traditional Friedel–Crafts reactions. A Heck-type mechanism is postulated, wherein the π bond of the aldehyde takes the role of the olefin in the insertion/elimination steps.
Vandavasi, Jaya Kishore,Hua, XiYe,Halima, Hamdi Ben,Newman, Stephen G.
p. 15441 - 15445
(2017/11/10)

A phosphine-free, heterogeneous palladium-catalyzed atom-efficient carbonylative cross-coupling of triorganoindiums with aryl halides leading to unsymmetrical ketones
The first phosphine-free heterogeneous palladium-catalyzed carbonylative cross-coupling of aryl halides with triorganoindiums has been developed that proceeds smoothly under 1 or 2.5 atm of carbon monoxide in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable unsymmetrical ketones with high atom-economy, good yield, and recyclability of the catalyst. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
You, Shengyong,Xiao, Ruian,Liu, Haiyi,Cai, Mingzhong
p. 13862 - 13870
(2017/11/27)

A phosphine-free, atom-efficient cross-coupling reaction of triorganoindiums with acyl chlorides catalyzed by immobilization of palladium(0) in MCM-41
The first phosphine-free heterogeneous palladium(0)-catalyzed cross-coupling of triorganoindiums with acyl chlorides has been developed that proceeds smoothly in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable aryl ketones and α,β-acetylenic ketones with high atom-economy and high yield. This phosphine-free heterogeneous palladium(0) catalyst can be easily prepared from commercially available reagents and recovered by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
Miao, Jiankang,Huang, Bin,Liu, Haiyi,Cai, Mingzhong
p. 42570 - 42578
(2017/09/11)

Palladium-catalyzed Suzuki-Miyaura coupling of aryl esters
The Suzuki-Miyaura coupling is among the most important C-C bond-forming reactions available due to its reliability, chemoselectivity, and diversity. Aryl halides and pseudohalides such as iodides, bromides, and triflates are traditionally used as the electrophilic coupling partner. The expansion of the reaction scope to nontraditional electrophiles is an ongoing challenge to enable an even greater number of useful products to be made from simple starting materials. Herein, we present how an NHC-based Pd catalyst can enable Suzuki-Miyaura coupling where the C(acyl)-0 bond of aryl esters takes on the role of electrophile, allowing the synthesis of various ketone-containing products. This contrasts known reactions of similar esters that provide biaryls via nickel catalysis. The underlying cause of this mechanistic divergence is investigated by DFT calculations, and the robustness of esters compared to more electrophilic acylative coupling partners is analyzed.
Halima, Taoufik Ben,Zhang, Wanying,Yalaoui, Imane,Hong, Xin,Yang, Yun-Fang,Houk, Kendall N.,Newman, Stephen G.
supporting information
p. 1311 - 1318
(2017/05/16)

Synthesis and structural characterization of Pd(II) thiosemicarbazonato complex: Catalytic evaluation in synthesis of diaryl ketones from aryl aldehydes and arylboronic acids
A simple route to synthesize triphenylphosphinopalladium(II) thiosemicarbazonato complex has been described. Elemental analysis, spectral (IR, NMR) and single crystal X-ray diffraction techniques were employed for the complete characterization of the complex. The latter was found to be effective catalyst for carbon–carbon cross-coupling reaction of aryl- and heteroarylboronic acids with aromatic and heteroaromatic aldehydes to form the corresponding diaryl ketones. The influence of reaction parameters such as solvent, base, reaction temperature and catalyst loading was also investigated.
Prabhu, Rupesh Narayana,Ramesh, Rengan
supporting information
p. 405 - 409
(2017/01/10)

Method for preparing diaryl ketone from aryl sulfonate
The invention discloses a method for preparing diaryl ketone from aryl sulfonate. The method includes following steps: in the presence of a catalyst and carbon monoxide, allowing aryl sulfonate and aryl boronic acid to react in an organic solvent; after reaction is finished, performing aftertreatment to obtain diaryl ketone. Aryl sufonate is adopted as an electrophilic reagent for Suzuki cross carbonylation coupling reaction, diaryl ketone is directly synthesized through carbon monoxide, aryl sulfonate and aryl boronic acid, reaction conditions are milk, functional groups are high in tolerance, a substrate is cheap and easy to get, and diaryl ketone can be prepared with high yield.
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Paragraph 0051

(2017/01/12)

Palladium-Catalyzed suzuki?Miyaura cross-Coupling of amides via site-Selective n?C bond cleavage by cooperative catalysis
Palladium-catalyzed Suzuki?Miyaura cross-coupling of primary benzamides enabled by a merger of site-selective N,N-di-Boc-activation and cooperative catalysis via N?C bond cleavage for the synthesis of biaryl ketones is reported. We present the synergistic combination of Lewis base and palladium catalysis as a concept to activate inert amide N?C bonds. The mild reaction conditions provide a direct route to structurally diverse ketones. The reaction tolerates a wide range of electrophilic functional groups. Considering the fundamental importance of primary amides as pharmaceutical and synthetic intermediates, the strategy has a potential for developing a diverse array of valuable amide N?C bond functionalization reactions by the synergistic merger of Lewis base and organometallic catalysis.
Meng, Guangrong,Shi, Shicheng,Szostak, Michal
p. 7335 - 7339
(2018/05/22)

Magnesium salt promoted tandem nucleophilic addition-Oppenauer oxidation of aldehydes with organozinc reagents
A magnesium salt promoted synthesis of ketones via tandem nucleophilic addition-Oppenauer oxidation of aldehydes using organozinc chemistry was demonstrated. Magnesium salts concomitantly generated via magnesium metal mediated organohalide zincation exhibit high efficacy for nucleophilic addition of organozinc reagents to aromatic aldehydes and thereafter Oppenauer oxidation whereby ketones are formed in high to excellent yields.
Fu, Ying,Zhao, Xing Ling,Hügel, Hulmet,Huang, Danfeng,Du, Zhengyin,Wang, Kehu,Hu, Yulai
supporting information
p. 9720 - 9724
(2016/10/31)

Carbonylative coupling of aryl tosylates/triflates with arylboronic acids under CO atmosphere
The carbonylative Suzuki-Miyaura reaction between aryl tosylates/triflates with arylboronic acid is herein reported, using base-free conditions and a balloon pressure of carbon monoxide. Under these conditions, unsymmetrical biaryl ketones were obtained in modest to excellent yields. This method was adapted to the synthesis of oxybenzone and ketoprofen in good yields under mild conditions.
Hao, Cheng Yi,Wang, Dan,Li, Ya Wei,Dong, Lin Lin,Jin, Ying,Zhang, Xiu Rong,Zhu, He Yun,Chang, Sheng
p. 86502 - 86509
(2016/09/23)

Palladium-Catalyzed Environmentally Benign Acylation
Recent trends in research have gained an orientation toward developing efficient strategies using innocuous reagents. The earlier reported transition-metal-catalyzed carbonylations involved either toxic carbon monoxide (CO) gas as carbonylating agent or functional-group-assisted ortho sp2 C-H activation (i.e., ortho acylation) or carbonylation by activation of the carbonyl group (i.e., via the formation of enamines). Contradicting these methods, here we describe an environmentally benign process, [Pd]-catalyzed direct carbonylation starting from simple and commercially available iodo arenes and aldehydes, for the synthesis of a wide variety of ketones. Moreover, this method comprises direct coupling of iodoarenes with aldehydes without activation of the carbonyl and also without directing group assistance. Significantly, the strategy was successfully applied to the synthesis n-butylphthalide and pitofenone.
Suchand, Basuli,Satyanarayana, Gedu
p. 6409 - 6423
(2016/08/16)

Phosphine-Free, Heterogeneous Palladium-Catalyzed Atom-Efficient Carbonylative Cross-Coupling of Triarylbismuths with Aryl Iodides: Synthesis of Biaryl Ketones
A novel and highly efficient heterogeneous palladium-catalyzed carbonylative cross-coupling of aryl iodides with triarylbismuths has been developed that proceeds smoothly at atmospheric CO pressure and provides a general and powerful tool for the preparation of various valuable biaryl ketones with high atom economy, good to excellent yield, and recyclability of the catalyst. The reaction is the first example of Pd-catalyzed carbonylative cross-coupling for the construction of biaryl ketones using triarylbismuths as substrates.
Hao, Wenyan,Liu, Haiyi,Yin, Lin,Cai, Mingzhong
p. 4244 - 4251
(2016/06/09)

Carbonylative Hiyama coupling of aryl halides with arylsilanes under balloon pressure of CO
An efficient protocol has been developed for the carbonylative Hiyama coupling of aryl halides using the cesium fluoride as a promoter by palladium-catalyzed in NMP. This protocol was applied to a wide variety of functionalized and hindered aryl iodides and bromides with arylsilanes, to afford the desired biaryl ketones in good to excellent yields.
Chang, Sheng,Jin, Ying,Zhang, Xiu Rong,Sun, Yong Bing
supporting information
p. 2017 - 2020
(2016/04/26)

A Convenient Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Halides with Formic Acid as the Carbon Monoxide Source
A practical palladium-catalyzed carbonylative Suzuki coupling of aryl halides under carbon monoxide gas-free conditions has been developed. Here, formic acid was utilized as the carbon monoxide source for the first time with acetic anhydride as the additive. A variety of diarylketones were produced in moderate to excellent yields from the corresponding aryl halides and arylboronic acids.
Qi, Xinxin,Jiang, Li-Bing,Li, Hao-Peng,Wu, Xiao-Feng
supporting information
p. 17650 - 17656
(2015/12/05)

Efficient synthetic route to bisaryl ketones via copper-catalyzed C-C triple bonds cleavage
An efficient copper-catalyzed aerobic synthesis of bisaryl ketones from 1,2-diarylalkynes via C-C triple bonds cleavage has been demonstrated. The aniline compounds were found to be crucial in our conditions and a plausible mechanism was put forward. This reaction constitutes a new transformation from 1,2-diarylalkynes into bisaryl ketones with a practical, neutral, and mild synthetic approach.
Li, Xiangguang,Huang, Wenzhong,Liang, Deqiang,Yuan, Lin,Ma, Yinhai,Gu, Lijun
p. 1045 - 1049
(2015/01/30)

Synthesis of α-Keto-1,2,3-triazoles through copper iodide catalyzed oxygenation
Benzyltriazoles have been catalytically oxidized by using CuI and tert-butyl hydroperoxide to yield phenyl(1H-1,2,3-triazol-4-yl)methanone derivatives in good yields at room temperature. Benzyltriazoles have been catalytically oxidized by using CuI and tert-butyl hydroperoxide to yield phenyl(1H-1,2,3-triazol-4-yl)methanone derivatives in good yields at room temperature. Copyright
Nawratil, Swantje,Grypioti, Maria,Menendez, Christophe,Mallet-Ladeira, Sonia,Lherbet, Christian,Baltas, Michel
p. 654 - 659
(2014/02/14)

Synthesis of α-keto-1,2,3-triazoles through copper iodide catalyzed oxygenation
Benzyltriazoles have been catalytically oxidized by using CuI and tert-butyl hydroperoxide to yield phenyl(1H-1,2,3-triazol-4-yl)methanone derivatives in good yields at room temperature.
Nawratil, Swantje,Grypioti, Maria,Menendez, Christophe,Mallet-Ladeira, Sonia,Lherbet, Christian,Baltas, Michel
p. 654 - 659
(2015/10/05)

Aerobic oxidation of secondary pyridine-derivative alcohols in the presence of carbon-supported noble metal catalysts
Pt/C and PtBi/C catalysts prepared on a synthetic mesoporous carbon were evaluated in the oxidation of secondary aromatic alcohols (1-phenylethanol, α-methyl or phenyl pyridinemethanol) with air in different dioxane/water mixtures at 100 °C under 10 bar air. The observed activity for all substrates over both types of catalysts was strongly improved with the addition of water to the dioxane solvent as a result of different interactions of the alcohols with the metallic surface in the apolar dioxane solvent or polar aqueous medium. A promoting effect of bismuth was observed for all substrates. However, the reaction rate was also dramatically influenced by the nature of the aromatic moiety, the nature of the α-group, and the position of the substituent on the pyridine moiety. As a general rule the reactivity was meta para ortho and the pyridine derivatives with a phenyl group were more reactive. α-Phenyl-2-pyridinemethanol was totally converted to 2-benzoylpyridine with a selectivity of 96% in dioxane/water 50/50 vol% in the presence of a 2.7% Pt-0.9% Bi/C. Nevertheless, platinum leaching was detected, which could be limited with the promotion by bismuth.
Frassoldati, Antonio,Pinel, Catherine,Besson, Michèle
p. 133 - 138
(2013/08/24)

Efficient, recyclable and phosphine-free carbonylative Suzuki coupling reaction using immobilized palladium ion-containing ionic liquid: Synthesis of aryl ketones and heteroaryl ketones
The carbonylative Suzuki coupling reaction of aryl and heteroaryl iodides was studied by using immobilized palladium ion-containing ionic liquid (ImmPd-IL). The protocol was optimized with respect to various reaction parameters, applied to a wide variety of substituted aryl/heteroaryl iodides and various aryl/heteroaryl boronic acids with different steric and electronic properties, and afforded the corresponding products in good to excellent yield. This is an efficient, heterogeneous catalyst which avoids the use of phosphine ligands, and its reusability was tested in up to four consecutive cycles. The recycled catalyst was characterized by using XPS analysis.
Khedkar, Mayur V.,Sasaki, Takehiko,Bhanage, Bhalchandra M.
p. 7791 - 7797
(2013/06/27)