- Mechanochemical Solvent-Free Suzuki–Miyaura Cross-Coupling of Amides via Highly Chemoselective N?C Cleavage
-
Although cross-coupling reactions of amides by selective N?C cleavage are one of the most powerful and burgeoning areas in organic synthesis due to the ubiquity of amide bonds, the development of mechanochemical, solid-state methods remains a major challe
- Ma, Yangmin,Shao, Lei,Szostak, Michal,Wang, Ruihong,Zhang, Jin,Zhang, Pei
-
supporting information
(2022/01/04)
-
- Palladium supported on MRGO@CoAl-LDH catalyzed reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as liquid CO and H2 source
-
In the present study, a heterogeneous palladium catalyst system, Pd nanoparticles supported on MRGO@CoAl-LDH, was synthesized and employed in reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as CO and H2 source. The as-obtained heterogeneous catalyst was characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDAX), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The nanocatalyst was reused for 5 cycles with a negligible reduction in the yield of products. All reactions were carried out with high yields and under suitable and safe conditions. Also, we have successfully applied formic acid as a good and safe alternative to CO and H2 gases.
- Jadidi Nejad, Masoumeh,Heydari, Akbar
-
-
- 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)
-
- Method for preparing aldehyde ketone compound through olefin oxidation
-
The invention provides a method for preparing an aldehyde ketone compound by olefin oxidation, which relates to an olefin oxidative cracking reaction in which oxygen participates. The method comprises the following specific steps: in the presence of a solvent and an oxidant, carrying out oxidative cracking on an olefin raw material to obtain a corresponding aldehyde ketone product. Compared with the traditional method, the method does not need to add any catalyst or ligand, does not need to use high-pressure oxygen, has the advantages of simple and mild reaction conditions, environment friendliness, low cost, high atom economy and the like, is wide in substrate application range and high in yield, and has a wide application prospect in the aspects of synthesis of aldehyde ketone medical intermediates and chemical raw materials.
- -
-
Paragraph 0019
(2021/04/07)
-
- Poly(ethylene glycol) dimethyl ether mediated oxidative scission of aromatic olefins to carbonyl compounds by molecular oxygen
-
A simple, and practical oxidative scission of aromatic olefins to carbonyl compounds using O2as the sole oxidant with poly(ethylene glycol) dimethyl ether as a benign solvent has been developed. A wide range of monosubstituted,gem-disubstituted, 1,2-disubstituted, trisubstituted and tetrasubstituted aromatic olefins was successfully converted into the corresponding aldehydes and ketones in excellent yields even with gram-scale reaction. Some control experiments were also conducted to support a possible reaction pathway.
- Yu, Tao,Guo, Mingqing,Wen, Simiaomiao,Zhao, Rongrong,Wang, Jinlong,Sun, Yanli,Liu, Qixing,Zhou, Haifeng
-
p. 13848 - 13852
(2021/04/22)
-
- 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)
-
- 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)
-
- 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)
-
- Carbonylative Suzuki-Miyaura Coupling Reactions of Aryl Iodides with Readily Available Polymer-Immobilized Palladium Nanoparticles
-
Polysilane/alumina-supported palladium nanoparticle catalyzed carbonylative Suzuki-Miyaura coupling reactions under ligand-free conditions have been developed to synthesize diaryl ketones. High yields and selectivities were achieved even with low catalyst loading under atmospheric pressure of CO gas. A variety of aryl iodides and arylboronic acids could be utilized to afford the diaryl ketones in excellent yields. Moreover, the ligand-free immobilized palladium nanoparticles could be recovered by simple filtration and the catalytic activity could be maintained for several runs.
- Yasukawa, Tomohiro,Zhu, Zhiyuan,Yamashita, Yasuhiro,Kobayashi, Shu
-
p. 502 - 504
(2020/09/21)
-
- Feeding Carbonylation with CO2via the Synergy of Single-Site/Nanocluster Catalysts in a Photosensitizing MOF
-
Solar-driven carbonylation with CO2 replacing toxic CO as a C1 source is of considerable interest; however it remains a great challenge due to the inert CO2 molecule. Herein, we integrate cobalt single-site and ultrafine CuPd nanocluster catalysts into a
- Fu, Shanshan,Guo, Guang-Chen,Guo, Song,Lu, Tong-Bu,Yao, Shuang,Yuan, Wenjuan,Zhang, Zhi-Ming
-
p. 20792 - 20801
(2021/12/14)
-
- 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)
-
- Pd-Catalysed carbonylative Suzuki-Miyaura cross-couplings using Fe(CO)5under mild conditions: generation of a highly active, recyclable and scalable ‘Pd-Fe’ nanocatalyst
-
The dual function and role of iron(0) pentacarbonyl [Fe(CO)5] has been identified in gaseous CO-free carbonylative Suzuki-Miyaura cross-couplings, in which Fe(CO)5supplied COin situ, leading to the propagation of catalytically active Pd-Fe nanoparticles. Compared with typical carbonylative reaction conditions, CO gas (at high pressures), specialised exogenous ligands and inert reaction conditions were avoided. Our developed reaction conditions are mild, do not require specialised CO high pressure equipment, and exhibit wide functional group tolerance, giving a library of biaryl ketones in good yields.
- Zhu, Zhuangli,Wang, Zhenhua,Jian, Yajun,Sun, Huaming,Zhang, Guofang,Lynam, Jason M.,McElroy, C. Robert,Burden, Thomas J.,Inight, Rebecca L.,Fairlamb, Ian J. S.,Zhang, Weiqiang,Gao, Ziwei
-
supporting information
p. 920 - 926
(2021/02/09)
-
- Palladium nanoparticles on amino-modified silica-catalyzed C–C bond formation with carbonyl insertion
-
Abstract: A practical and heterogeneously catalyzed Stille, homo-coupling, and Suzuki carbonylation reaction has been reported using Pd nanoparticles supported on amino-vinyl silica-functionalized magnetic carbon nanotube (CNT@Fe3O4@SiO2-Pd) for the efficient synthesis of symmetrical and unsymmetrical diaryl ketones from aryl iodides. A wide variety of symmetrical and unsymmetrical diaryl ketones were obtained in high yields under CO gas-free conditions using Mo(CO)6 as an efficient carbonyl source. Considering the atom economy of Ph3SnCl, less than an equimolar amount can be applied in Stille transformation, which is of great importance due to the toxicity of organotin derivatives. Moreover, no phosphine ligand and external reducing agent were necessary in these coupling carbonylation reactions. This heterogeneous Pd catalyst offers high activity with very low palladium leaching. Finally, the catalyst can be reused and recycled for six steps without loss in activity, exhibiting good example of sustainable methodology. Graphic abstract: [Figure not available: see fulltext.].
- Etemadi-Davan, Elham,Khalili, Dariush,Banazadeh, Ali Reza,Sadri, Ghazal,Arshad, Pourya
-
p. 1891 - 1903
(2021/02/01)
-
- Palladium(II) Complexes of a Neutral CCC-Tris(N-heterocyclic carbene) Pincer Ligand: Synthesis and Catalytic Applications
-
Treatment of tris-azolium precursor 1 with palladium acetate under thermal conditions provided a CCC-pincer palladium(II) complex (2) bearing three NHCs (one imidazolylidene and two triazolylidenes) and one iodide ligand. Further treatment of complex 2 with an excess of AgSbF6 generates tris(carbene) dicationic palladium complex 3 in which the iodine ligands are exchanged with SbF6 anions and the metal center is stabilized by one acetonitrile ligand. Complexes 2 and 3 were tested in several cross coupling reactions showing high conversions under low catalyst loadings and mild reaction conditions. Additionally, complexes 2 and 3 performed well in the hydrosilylation of terminal alkynes with good selectivity toward the E-isomer.
- Angeles-Beltrán, Deyanira,Mendoza-Espinosa, Daniel,Rendón-Nava, David,Rheingold, Arnold L.
-
supporting information
p. 2166 - 2177
(2021/07/20)
-
- Novelmeta-benzothiazole and benzimidazole functionalised POCOP-Ni(ii) pincer complexes as efficient catalysts in the production of diarylketones
-
The synthesis of four novel non-symmetric Ni(ii)-POCOP pincer complexesmeta-functionalized with either benzothiazole or benzimidazole at the central aryl ring is described. All complexes were fully characterised in solution by various analytical techniques and the molecular structures in the solid state of complexes1b,2aand2bwere unequivocally determined by single crystal X-ray diffraction analysis. In addition, the Ni(ii)-POCOP pincer complexes were efficiently used as catalysts in the synthesis of diarylketones by cross-coupling reactions of functionalized benzaldehydes and boronic acid derivatives under relatively mild conditions. An important aspect of this transformation is the dependence on the steric properties of the donor groups (OPR2) of the pincer ligands, the more active compounds having the phosphinitos bearing isopropyl groups (1aand2a) than those containingtert-butyl substituents (1band2b).
- Castillo-García, Antonio A.,González-Sebastián, Lucero,Lomas-Romero, Leticia,Hernandez-Ortega, Simon,Toscano, Ruben A.,Morales-Morales, David
-
p. 10204 - 10216
(2021/06/18)
-
- AIBN initiated functionalization of the benzylic sp3 C[sbnd]H and C[sbnd]C bonds in the presence of dioxygen
-
A sp3 C[sbnd]H bond functionalization and C[sbnd]C bond cleavage were realized by AIBN/O2 catalyst system, providing a series of benzophenones under mild reaction conditions. The mechanistic study shows that a peroxide intermediate is involved in this transformation, and in the case of diphenylmethanes, the sp3 C[sbnd]C bond is cleaved through the peroxide rearrangement, which might provides a new way to cleave relatively strong C[sbnd]C bond and be applied to more general C[sbnd]C bond activation.
- Hu, Yingying,Shao, Yu,Zhang, Shuwei,Yuan, Yuan,Sun, Zheng,Yuan, Yu,Jia, Xiaodong
-
supporting information
(2021/02/01)
-
- Acyl radicals from α-keto acids using a carbonyl photocatalyst: Photoredox-catalyzed synthesis of ketones
-
Acyl radicals have been generated from α-keto acids using inexpensive and commercially available 2-chloro-thioxanthen-9-one as the photoredox catalyst under visible light illumination. These reactive species added to olefins or coupled with aryl halides via a bipyridylstabilized Ni(II) catalyst, enabling easy access to a diverse range of ketones. This reliable, atom-economical, and eco-friendly protocol is compatible with a wide range of functional groups.
- Zhu, Da-Liang,Wu, Qi,Young, David James,Wang, Hao,Ren, Zhi-Gang,Li, Hong-Xi
-
supporting information
p. 6832 - 6837
(2020/10/12)
-
- Palladium-Catalyzed Amide N-C Hiyama Cross-Coupling: Synthesis of Ketones
-
N-Acylglutarimides and arylsiloxanes reacted in the presence of Pd(OAc)2/PCy3, Et3N·3HF, and LiOAc to provide the corresponding arylketones in good yields. Aryl-, vinyl-, and alkyl-substituted N-acylglutarimides showed good activity in the coupling reactions of arylsiloxanes. The reaction had a broad substrate scope and showed good functional group tolerance. N-Benzoylsuccinimide and N-protected N-phenylbenzamides showed good activities in coupling reactions with phenylsiloxane. The employment of CuF2 as an activor afforded the decarbonylative products at 160 °C.
- Idris, Muhammad Aliyu,Lee, Sunwoo
-
supporting information
p. 9190 - 9195
(2020/11/18)
-
- 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)
-
- Palladium-Catalyzed Suzuki Coupling of N-Acyloxazolidinones via Selective Cleavage of C–N Bonds
-
By implementing a palladium-catalyzed Suzuki coupling reaction of N-acyloxazolidinones with arylboronic acid, we herein report on the preparation of substituted diaryl ketones via selective cleavage of exocyclic C–N Bonds. The reaction was carried out under mild reaction conditions with excellent functional group compatibility in good yields (up to 93 %).
- Jian, Junsheng,He, Zhanyu,Zhang, Yuqi,Liu, Tingting,Liu, Lizhen,Wang, Zijia,Wang, Hui,Wang, Sanyong,Zeng, Zhuo
-
supporting information
p. 4176 - 4180
(2020/07/13)
-
- Water Phase, Room Temperature, Ligand-Free Suzuki–Miyaura Cross-Coupling: A Green Gateway to Aryl Ketones by C–N Bond Cleavage
-
We report herein a green strategy for synthesis of aryl ketones from twisted amides by using Pd(OAc)2 as catalysts. This method shows high functional group tolerance to offer a variety of ketones in good yields under mild conditions (up to 94 %). Notably, this methodology demonstrates the first water phase, room temperature, ligand-free Suzuki–Miyaura coupling through C–N bond cleavage, which is environmentally friendly and might facilitate the development of amide based green chemistry.
- Zhang, Yuqi,Wang, Zijia,Tang, Zhao,Luo, Zhongfeng,Wu, Hongxiang,Liu, Tingting,Zhu, Yulin,Zeng, Zhuo
-
p. 1620 - 1628
(2020/03/04)
-
- Friedel–Crafts benzylation of toluene catalyzed by ZnCl2/SiO2 heterogeneous catalyst to para- and ortho-mono-benzylated toluene
-
A series of catalysts was prepared for the liquid-phase Friedel–Crafts benzylation of toluene with benzyl chloride (BC) by impregnating rice husk ash silica with ZnCl2 (3?wt%, 6?wt%, 9?wt%, and 12?wt%) via a wet impregnation method. The XRD analysis indicates that the catalysts were amorphous with ill-defined pore systems. The XPS analysis detected the coexistence of ZnO nanoparticles together with ZnCl2 on the catalyst surface, whereas the 29Si NMR analysis indicates the formation of Si–O–Zn bond. Quantitative conversion of benzyl chloride (100%) was achieved within 3?h at 353?K when a catalyst with 9?wt% ZnCl2 was used due to its narrow pore size and high surface area (635?m2?g?1). Para- and ortho-mono-benzylated toluene was obtained as the products. The reaction is proposed to take place via weak attraction between benzyl chloride and the Zn through its chlorine atom. The catalyst was recycled four times with minimum loss (8%) in activity. The benzylation of benzene, toluene, p-xylene, and anisole followed the classical mechanism of Friedel–Craft-type acid-catalyzed benzylation reaction. The BC conversion increased in the order of toluene = p-xylene > anisole > benzene. The catalyst was also screened to be active in the benzoylation of toluene with benzoyl chloride (BOC). The conversion of BOC was 45% with selectivity toward 2-methylbenzophenone (50%) and 3-methylbenzophenone (50%).
- Iqbal, Anwar,Tan, Kok-Hou,Shaari,Ahmad,Adam, Farook,Lee, Hwei Voon,Yusop, Rahimi M.,Abu Bakar,Lee, Hooi Ling,Pauzi, Hariy,Malik, Muhammad Fadhirul Izwan Abd,Jusoh, Ahmad Fadly,Wilson, Lee D.,Ahmad,Hazwan Hussain,Ibrahim, Mohamad Nasir Mohamad
-
p. 1615 - 1626
(2020/03/05)
-
- 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.
-
-
- Ionic liquid-mediated benzoyl transfer-coupling in the Suzuki and Sonogashira reactions and aryl transfer-coupling by decarbonylative Heck reaction, using N-Benzoyl-saccharin (NBSac) as reagent
-
The efficacy of N-benzoyl-saccharin (NBSac) as reagent for selective benzoyl transfer-coupling in the Suzuki reaction in BMIM-IL/[PAIM][NTf2] as solvent/base, and in the Sonogashira reaction employing guanidinium-IL (GIL) as solvent, are demonstrated. Decarbonylative aryl transfer-coupling occurs in the Heck reaction employing GIL as solvent. The reactions are catalyzed by Pd(OAc)2 or NiCl2(dppp), are performed under mild conditions in good yields, and have the potential for recycling/reuse of the IL solvent. Collectively, these methods provide facile access to diverse libraries of diarylketones, keto-ethynes and diaryl-ethenes.
- Malunavar, Shruti S.,Sutar, Suraj M.,Prabhala, Pavankumar,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
-
-
- Xantphos-ligated palladium dithiolates: An unprecedented and convenient catalyst for the carbonylative Suzuki–Miyaura cross-coupling reaction with high turnover number and turnover frequency
-
Xantphos- and dithiolate-ligated macrocyclic palladium complexes as an efficient and stable catalyst for the carbonylative Suzuki–Miyaura cross-coupling reaction have been synthesized. The catalysts were characterized by 1H-nuclear magnetic resonance (NMR), CHNS (carbon, hydrogen, nitrogen, and sulfur) analysis, melting point analysis, and 31P-NMR spectroscopy. Several sensitive functional groups (e.g., –NO2, –F, –Cl, –Br, –NH2, and –CN) on the aromatic ring were well tolerated in the carbonylative Suzuki–Miyaura coupling reaction. The present palladium complexes produce six times higher turnover number (TON) and five times higher turnover frequency (TOF) compared with conventional homogeneous palladium precursors. Maximum TONs in the range of 105 to 106 and TOF in the range of 104 to 105 could be generated by a very low amount of catalyst loading (10–5?mol%).
- Gaikwad, Vinayak V.,Mane, Pravin A.,Dey, Sandip,Bhanage, Bhalchandra M.
-
-
- Scalable Aerobic Oxidation of Alcohols Using Catalytic DDQ/HNO3
-
A selective, practical, and scalable aerobic oxidation of alcohols is described that uses catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HNO3, with molecular oxygen serving as the terminal oxidant. The method was successfully applied to the oxidation of a wide range of benzylic, propargylic, and allylic alcohols, including two natural products, namely, carveol and podophyllotoxin. The conditions are also applicable to the selective oxidative deprotection of p-methoxybenzyl ethers.
- Arseniyadis, Stellios,Clavier, Louis,Copin, Chloé,Fournier, Jean,Giffard, Jean-Fran?ois,Jean, Alexandre,Katsina, Tania,Macedo Portela Da Silva, Nayane,Tamion, Rodolphe
-
supporting information
p. 856 - 860
(2020/07/14)
-
- 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)
-
- Redox-Neutral ortho Functionalization of Aryl Boroxines via Palladium/Norbornene Cooperative Catalysis
-
Palladium/norbornene (Pd/NBE) cooperative catalysis, also known as the Catellani reaction, has become an increasingly useful method for site-selective arene functionalization; however, certain constraints still exist because of its intrinsic mechanistic pathway. Herein, we report a redox-neutral ortho functionalization of aryl boroxines via Pd/NBE catalysis. An electrophile, such as carboxylic acid anhydrides or O-benzoyl hydroxylamines, is coupled at the boroxine ortho position, and a proton as the second electrophile is introduced at the ipso position. This reaction does not require extra oxidants or reductants and avoids stoichiometric bases or acids, thereby tolerating a wide range of functional groups. In particular, orthogonal chemoselectivity between aryl iodide and boroxine moieties is demonstrated, which could be used to control reaction sequences. Finally, a deuterium-labeling study supports the ipso protonation pathway. This unique mechanistic feature could inspire the development of a new class of Pd/NBE-catalyzed transformations.Poly-substituted aromatics are ubiquitously found in drugs and agrochemicals. To realize streamlined synthesis, it is highly attractive if functional groups can be site-selectively introduced at unactivated positions with common arene starting materials. Here, a method is developed to directly introduce acyl and amino groups at unactivated ortho positions of readily available aryl boron compounds. Compared with the known ortho functionalization approaches, this method does not require stoichiometric bases, external oxidants, or reductants. Consequently, the reaction is chemoselective: a wide range of functional groups, including highly reactive aryl iodides, can be tolerated. The primary innovation lies in the use of a proton to terminate the ipso aryl intermediate and regenerate the active palladium catalyst. This unique mode of reactivity in the palladium/norbornene catalysis should open the door for developing new redox-neutral methods for site-selective arene functionalization.A redox-neutral ortho functionalization of aryl boroxines via palladium/norbornene cooperative catalysis is developed. The ortho amination and acylation are achieved with carboxylic acid anhydrides and O-benzoyl hydroxylamines as an electrophile, respectively, whereas protonation occurs at the ipso position. This transformation avoids using either extra oxidants and reductants or stoichiometric bases and acids. In addition, orthogonal chemoselectivity between aryl iodide and boroxine moieties is demonstrated for pathway divergence.
- Li, Renhe,Liu, Feipeng,Dong, Guangbin
-
supporting information
p. 929 - 939
(2019/04/10)
-
- 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
-
-
- Carbonylative Suzuki coupling and alkoxycarbonylation of aryl halides using palladium supported on phosphorus-doped porous organic polymer as an active and robust catalyst
-
Developing highly active catalysts with the combined advantages of molecular and solid catalysis is considered as the “Holy Grail” in the area of catalysis research. Herein, a phosphorus-doped porous polymer-immobilized palladium was successfully developed as an efficient, robust, and recyclable catalyst for the carbonylative Suzuki coupling and alkoxycarbonylation reactions of aryl halides. Rather than just as an immobilizing molecular catalyst, palladium supported on phosphorus-doped porous organic polymer exhibits even better catalytic performances than that of its analogue homogeneous catalysts in both carbonylation reactions. Moreover, the catalyst can be easily separated and reused for at least 5 times without significant loss in reactivity. Importantly, the catalyst was highly stable under carbonylation reaction conditions, and no palladium nanoparticle was observed even after the 5th reuse.
- Wan, Yali,Song, Fangxiang,Ye, Tao,Li, Guangxing,Liu, Dingfu,Lei, Yizhu
-
-
- Palladium-Catalyzed Direct Oxidative Coupling of Iodoarenes with Primary Alcohols Leading to Ketones: Application to the Synthesis of Benzofuranones and Indenones
-
In the present study, a palladium-catalyzed direct oxidative acylation through cross-dehydrogenative coupling has been investigated, utilizing readily available primary alcohols as acylating sources. Overall, this oxidative coupling proceeds via three distinct transformations such as oxidation, radical formation, and cross-coupling in one catalytic process. This protocol does not involve the assistance of a directing group or activation of the carbonyl group by any other means. Furthermore, this reaction made use of no toxic CO gas as carbonylating agent; instead, feedstock primary alcohols have been utilized as acylation source. Notably, the synthesis of benzofuranones and indenones is enabled. This strategy was also applied to the synthesis of n-butylphthalide, fenofibrate, pitofenone, and neo-lignan.
- Suchand, Basuli,Sreenivasulu, Chinnabattigalla,Satyanarayana, Gedu
-
p. 4832 - 4843
(2019/07/31)
-
- Heterogeneous Suzuki-Miyaura coupling of heteroaryl ester: Via chemoselective C(acyl)-O bond activation
-
A site-selective supported palladium nanoparticle catalyzed Suzuki-Miyaura cross-coupling reaction with heteroaryl esters and arylboronic acids as coupling partners was developed. This methodology provides a heterogeneous catalytic route for aryl ketone formation via C(acyl)-O bond activation of esters by successful suppression of the undesired decarbonylation phenomenon. The catalyst can be reused and shows high activity after eight cycles. The XPS analysis of the catalyst before and after the reaction suggested that the reaction might be performed via a Pd0/PdII catalytic cycle that began with Pd0.
- Ma, Hongpeng,Bai, Chaolumen,Bao, Yong-Sheng
-
p. 17266 - 17272
(2019/06/24)
-
- Transition-Metal-Free Carbonylative Suzuki-Miyaura Reactions of Aryl Iodides with Arylboronic Acids Using N-Formylsaccharin as CO Surrogate
-
Unprecedented, high yielding, transition-metal-free carbonylative Suzuki-Miyaura reactions of aryl iodides with arylboronic acids using N-formylsaccharin as CO surrogate have been developed. Notably, this general protocol was adapted to the synthesis of the triglyceride and cholesterol regulator drug, fenofibrate, and carbon-13 labeled biaryl ketone. (Figure presented.).
- Yu, Dezhong,Xu, Fangning,Li, Dan,Han, Wei
-
supporting information
p. 3102 - 3107
(2019/05/21)
-
- A Deoximation Method for Deprotection of Ketones and Aldhydes Using a Graphene-Oxide-Based Co-catalysts System
-
The deoximation of a wide range of ketoximes and aldoximes to their corresponding carbonyl compounds with high yields has been achieved using graphene oxide (GO) and sodium nitrite (NaNO2) as highly efficient catalysts and air as the green oxidant under mild conditions. The mechanism of deprotection and recycling use of catalyst were revealed in deep experiment. The carboxylic acid groups on the GO were essential for high catalytic activity. (Figure presented.).
- Tong, Qiaolin,Liu, Yang,Gao, Xuezhi,Fan, Zhanfang,Liu, Tianfu,Li, Bo,Su, Dangsheng,Wang, Qinghe,Cheng, Maosheng
-
supporting information
p. 3137 - 3145
(2019/05/01)
-
- 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)
-
- Continuous flow synthesis of diaryl ketones by coupling of aryl Grignard reagents with acyl chlorides under mild conditions in the ecofriendly solvent 2-methyltetrahydrofuran
-
An efficient continuous flow sequential synthesis of diaryl ketones was achieved by coupling of aryl Grignard reagents with acyl chlorides in the bio-derived “green” solvent 2-methyltetrahydrofuran (2-MeTHF) under mild reaction conditions (ambient temperature, 1 hour), allowing a safe and on-demand generation of 2-(3-benzoylphenyl)propionitrile with a productivity of 3.16 g hour?1
- Zhang, Chuan-Tao,Zhu, Rui,Wang, Zheng,Ma, Bing,Zajac, Adrian,Smiglak, Marcin,Xia, Chun-Nian,Castle, Steven L.,Wang, Wen-Long
-
p. 2199 - 2204
(2019/01/26)
-
- Transition-metal-free carbonylation of aryl halides with arylboronic acids by utilizing stoichiometric CHCl3 as the carbon monoxide-precursor
-
Under transition-metal-free conditions, carbonylative Suzuki couplings of aryl halides with arylboronic acid using stoichiometric CHCl3 as the carbonyl source has been developed. The simple, efficient, and environmentally benign method was successfully applied to the synthesis of Fenofibric acid, naphthyl phenstatin, and carbon-13 labeled biaryl ketone.
- Xu, Fangning,Li, Dan,Han, Wei
-
supporting information
p. 2911 - 2915
(2019/06/18)
-
- Hydroxyl-functionalized triazolylidene-based PEPPSI complexes: Metallacycle formation effect on the Suzuki coupling reaction
-
We report the preparation and full characterization of a series of hydroxyl functionalized 1,2,3-triazolylidene-based PEPPSI complexes 2a-c and their catalytic application in the Suzuki cross coupling reaction of aryl chlorides/amides with boronic acids. Under basic reaction conditions, complexes 2a-c show a notable increase in their catalytic efficiency compared with two ether-wingtip functionalized PEPPSI analogues (3 and 4) and a commercially available NHC-Pd complex (5). The catalytic results suggest that deprotonation of the hydroxyl group in complexes 2a-c plays an important role in the overall process. Deprotonation of the alcohol moiety of complexes 2a-b with sodium tert-butoxide allows for the isolation of metallacycles 6a-b, which are proposed as the active species of cross coupling reactions.
- Rendón-Nava, David,álvarez-Hernández, Alejandro,Rheingold, Arnold L.,Suárez-Castillo, Oscar R.,Mendoza-Espinosa, Daniel
-
supporting information
p. 3214 - 3222
(2019/03/13)
-
- Synthesis of some ketones via nano-nickel oxide catalyzed acylation of arylzinc reagents; strategy involving the use of mixed (methyl)(aryl)zincs
-
Nano-NiO catalyzed acylation of mixed (methyl)(aryl)zincs with aromatic acyl halides in THF at room temperature provides a new facile route for aryl–aroyl coupling. Among NiCl2 .L2 and NiCl2 .L (L = monodentate and bidentate phosphine ligand) catalysts, the lower catalyst loading of NiCl2 (dppf) may seem attractive; however, nano-NiO, being the lowest cost catalyst, is more favorable for aroylation of (methyl)(aryl)zincs. This procedure also provides a supplement to Cu and Pd catalyzed acylation of diorganozincs.
- Pekel, ?zgen ?MüR,Erdik, Ender,Kalkan, Melike
-
p. 759 - 767
(2018/06/07)
-
- Introducing Glycerol as a Sustainable Solvent to Organolithium Chemistry: Ultrafast Chemoselective Addition of Aryllithium Reagents to Nitriles under Air and at Ambient Temperature
-
Edging closer towards developing air and moisture compatible polar organometallic chemistry, the chemoselective and ultrafast addition of a range of aryllithium reagents to nitriles has been accomplished by using glycerol as a solvent, at ambient temperature in the presence of air, establishing a novel sustainable access to aromatic ketones. Addition reactions occur heterogeneously (“on glycerol conditions”), where the lack of solubility of the nitriles in glycerol and the ability of the latter to form strong intermolecular hydrogen bonds seem key to favouring nucleophilic addition over competitive hydrolysis. Remarkably, PhLi exhibits a greater resistance to hydrolysis working “on glycerol” conditions than “on water”. Introducing glycerol as a new solvent in organolithium chemistry unlocks a myriad of opportunities for developing more sustainable, air and moisture tolerant main-group-metal-mediated organic synthesis.
- Rodríguez-álvarez, María J.,García-álvarez, Joaquín,Uzelac, Marina,Fairley, Michael,O'Hara, Charles T.,Hevia, Eva
-
p. 1720 - 1725
(2018/01/27)
-
- Highly efficient synthesis of aryl ketones by PEPPSI-palladium catalyzed acylative Suzuki coupling of amides with diarylborinic acids
-
An improved acylative cross-coupling of various N-methyl-N-tosyl amides with diarylborinic acids for synthesis of aryl ketones is developed. In most cases, aryl ketones could be obtained in excellent yields by using 1 mol% 2,6-diisopropylphenylimidazolylidene and 3-chloropyridine co-supported palladium chloride as catalyst in the presence of 3 equiv. K2CO3 as base in refluxing THF. The readily prepared and cost-effective substrates, N-methyl-N-tosylamides and diarylborinic acids, and the commercially available catalyst system promise a practical and efficient access to aryl ketones.
- Wang, Chen,Huang, Lingyun,Wang, Fengze,Zou, Gang
-
p. 2299 - 2301
(2018/05/16)
-
- Hydrogen bond directed aerobic oxidation of amines via photoredox catalysis
-
An application of H-bonding interactions for directing the α-C-H oxidation of amines to amides and amino-ketones catalyzed by an organic photocatalyst is reported. The high efficiency of this method is demonstrated by the aerobic oxidation of pyrrolidines, diarylamines and benzylamines bearing urea groups with high yields and a wide substrate scope.
- Wang, Hongyu,Man, Yunquan,Wang, Kaiye,Wan, Xiuyan,Tong, Lili,Li, Na,Tang, Bo
-
p. 10989 - 10992
(2018/10/08)
-
- Integrative Photoreduction of CO2 with Subsequent Carbonylation: Photocatalysis for Reductive Functionalization of CO2
-
Efficient conversion of CO2 into fuels and chemicals with solar energy would be promising, but also faces great challenge. In this context, we describe the photoreductive functionalization of CO2 to construct new C?C, C?N, and C?O bonds through the respective Pd-catalyzed Suzuki carbonylation, aminocarbonylation, and alkoxycarbonylation of aryl iodides with CO in situ generated through the photoreduction of CO2. This protocol opens up an alternative avenue for CO2 utilization by harnessing solar energy.
- He, Xing,Cao, Yu,Lang, Xian-Dong,Wang, Ning,He, Liang-Nian
-
p. 3382 - 3387
(2018/09/14)
-
- Synthesis, Coordination, and Catalytic Use of 1′-(Diphenylphosphino)ferrocene-1-sulfonate Anion
-
Sulfonation of (diphenylphosphinothioyl)ferrocene (1) with chlorosulfonic acid in acetic anhydride affords the crude sulfonic acid Ph2P(S)fcSO3H (2; fc = ferrocene-1,1′-diyl), which can be efficiently purified and isolated after conversion to Ph2P(S)fcSO3(HNEt3) (3). Methyl triflate/P(NMe2)3 can be used to convert compound 3 to the stable sulfonate salt Ph2PfcSO3(HNEt3) (4) and Ph2P(Me)fcSO3 (5) as a minor, zwitterionic byproduct. Alternatively, compound 4 can be prepared by lithiation of 1′-(diphenylphosphino)-1-bromoferrocene (6; Ph2PfcBr) and trapping of the lithiated intermediate with SO3·NMe3. Reactions of [(LNC)PdX]2 and [(LSC)PdX]2, where X = Cl, AcO, LNC = 2-[(dimethylamino-κN)methyl]phenyl-κC1, and LSC = 2-[(methylthio-κS)methyl]phenyl-κC1, with 4 uniformly produced the bis-chelate complexes [(LNC)Pd(Ph2PfcSO3-κ2O,P)] (7) and [(LSC)Pd(Ph2PfcSO3-κ2O,P)] (8), respectively. The reaction of [PdCl2(MeCN)2] with 4 afforded the bis(phosphine) complex trans-(Et3NH)2[PdCl2(Ph2PfcSO3-κP)2] (9). Complexes 7-9 were used as defined catalyst precursors for the Suzuki-Miyaura cross-coupling of boronic acids with acyl chlorides to give ketones. Reactions of aromatic substrates in the presence of Na3PO4 and 9, the base and Pd source that showed the best performance, in a toluene/water biphasic system provided the coupling products in good yields; however, aliphatic substrates typically resulted in poor conversions. Extensive tests of the reaction scope revealed that the transposition of the substituents between the reaction partners can have a substantial effect on the yield of the coupling product in otherwise complementary reactions, which highlights the importance of the judicious choice of starting materials for this particular reaction.
- Zábransky, Martin,Císa?ová, Ivana,?těpni?ka, Petr
-
p. 1615 - 1626
(2018/06/11)
-
- 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.
- -
-
Paragraph 0041; 0042; 0043; 0045
(2018/09/11)
-
- Method for preparing aromatic ketone in aqueous phase
-
The invention discloses a method for preparing aromatic ketone in an aqueous phase, comprising the following steps: enabling aryl formyl potassium formate and aryl potassium fluoborate to generate decarboxylation acylation reaction in water under the actions of a silver catalyst and an oxidizing agent, and performing treatment after reaction is ended to obtain the disclosed aromatic ketone. According to the preparation method, the silver catalyst replaces a noble metal catalyst, water is taken as a solvent, an aromatic ketone product is obtained with relatively high yield, the adopted catalystis low in cost and easy to obtain, reaction conditions are mild, and meanwhile, the product is good in university, and therefore, the method has good application potential.
- -
-
Paragraph 0042-0045
(2018/04/26)
-
- N-heterocyclic carbene palladium(II)-catalyzed Suzuki-Miyaura cross coupling of N-acylsuccinimides by C-N cleavage
-
An easily prepared, well-defined N-heterocyclic carbene-palladium(II) complex was found to be an efficient catalyst for the Suzuki-Miyaura cross-coupling of N-acylsuccinimides with arylboronic acids via C-N bond activation. Under the optimal conditions, a
- Guo, Han,Guo, Jiarui,Jia, Dingli,Liu, Lantao,Wang, Hengjin,Wang, Tao,Zhang, Wen
-
-
- 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)
-
- N-Acyl-5,5-dimethylhydantoin, a New Mild Acyl-Transfer Reagent in Pd Catalysis: Highly Efficient Synthesis of Functionalized Ketones
-
The palladium-catalyzed Suzuki-Miyaura cross-coupling of N-acyl-5,5-dimethylhydantoins with arylboronic acids has been developed via selective amides C-N bond cleavage. The new reagent is commercially available and air-/moisture-stable, and it offers a variety of ketones in good yields through Suzuki coupling under mild conditions (up to 95%).
- Luo, Zhongfeng,Liu, Tingting,Guo, Weijie,Wang, Zijia,Huang, Jingjun,Zhu, Yulin,Zeng, Zhuo
-
p. 1188 - 1199
(2018/09/06)
-
- Method of utilizing continuous flow microreactor to synthesize benzophenone derivative
-
The invention belongs to the technical field of organic synthesis, and particularly relates to a method of utilizing a continuous flow microreactor to synthesize a benzophenone derivative. The methodincludes: using aryl Grignard reagent and acyl chloride as raw materials; at normal temperature, continuously synthesizing the benzophenone derivative in the microreactor; recycling a reaction solvent2-methyl tetrahydrofuran. Problems of environmental pollution and reaction operation safety caused by the fact that conventional Fridel-Crafts reaction is excessively dependent on reagents like aluminum trichloride, ferric trichloride and zinc dichloride are avoided, the defect that novel catalytic processes are expensive in catalytic reagent and harsh in operation condition is made up, and continuous synthesis of a medical intermediate ketoprofen nitrile is realized efficiently. The method has the advantages of high operation convenience, high reaction safety, high yield, high efficiency andreaction solvent reusability and is environment-friendly and efficient.
- -
-
Paragraph 0041-0045
(2018/09/11)
-
