cas 5395-79-9, 4-CHLORO-4'-METHYLBENZOPHENONE

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An Anthyridine-Based Pentanitrogen Donor Switches from Mono- To Tetradentate with Pd(II) Ions
Treatment of 5-phenyl-2,8-bis(2-pyridinyl)anthyridine (L) with (PPh3)2PdCl2 or (dppe)PdCl2 in the presence of a silver salt resulted in the formation of [trans-(PPh3)2PdLCl](BF4) (1a), [trans-(PPh3)2PdL(MeCN)](BF4)2 (1b), [trans-(PPh3)2PdLCl](PF6) (1c),or [cis-(dppe)PdLCl](BF4) (4), respectively. The ligand L in these complexes acts as a monodentate ligand with N(10) of anthyridine binding to the metal center. In the presence of PPh3, dinuclear complexes [Pd2L(CH3CN)2Cl2](BF4)2 (2) and [Pd2L(CH3CN)4](BF4)4 (3) readily underwent dechelation to yield 1a,b, respectively, whereas the reaction of 2 with dppe gave 4. On the other hand, treatment of 1a and 4 with S8 in the presence of a sufficient amount of palladium ions provided the corresponding dinuclear complex 2. Furthermore, this kind of substitution is also applicable with the Pd-Me complex [Pd2L(CH3CN)2Me2](BF4)2 (5), which could be prepared from complexation of L with 2 equiv of [(COD)Pd(CH3CN)Me](BF4). Thus, [trans-(PPh3)2PdLMe](BF4) (7) was obtained by the reaction of 5 with PPh3. However, the reaction of PPh3 with [Pd2L(CH3CN)2(MeCO)2](BF4)2 (6), a CO insertion product of 5, gave a messy result. The catalytic activity of these complexes in the Suzuki-Miyaura coupling of aryl halide with arylboronic acid under a CO atmosphere was investigated. Crystal structures of 1c, 4, 5, and 7 are reported to confirm their structural details. This work demonstrates the novelty of L as a hypodentate ligand toward palladium ions.
Liu, Shiuh-Tzung,Liu, Yi-Hung,Peng, Shie-Ming,Su, Bo-Kai
p. 4110 - 4119
(2021/12/17)

Tetra- And Dinuclear Palladium Complexes Based on a Ligand of 2,8-Di-2-pyridinylanthyridine: Preparation, Characterization, and Catalytic Activity
Complexation of L [L = 5-phenyl-2,8-di-2-pyridinyl-anthyridine] with [Pd(CH3CN)4](BF4)2 and [Pd(CH3CN)3Cl](BF4) in a molar ratio of 1:2 rendered the corresponding dinuclear complexes [Pd2L (CH3CN)4](BF4)4 (1) and [Pd2L (CH3CN)2Cl2](BF4)2 (2), respectively. However, treatment of L with (COD)PdCl2 followed by anion exchange yielded a tetranuclear complex [Pd4L3Cl4](PF6)4(4a). Structures of these complexes are characterized by both spectroscopy and X-ray crystallography. Interconversion of these three complexes was studied via the manipulation of stoichiometric ratio of ligand to metal precursor. The catalytic activity of these complexes for carbonylative Suzuki-Miyaura cross-coupling was investigated. Complex 2 shows an excellent catalytic activity on the reaction of aryl iodide with arylboronic acid in the presence of atmospheric pressure of CO to give the corresponding benzophenones.
Lin, Shih-Chieh Aaron,Liu, Shiuh-Tzung,Liu, Yi-Hung,Peng, Shie-Ming,Su, Bo-Kai
p. 2081 - 2089
(2021/07/26)

Supported Palladium-Catalyzed Carbonylative Synthesis of Diaryl Ketones from Aryl Bromides and Arylboronic Acids
A palladium supported on graphitic carbon nitride (Pd/g-C3N4) catalyzed carbonylative reaction of aryl bromides and arylboronic acids by has been developed for the construction of diaryl ketones. Using benzene-1,3,5-triyl triformate (TFBen) as the CO source, the reaction proceeded well to give various diaryl ketones in moderate to good yields.
Xu, Tiefeng,Wang, Qi,Yang, Zeyi,Yi, Lili,Wang, Jian-Shu,Lu, Wangyang,Ying, Jun,Wu, Xiao-Feng
supporting information
p. 2027 - 2030
(2021/06/21)

Selective oxidation of alkenes to carbonyls under mild conditions
Herein, a practical and sustainable method for the synthesis of aldehydes, ketones, and carboxylic acids from an inexpensive olefinic feedstock is described. This transformation features very sustainable and mild conditions and utilizes commercially available and inexpensive tetrahydrofuran as the additive, molecular oxygen as the sole oxidant and water as the solvent. A wide range of substituted alkenes were found to be compatible, providing the corresponding carbonyl compounds in moderate-to-good yields. The control experiments demonstrated that a radical mechanism is responsible for the oxidation reaction.
Huo, Jie,Xiong, Daokai,Xu, Jun,Yue, Xiaoguang,Zhang, Pengfei,Zhang, Yilan
supporting information
p. 5549 - 5555
(2021/08/16)

Photo-induced oxidative cleavage of C-C double bonds of olefins in water
The carbonyl compounds, synthesized by the oxidative cleavage of their corresponding olefins, are of great significance in organic synthesis, especially aryl ketones. We have developed a gentle and effective protocol, using acid red 94 as the organic metal-free photocatalyst, O2 as the oxidant, and water as the solvent. Under visible light irradiation, aryl ketone derivatives were obtained in moderate to excellent yields, showing good economic and environmental advantages.
Zhang, Yilan,Yue, Xiaoguang,Liang, Chenfeng,Zhao, Jianming,Yu, Wenbo,Zhang, Pengfei
supporting information

(2021/08/27)

Self-Assembled 2,3-Dicyanopyrazino Phenanthrene Aggregates as a Visible-Light Photocatalyst
In this study, 2,3-dicyanopyrazino phenanthrene (DCPP), a commodity chemical that can be prepared at an industrial scale, was used as a photocatalyst in lieu of Ru or Ir complexes in C-X (X = C, N, and O) bond-forming reactions under visible-light irradiation. In these reactions, [DCPP]n aggregates were formed in situ through physical π-πstacking of DCPP monomers in organic solvents. These aggregates exhibited excellent photo- and electrochemical properties, including a visible light response (430 nm), long excited-state lifetime (19.3 μs), high excited-state reduction potential (Ered([DCPP]n*/[DCPP]n·-) = +2.10 V vs SCE), and good reduction stability. The applications of [DCPP]n aggregates as a versatile visible-light photocatalyst were demonstrated in decarboxylative C-C cross-coupling, amidation, and esterification reactions.
He, Min,Yu, Xiaoqiang,Wang, Yi,Li, Fei,Bao, Ming
p. 5016 - 5025
(2021/04/12)

Selective Oxidation of Alkylarenes to the Aromatic Ketones or Benzaldehydes with Water
Here a palladium-catalyzed oxidation method for converting alkylarenes into the aromatic ketones or benzaldehydes with water as the only oxygen donor is reported. This C-H bond oxidation functionalization does not require other oxidants and hydrogen accep
Du, Jihong,Duan, Baogen,Liu, Kun,Liu, Renhua,Yu, Feifei,Yuan, Yongkun,Zhang, Chenyang,Zhang, Jin
supporting information

(2022/02/09)

Carbonylative Suzuki coupling reactions catalyzed by ONO pincer–type Pd(II) complexes using chloroform as a carbon monoxide surrogate
Benzoylhydrazone Schiff base–ligated three new ONO pincer–type palladium(II) complexes, [(PdL1(PPh3)] (1), [(PdL2(PPh3)] (2), and [(PdL3(PPh3)] (3), were synthesized by the reaction of the respective ligand, N-(2-hydroxybenzylidene)benzohydrazide (HL1), N-(2-hydroxy-3-methoxybenzylidene)benzohydrazide (HL2), or N-(5-bromo-2-hydroxybenzylidene) benzohydrazide (HL3), with Pd(OAc)2 and PPh3 in methanol and isolated as air-stable reddish-orange crystalline solids in high yields (78%–83%). All three complexes were fully characterized by elemental analysis, Fourier-transform infrared spectroscopy, UV–Visible, 1H nuclear magnetic resonance (NMR), 13C{1H} NMR, and 31P{1H} NMR spectroscopic studies. The molecular structure of all three complexes was established unambiguously by single-crystal X-ray diffraction studies which revealed a distorted square planar geometry of all three complexes. The ONO pincer–type ligands occupied three coordination sites at the palladium, while the fourth site is occupied by the monodentate triphenylphosphine ligand. The catalytic potential of all three complexes was explored in the carbonylative Suzuki coupling of aryl bromides and iodides with arylboronic acids to yield biaryl ketones, using CHCl3 as the source of carbonyl. The reported protocol is convenient and safe as it obviates the use of carbon monoxide (CO) balloons or pressured CO reactors which are otherwise needed for the carbonylation reactions. The methodology has been successfully applied to the synthesis of two antineoplastic drugs, namely, phenstatin and naphthylphenstatin, in good yields (81% and 85%, respectively). Under the optimized reaction conditions, complex 2 exhibited the best catalytic activity in the carbonylative Suzuki couplings. The reported catalysts have wide reaction scope with good functional group tolerance. All catalysts could be retrieved from the reaction after completion and recycled up to three times with insignificant loss in the catalytic activity.
Layek, Samaresh,Agrahari, Bhumika,Ganguly, Rakesh,Das, Parthasarathi,Pathak, Devendra D.
(2020/01/25)

Palladium on magnetic Irish moss: A new nano-biocatalyst for suzuki type cross-coupling reactions
A novel heterogeneous magnetic palladium nano-biocatalyst was designed by utilizing Irish moss, a family of sulfated polysaccharides extracted from algae, as a natural biopolymer. This magnetic Irish moss decorated with palladium (Pd–Fe3O4@IM) to form a biomagnetic catalytic system was synthesized and well characterized by FT–IR analysis, X-ray powder diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic absorption spectroscopy and transmission electron microscopy. The catalyst was stable to air and moisture and displayed high catalytic activity in ligand-free Suzuki–Miyaura cross-coupling reactions conducted under green chemistry reaction conditions. The aromatic ketones are produced by the cross-coupling reaction between acid chlorides and aryl boronic acid derivatives in high yields.
Dolatkhah, Zahra,Javanshir, Shahrzad,Bazgir, Ayoub,Hemmati, Behnaz
(2019/05/17)

Isinglass–palladium as collagen peptide–metal complex: a highly efficient heterogeneous biocatalyst for Suzuki cross-coupling reaction in water
The class of bio-nanocatalysts (BNCs) is an evolving innovation that synergistically assimilates advanced nanotechnology with biotechnology. BNCs promote green processes due to their low consumption of chemicals and the absence of toxic by-products. Isinglass (IG), from the Dutch huizenblaas (sturgeon bladder), containing approximately 98% protein collagen, is used to support the immobilization of palladium (Pd) nanoparticles. This process leads to Pd/IG composite, a new class of heterogeneous collagen peptides–metal BNCs that exhibit high catalytic activity and reusability for ligand-free Suzuki coupling reaction in water. Additionally, these BNCs are obviously active in the cross-coupling reaction between acid chloride and arylboronic acid, producing a high yield of the desired ketones. The synthesized BNCs are well-characterized by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma, and transmission electron microscopy.
Dolatkhah, Zahra,Javanshir, Shahrzad,Bazgir, Ayoob
p. 1473 - 1481
(2019/06/11)

Ligand-free Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Iodides in Aqueous CH3CN with Sub-stoichiometric Amount of Mo(CO)6 as CO Source
A new method for the synthesis of diaryl and heterodiaryl ketones has been established based on the palladium-catalyzed carbonylative Suzuki coupling approach with sub-stoichiometric Mo(CO)6 as CO source. Using 0.5 mol% of Pd(TFA)2 as catalyst, 0.5 equivalent of Mo(CO)6 as solid carbonyl reagent and 3 equivalent of K3PO4 as base, a wide range of functionalized (hetero)aryl iodides and (hetero)aryl boronic acids could smoothly proceed the carbonylative cross-coupling reaction in aqueous CH3CN at 50 °C, affording the corresponding ketones in good to excellent yields. The newly developed method was easy to operate under mild conditions with high efficiency. (Figure presented.).
Sun, Nan,Sun, Qingxia,Zhao, Wei,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
p. 2117 - 2123
(2019/03/28)

Sequential Organozinc Formation and Negishi Cross-Coupling of Amides Catalysed by Cobalt Salt
Herein, a cobalt-catalysed Negishi-type cross-coupling of amide derivatives is described. Apart from being the first example of cobalt-catalysed Negishi-type coupling of amides, the process described employs a unique, simple, and cheap catalytic system to perform both the organozinc formation and the Negishi-type coupling. Indeed, the same cobalt(II) bromide salt used to form the arylzinc species from aryl bromides is then re-used to perform the cross coupling of this resulting arylzinc with N-benzoyl glutarimides at room temperature. The main advantages of the reaction presented are its robustness and ease of use. Indeed, the reactions of organozinc formation and Negishi-type coupling are performed without precautions toward water or oxygen. (Figure presented.).
Dorval, Céline,Dubois, Elodie,Bourne-Branchu, Yann,Gosmini, Corinne,Danoun, Grégory
supporting information
p. 1777 - 1780
(2019/02/26)

Pd-Catalyzed Suzuki–Miyaura Cross-Coupling of Arylboronic Acids and α-Iminonitriles through C–CN Bond Activation
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
supporting information
p. 4769 - 4775
(2018/09/06)

Palladium-Catalyzed Ligand-Free Decarboxylative Coupling of α- Oxocarboxylic Acid with Aryl Diazonium Tetrafluoroborate: An Access to Unsymmetrical Diaryl Ketones
Diaryl ketones are of much importance in organic synthesis as versatile intermediates and in industry for their useful properties. A mild and efficient palladium-catalyzed traditional ligand-free decarboxylative coupling of aryl α-keto carboxylic acid with aryl diazonium fluoroborate has been developed. A series of unsymmetrical diaryl ketones has been synthesized in moderate to good yields using this procedure. A radical pathway involving the acyl radical has been suggested.
Panja, Subir,Maity, Pintu,Ranu, Brindaban C.
p. 12609 - 12618
(2018/10/20)

Design and synthesis of new benzophenone derivatives with in vivo anti-inflammatory activity through dual inhibition of edema and neutrophil recruitment
A series of novel benzophenone derivatives containing a thiazole heterocyclic nucleus were designed by molecular hybridization. Molecular docking studies have demonstrated the inhibitory potential of the designed compounds against cyclooxygenase (COX) isoenzymes. These compounds were synthesized, characterized, and evaluated for their anti-inflammatory properties by the croton oil-induced ear edema assay to examine their effect on both prostaglandin (PG) production and neutrophils recruitment. The thiazole derivatives displayed a potent effect in terms of reducing ear edema. The analysis suggested that the presence of 4-phenyl-2-hydrazinothiazole and the absence of C40-OCH3 on the benzophenone derivative structure are strongly related to the inhibition of PG production. In addition, the derivatives 2e, 3a and 3c concomitantly inhibit PG production and neutrophil recruitment, which may be a mechanism of action better than of common NSAIDs due to their inability to inhibit the neutrophil recruitment. Thus, these compounds can be considered as potential lead compounds toward the development of new anti-inflammatory drugs with an innovating mechanism of action.
Januario, Jaqueline P.,De Souza, Thiago B,Lavorato, Stefania N.,Maiolini, Tatiane C. S.,Domingos, Olívia S,Baldim, Jo?o L,Folquitto, Laís R. S.,Soares, Marisi G.,Chagas-Paula, Daniela A,Dias, Danielle F,Dos Santos, Marcelo H
(2018/08/04)

A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation
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.
p. 193 - 199
(2018/02/06)

The second aryl ketone compounds
The invention provides a synthetic method for diaryl ketone compounds. The method comprises the following steps: adding ester derivatives of raw material diaryl methanol, DDQ and water into an organic solvent, carrying out stirring, then carrying out heating to 110 to 140 DEG C and carrying out reaction for 0.5 to 12 h, and subjecting obtained reaction liquid to after-treatment so as to obtain the diaryl ketone compounds, wherein the ester derivatives of the raw material diaryl methanol have a structural formula as shown in a formula (V), (VI), (VII) or (VIII), and one-to-one correspondingly obtained products have the structural formula as shown in the formula (I), (II), (III) or (IV). The synthetic method for the diaryl ketone compounds provided by the invention has the advantages of simple, convenient and safe operation, mild reaction conditions and high product selectivity.
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Paragraph 0049; 0050

(2017/08/24)

Reactions catalyzed by a binuclear copper complex: Selective oxidation of alkenes to carbonyls with O2
Terminal alkenes were selectively cleaved into ketones and aldehydes catalyzed by a binuclear copper catalyst bearing a simple salicylate ligand with O2 as the oxidant. The reaction was carried out under an atmosphere of O2 (balloon) with 0.5 mol% of catalyst and could be performed on a gram scale, providing a convenient and practical method for the cleavage of terminal alkenes into carbonyl compounds.
Liu, Yuxia,Xue, Dong,Li, Chaoqun,Xiao, Jianliang,Wang, Chao
p. 5510 - 5514
(2017/12/08)

Transition metal-free Suzuki type cross-coupling reaction for the synthesis of dissymmetric ketones
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
supporting information
p. 3201 - 3204
(2017/07/27)

Synthesis technology of diarylketone derivative
The invention relates to a synthesis technology of a diarylketone derivative. The technology comprises the following steps: adding aryl halide, aryl boronic acid, trichloromethane, an iron-containing catalyst, an inorganic base, an activator and a solvent into a reaction container, and stirring and reacting above substances at 100 -180 DEG C for 12-15 h; diluting the obtained product with water after the above reaction is finished, carrying out ethyl acetate extraction three times, mixing obtained organic phases, and carrying out rotary evaporation to obtain a crude product; and carrying out petroleum ether/ether column chromatography on the crude product to obtain the purified diarylketone derivative. The technology has the advantages of mild technologic conditions, no dangerous gases or solvents, high reaction selectivity and high product yield, and is suitable for being promoted and used.
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Paragraph 0030-0032

(2017/09/01)

Diaryl a ketone compound catalytic oxidation synthesis method
The invention provides a catalytic oxidation synthesis method of a diaryl ketone compound. In an organic solvent, ester derivatives of diaryl methanol are used as reaction substrates, DDQ and TBN are used as catalysts, oxygen is used as an oxidant, so as to react for 1 to 12 h under the conditions of oxygen pressure of 0.1 to 0.4 MPa and temperature of 110 to 140 DEG C, and post processing is performed on reaction liquid, so as to obtain a product of the diaryl ketone compound; structural formulas of the ester derivatives of the diaryl methanol as the reaction substrates are shown in the formulas (V), (VI), (VII) or (VIII), and structural formulas of products which are correspondingly obtained one by one are shown in the formulas (I), (II), (III) or (IV). The catalytic oxidation synthesis method has the advantages of simplicity, convenience and safety in operation, mild reaction condition, high product selectivity and environmental friendliness.
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Paragraph 0049-0050

(2020/05/05)

Iron-catalyzed carbonylation of aryl halides with arylborons using stoichiometric chloroform as the carbon monoxide source
A general iron-catalyzed carbonylative Suzuki-Miyaura coupling of aryl halides with arylborons is reported, using stoichiometric CHCl3 as the CO source. The high efficiency, economy, selectivity, and operational simplicity of this transformation make this method a valuable tool in organic synthesis. Importantly, the presented strategy allows effective 13C labeling simply by using the commercially available 13C-labeled CHCl3. On the basis of the initial mechanistic exploration, an aryl radical intermediate is proposed in the present carbonylation process.
Zhao, Hongyuan,Du, Hongyan,Yuan, Xiaorong,Wang, Tianjiao,Han, Wei
supporting information
p. 5782 - 5787
(2016/11/06)

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)

A versatile approach for the synthesis of para -substituted arenes via palladium-catalyzed C-H functionalization and protodecarboxylation of benzoic acids
While a great number of ortho C-H functionalization reactions have been developed and several breakthroughs have been achieved in meta C-H activation, para C-H functionalization is still in its infancy stage. In this article, a versatile strategy for the synthesis of para-substituted arenes has been developed via a tandem process consisting of palladium-catalyzed C-H functionalization and subsequent copper-catalyzed protodecarboxylation of benzoic acids. Both electron-withdrawing and electron-donating functionalities can be introduced into the para positions of arenes bearing a variety of substituents.
Pan, Shulei,Zhou, Bo,Zhang, Yanghui,Shao, Changdong,Shi, Guangfa
supporting information
p. 277 - 281
(2016/01/20)

Visible light mediated efficient oxidative benzylic sp3 C-H to ketone derivatives obtained under mild conditions using O2
A photooxygenation of benzylic sp3 C-H reaction has been demonstrated using O2 mediated by visible light. This protocol provides a simple and mild route to obtain ketones from benzylic sp3 C-H bonds. Various benzylic sp3 C-H bonds can be transformed into the desired ketone derivatives in moderate to good yields. The 18O2 labelling experiments demonstrated that the oxygen introduced into ketone originated from dioxygen. A plausible mechanism has been proposed accordingly.
Yi, Hong,Bian, Changliang,Hu, Xia,Niu, Linbin,Lei, Aiwen
p. 14046 - 14049
(2015/09/15)

Room-Temperature Decarboxylative Couplings of α-Oxocarboxylates with Aryl Halides by Merging Photoredox with Palladium Catalysis
Enabled by merging iridium photoredox catalysis and palladium catalysis, α-oxocarboxylate salts can be decarboxylatively coupled with aryl halides to generate aromatic ketones and amides at room temperature. DFT calculations suggest that this reaction proceeds through a Pd0-PdII-PdIII pathway, in which the PdIII intermediate is responsible for reoxidizing IrII to complete the IrIII-IrIII-IrII photoredox cycle. Like a mergin': Enabled by merging iridium photoredox catalysis and palladium catalysis, palladium-catalyzed decarboxylative coupling of α-oxocarboxylates with aryl halides can proceed at room temperature. DFT calculations suggest that a Pd0-PdII-PdIII catalytic cycle is merged with an IrIII-IrIII-IrII photoredox cycle, in which PdIII is responsible for oxidizing IrII to complete the photoredox cycle.
Cheng, Wan-Min,Shang, Rui,Yu, Hai-Zhu,Fu, Yao
supporting information
p. 13191 - 13195
(2015/09/15)

DDQ/tert-Butyl nitrite-catalyzed aerobic oxidation of diarylmethane sp3 C-H bonds
An efficient 2,3-dichloro-5,6-dicyano-1,4-benzoquinone/tert-butyl nitrite-catalyzed aerobic oxidation of diarylmethane sp3 C-H bonds in the presence of acetic acid has been developed. Under the optimal reaction conditions, a number of diarylmethanes can be directly converted to their corresponding diarylketones in good to excellent yields. In addition, a plausible reaction mechanism has been investigated.
Ma, Jiaqi,Hu, Zhiming,Li, Meichao,Zhao, Weijuan,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Shen, Zhenlu
p. 6733 - 6739
(2015/08/24)

Agglomeration of Pd0 nanoparticles causing different catalytic activities of Suzuki carbonylative cross-coupling reactions catalyzed by PdII and Pd0 immobilized on dopamine-functionalized magnetite nanoparticles
Solvent-dispersible magnetite nanoparticles (Fe3O4) end-functionalized with amino groups were successfully prepared by a facile one-pot template-free method to immobilize PdII and Pd0 using a metal adsorption and reduction procedure. They were characterized by TEM, XRD, XPS, FT-IR and VSM. Interestingly, the PdII catalyst exhibited better catalytic activity for carbonylative cross-coupling reactions than the Pd0 catalyst. According to the catalytic activities of a variety of arylboronic acids and aryl iodides catalyzed by two kinds of Pd catalysts, the proposed reaction mechanism of Suzuki carbonylative cross-coupling reactions using the Pd catalyst was also inferred. More importantly, agglomeration of Pd0 nanoparticles was obviously observed in the TEM images of the catalysts after reactions. Therefore, agglomeration of Pd0 nanoparticles should be considered as a significant reason for different catalytic activities of the reactions catalyzed by immobilized PdII and Pd0 catalysts. Furthermore, the PdII catalyst revealed high efficiency and stability during recycling stages.
Long, Yu,Liang, Kun,Niu, Jianrui,Tong, Xin,Yuan, Bing,Ma, Jiantai
p. 2988 - 2996
(2015/04/14)

Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: Scope, limitations, and mechanistic studies
A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate. The palladium(II) intermediates detected by ESI-MS and the DFT calculations provide a detailed understanding of the catalytic cycle. (Figure Presented).
Skillinghaug, Bobo,Sk?ld, Christian,Rydfjord, Jonas,Svensson, Fredrik,Behrends, Malte,S?vmarker, Jonas,Sj?berg, Per J. R.,Larhed, Mats
p. 12018 - 12032
(2015/01/16)

Stabilizing PdII on hollow magnetic mesoporous spheres: A highly active and recyclable catalyst for carbonylative cross-coupling and Suzuki coupling reactions
A hollow magnetic mesoporous silica sphere (HMMS) catalyst has been synthesized using polystyrene microspheres as a chemical template. The catalyst was characterized by TEM, XRD, XPS and vibrating sample magnetometry (VSM). The catalyst shows high activity for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids and Suzuki coupling reactions. The newly developed catalyst is easy to recover by magnetic separation from the liquid phase of the reaction and can be recycled. Importantly, the catalyst revealed high efficiency and high stability under the reaction conditions and during recycling stages.
Niu, Jianrui,Liu, Mengmeng,Wang, Peng,Long, Yu,Xie, Miao,Li, Rong,Ma, Jiantai
p. 1471 - 1476
(2014/05/06)

Preparation of recoverable Fe3O4/PPy-PdII catalysts for carbonylative cross-coupling reactions
The hierarchical porous Fe3O4/PPy-PdII catalyst has been synthesized using Fe3O4 microspheres both as chemical template and oxidant source under sonication. The catalyst characterized by TEM, XRD, FT-IR, XPS and vibrating sample magnetometry (VSM). The catalyst showed high reactivity for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids. This newly developed catalyst could be easily recovered and revealed high efficiency and high stability under the reaction conditions and during recycling stages.
Niu, Jianrui,Xie, Miao,Zhu, Xiaohang,Long, Yu,Wang, Peng,Li, Rong,Ma, Jiantai
p. 247 - 252
(2014/07/07)

Preparation of recoverable Fe3O4@PANI-PdII core/shell catalysts for Suzuki carbonylative cross-coupling reactions
We report on the synthesis, characterization and catalytic performance of a palladium-based superparamagnetic catalyst of Fe3O 4@polyaniline core/shell microspheres (Fe3O 4@PANI-PdII). The material was characterized by TEM, FT-IR, vibrating sample magnetometry (VSM), XRD, and XPS. The catalyst showed high activity for the carbonylative cross-coupling reaction of aryl iodide with arylboronic acid. Moreover it could selectively reduce the formation of a direct-coupling product. The newly developed catalyst could be recovered from the liquid phase easily by magnetic separation and recycled 5 times without any significant loss of activity. the Partner Organisations 2014.
Zhu, Xiaohang,Niu, Jianrui,Zhang, Fengwei,Zhou, Jinghui,Li, Xinzhe,Ma, Jiantai
p. 4622 - 4627
(2014/10/15)

Tetraethylammonium iodide catalyzed synthesis of diaryl ketones via the merger of cleavage of C-C double bonds and recombination of aromatic groups
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
p. 46494 - 46497
(2014/12/10)

Chloro-ruthenium complexes with carbonyl and N-(aryl)pyridine-2-aldimines as ancillary ligands. Synthesis, characterization and catalytic application in C-C cross-coupling of arylaldehydes with arylboronic acids
Reaction of N-(aryl)pyridine-2-aldimines (L-R, R = OCH3, CH 3, H, Cl and NO2) with [Ru(CO)2Cl 2]n in refluxing ethanol affords a group of complexes of type [Ru(L-R)(CO)2Cl2]. In these complexes the diimine ligands (L-R) are coordinated to the metal center as NN-donors forming five-membered chelate rings, the carbonyls are mutually cis and the two chlorides are trans. Crystal structure of [Ru(L-OCH3)(CO) 2Cl2] has been determined. All the complexes show characteristic 1H NMR signals, and in dichloromethane solution they display intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on the complexes shows an irreversible oxidation of the metal center within 1.15-1.23 V vs SCE, and reduction(s) of the diimine ligand within -0.70 to -0.96 V vs SCE. The [Ru(L-R)(CO)2Cl2] complexes efficiently catalyze cross-coupling of arylaldehydes with arylboronic acids yielding diaryl ketones.
Dey, Bikash Kali,Dutta, Jayita,Drew, Michael G.B.,Bhattacharya, Samaresh
p. 176 - 184
(2014/01/06)

A phosphane-free, atom-efficient cross-coupling reaction of triarylbismuths with acyl chlorides catalyzed by MCM-41-immobilized palladium complex
The first phosphane-free, heterogeneous, atom-efficient cross-coupling reaction of triarylbismuths and acyl chlorides was achieved in N-methylpyrrolidone (NMP) with Bu3N as the base at 80 °C in the presence of 1.5 mol-% MCM-41-immobilized bidentate nitrogen palladium complex [MCM-41-2N-Pd(OAc)2, MCM = mobile crystalline material] to yield a variety of unsymmetrical biaryl ketones in good to excellent yields. This heterogeneous palladium catalyst exhibited a high activity, which was similar to that of Pd(PPh3)4. The catalyst can be recovered by a simple filtration of the reaction solution and recycled in at least 10 consecutive trials without any decrease in activity. Our system not only avoids the use of phosphane ligands, but also solves the basic problem of palladium catalyst recovery and reuse. The first phosphane-free, heterogeneous, atom-efficient cross-coupling reaction of triarylbismuth compounds and acyl chlorides was achieved in N-methylpyrrolidone with Bu3N as the base at 80 °C in the presence of 1.5 mol-% MCM-41-immobilized bidentate nitrogen palladium complex [MCM-41-2N-Pd(OAc)2] to yield a variety of unsymmetrical biaryl ketones in good to excellent yields. Copyright
Zhao, Hong,Yin, Lin,Cai, Mingzhong
p. 1337 - 1345
(2013/04/10)

Catalytic Friedel-Crafts acylation: Magnetic nanopowder CuFe 2O4 as an efficient and magnetically separable catalyst
Catalytic regioselective Friedel-Crafts acylation of an array of anisoles/arenes with various acid chlorides using 5-20 mol % of magnetic nanopowder CuFe2O4 is reported. Unlike the conventional Friedel-Crafts reactions, which are catalyzed by moisture sensitive homogeneous catalysts/promoters, the nanopowder CuFe2O4 catalyst is moisture insensitive and the product/ketone-catalyst isolation is easily achieved using the magnetic properties of CuFe2O4.
Parella, Ramarao,Naveen,Kumar, Amit,Babu, Srinivasarao Arulananda
p. 1738 - 1742
(2013/03/28)

Preparation of Recoverable Pd Catalysts for Carbonylative Cross-Coupling and Hydrogenation Reactions
We report on the synthesis, characterization and catalytic performance of new, supported PdII and Pd0 catalysts. The catalysts are characterized by TEM, XRD, FTIR, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. The catalysts are found to be active in both forms, PdII and Pd0, for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids, and for the hydrogenation of aromatic nitro- and unsaturated compounds. The newly developed catalysts are prepared by a synthetic strategy that is similar to the one used for other supported catalysts but are easier to recover-they can be recycled by magnetic separation from liquid phase reactions-and can be used for at least 5 consecutive trials without any decrease in activity.
Niu, Jian-Rui,Huo, Xing,Zhang, Feng-Wei,Wang, Hai-Bo,Zhao, Ping,Hu, Wu-Quan,Ma, Jiantai,Li, Rong
p. 349 - 354
(2013/03/13)

Penicillin inhibitors of purple acid phosphatase
Purple acid phosphatases (PAPs) are binuclear metallohydrolases that have a multitude of biological functions and are found in fungi, bacteria, plants and animals. In mammals, PAP activity is linked with bone resorption and over-expression can lead to bone disorders such as osteoporosis. PAP is therefore an attractive target for the development of drugs to treat this disease. A series of penicillin conjugates, in which 6-aminopenicillanic acid was acylated with aromatic acid chlorides, has been prepared and assayed against pig PAP. The binding mode of most of these conjugates is purely competitive, and some members of this class have potencies comparable to the best PAP inhibitors yet reported. The structurally related penicillin G was shown to be neither an inhibitor nor a substrate for pig PAP. Molecular modelling has been used to examine the binding modes of these compounds in the active site of the enzyme and to rationalise their activities.
Faridoon,Hussein, Waleed M.,Ul Islam, Nazar,Guddat, Luke W.,Schenk, Gerhard,McGeary, Ross P.
supporting information; experimental part
p. 2555 - 2559
(2012/05/20)

Facile preparation of aromatic ketones from aromatic bromides and arenes with aldehydes
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
experimental part
p. 1436 - 1442
(2012/03/09)

Practical one-pot preparation of ketones from aryl and alkyl bromides with aldehydes and DIH via Grignard reagents
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
experimental part
p. 6557 - 6564
(2012/08/27)

Analogues of fenarimol are potent inhibitors of trypanosoma cruzi and are efficacious in a murine model of chagas disease
We report the discovery of nontoxic fungicide fenarimol (1) as an inhibitor of Trypanosoma cruzi (T. cruzi), the causative agent of Chagas disease, and the results of structure-activity investigations leading to potent analogues with low nM IC50s in a T. cruzi whole cell in vitro assay. Lead compounds suppressed blood parasitemia to virtually undetectable levels after once daily oral dosing in mouse models of T. cruzi infection. Compounds are chemically tractable, allowing rapid optimization of target biological activity and drug characteristics. Chemical and biological studies undertaken in the development of the fenarimol series toward the goal of delivering a new drug candidate for Chagas disease are reported.
Keenan, Martine,Abbott, Michael J.,Alexander, Paul W.,Armstrong, Tanya,Best, Wayne M.,Berven, Bradley,Botero, Adriana,Chaplin, Jason H.,Charman, Susan A.,Chatelain, Eric,Von Geldern, Thomas W.,Kerfoot, Maria,Khong, Andrea,Nguyen, Tien,McManus, Joshua D.,Morizzi, Julia,Ryan, Eileen,Scandale, Ivan,Thompson, R. Andrew,Wang, Sen Z.,White, Karen L.
supporting information; experimental part
p. 4189 - 4204
(2012/07/27)

Solvent-free C-benzoylation and N-benzoylation reactions using
An ecofriendly and efficient microwave-irradiated solvent-free benzoylation method was developed. The procedure for C-benzoylation used 50 mol% AlCl 3 as a Lewis acid catalyst at 130°C and was completed in 10 min. The isolated yield was between 71% and 100%. N-benzoylation was conducted in a catalyst-free environment at 130°C in 10 min. The isolated yield was between 80% and 100%. Taylor & Francis Group, LLC.
Al-Masum, Mohammad,Wai, Maya Chen,Dunnenberger, Henry
experimental part
p. 2888 - 2898
(2011/09/13)

A phosphine-free carbonylative cross-coupling reaction of aryl iodides with arylboronic acids catalyzed by immobilization of palladium in MCM-41
The phosphine-free heterogeneous carbonylative cross-coupling of aryl iodides with arylboronic acids under an atmospheric pressure of carbon monoxide was achieved in anisole at 80 °C in the presence of a 3-(2-aminoethylamino) propyl-functionalized MCM-41-immobilized palladium(ii) complex [MCM-41-2N-Pd(ii)], yielding a variety of unsymmetrical biaryl ketones in good to high yield. This heterogeneous palladium catalyst exhibited higher activity and selectivity than PdCl2(PPh3)2, can be recovered and recycled by a simple filtration of the reaction solution, and used for at least 10 consecutive trials without any decrease in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
Cai, Mingzhong,Peng, Jian,Hao, Wenyan,Ding, Guodong
experimental part
p. 190 - 196
(2011/03/20)

Development of decarboxylative coupling processes for the synthesis of azomethines and ketones
A bimetallic catalyst system has been developed that allows the synthesis of azomethines by a one-pot three-component decarboxylative coupling, starting from simple, nontoxic precursors, i.e. potassium α-oxo carboxylates, aryl halides and primary amines. In the presence of 15 mol-% copper/phenanthroline and 1 mol-% Pd/dppf, a wide range of valuable imines is conveniently accessible in high yields at 100 °C, an unprecedentedly low temperature for redox-neutral decarboxylative cross-coupling reactions. Hydrogenation of the azomethine products leads to secondary amines. Alternatively, they can be hydrolyzed in situ to aryl ketones. The resulting ketone synthesis via azomethine intermediates is also of interest as it gives higher yields at much lower temperatures than the direct decarboxylative coupling of α-oxo carboxylates with aryl halides. A convenient synthesis of azomethines by a one-pot three-component decarboxylative coupling, starting from potassium α-oxo carboxylates, aryl halides and primary amines is described. Combined with in situ hydrolysis, ketones are obtained. Thisamine-mediated ketone synthesis gives higher yields at lower temperatures than the direct coupling of α-oxo carboxylates. Copyright
Collet, Florence,Song, Bingrui,Rudolphi, Felix,Goossen, Lukas J.
experimental part
p. 6486 - 6501
(2011/12/05)

Synthesis of ketones by palladium-catalysed desulfitative reaction of arylsulfinic acids with nitriles
Palladium-catalysed desulfitative addition of arylsulfinic acids to aryl and alkyl nitriles with 2,2′-bipyridine as a ligand afforded a variety of aryl ketones via hydrolysis of ketimine intermediates.
Miao, Tao,Wang, Guan-Wu
p. 9501 - 9503
(2011/10/01)

Towards applications of metal-organic frameworks in catalysis: Friedel-Crafts acylation reaction over IRMOF-8 as an efficient heterogeneous catalyst
A highly porous metal-organic framework (IRMOF-8) was synthesized by a solvothermal method, and used as an efficient heterogeneous catalyst for the Friedel-Crafts acylation reaction. The solid catalyst was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), atomic absorption spectrophotometry (AAS), and nitrogen physisorption measurements. High conversions were achieved in the presence of a catalytic amount of the IRMOF-8 (1-5 mol%) without the need for an inert atmosphere. The solid catalyst could be facilely separated from the reaction mixture by simple centrifugation, and could be reused without a significant degradation in catalytic activity. No contribution from homogeneous catalysis of active acid species leaching into the reaction solution was detected.
Nguyen, Lien T.L.,Nguyen, Chi V.,Dang, Giao H.,Le, Ky K.A.,Phan, Nam T.S.
body text
p. 28 - 35
(2011/11/30)

Direct synthesis of aryl ketones by palladium-catalyzed desulfinative addition of sodium sulfinates to nitriles
Mild yet direct: A convenient and efficient method for the synthesis of various aryl ketones by palladium-catalyzed desulfinative addition of aromatic sulfinic acid sodium salts to various nitriles is described (see scheme). Aromatic and aliphatic nitriles are successfully reacted with arenesulfinic acid sodium salts to form aryl ketones in good yields.
Liu, Jing,Zhou, Xianya,Rao, Honghua,Xiao, Fuhong,Li, Chao-Jun,Deng, Guo-Jun
supporting information; experimental part
p. 7996 - 7999
(2011/08/22)

Copper-catalyzed arylation of arylboronic acids with aldehydes
A novel copper-catalyzed arylation of arylboronic acids with aldehydes under oxygen atmosphere was achieved in the presence of Cu(OTf)2 and Xantphos, affording diaryl ketone derivatives in moderate to good yields. The efficiency of this reaction was demonstrated by the compatibility with fluoro, bromo, chloro, nitro, -methylsulfonyl, and trifluoromethyl groups. Georg Thieme Verlag Stuttgart ? New York.
Zheng, Hanmei,Ding, Jinchang,Chen, Jiuxi,Liu, Miaochang,Gao, Wenxia,Wu, Huayue
experimental part
p. 1626 - 1630
(2011/08/03)

Mobilizing Cu(I) for carbon-carbon bond forming catalysis in the presence of thiolate. Chemical mimicking of metallothioneins
Copper(I) is rendered catalytically viable in the presence of thiolate by the design of a small molecule chemical analogue of the metallothionein system in which an N-O reactant serves the same conceptual purpose of the S-S reactant of the biological system.
Zhang, Zhihui,Lindale, Matthew G.,Liebeskind, Lanny S.
supporting information; experimental part
p. 6403 - 6410
(2011/06/19)

NOVEL 4-AMINO-QUINOLINE DERIVATIVES USEFUL AS ANTI-MALARIA DRUGS
The present invention relates to clotrimazole/quinoline hybrids useful as active ingredients of anti-malaria drugs. The compounds show a remarkable in vitro biological activity especially against the chloroquine-resistant Plasmodium falciparum strains and
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(2010/04/30)