- Oxidative esterification of alcohols by a single-side organically decorated Anderson-type chrome-based catalyst
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The direct esterification of alcohols with non-noble metal-based catalytic systems faces great challenges. Here, we report a new chrome-based catalyst stabilized by a single pentaerythritol decorated Anderson-type polyoxometalate, [N(C4H9)4]3[CrMo6O18(OH)3C{(OCH2)3CH2OH}], which can realize the efficient transformation from alcohols to esters by H2O2oxidation in good yields and high selectivity without extra organic ligands. A variety of alcohols with different functionalities including some natural products and pharmaceutical intermediates are tolerated in this system. The chrome-based catalyst can be recycled several times and still keep the original configuration and catalytic activity. We also propose a reasonable catalytic mechanism and prove the potential for industrial applications.
- Wang, Jingjing,Jiang, Feng,Tao, Chaofu,Yu, Han,Ruhlmann, Laurent,Wei, Yongge
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supporting information
p. 2652 - 2657
(2021/04/21)
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- Pd salen complex@CPGO as a convenient, effective heterogeneous catalyst for Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions
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A Pd(II) Schiff base complex supported on graphene oxide nanosheets (Pd(II) salen@CPGO) has been synthesized and characterized by FT-IR, ICP-AES, XRD, SEM/EDX and TEM. The synthesized nanocatalyst has been found to be an efficient heterogeneous catalyst for Suzuki–Miyaura and Heck–Mizoroki coupling reactions. Pd(II) salen@CPGO could be separated and recovered easily from the reaction mixture and recycled several times without a discernible decrease in its catalytic activity. The construction of a solid sheet-supported Pd catalyst would be expected to be a promising system to perform heterogeneous catalytic reactions.
- Ghabdian, Mahdieh,Nasseri, Mohammad Ali,Allahresani, Ali,Motavallizadehkakhky, Alireza
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p. 1713 - 1728
(2018/05/25)
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- Palladium Ion Catalysed Oxidative C–C Bond Formation Reactions in Arylboronic Acid: Application of Cordierite Monolith Coated Catalyst
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Abstract: Catalytic efficiency of palladium ion substituted in TiO2, Ti0.97Pd0.03O1.97 is successfully exploited for the oxidative homocoupling of arylboronic acid and oxidative Heck coupling reactions between arylboronic acid and olefins. The reaction protocol provides direct approach to synthesize biphenyls and cinnamates from moderate to good yield with good functional group tolerance. As a result, 11 symmetrical biaryls and 14 cinnamates were synthesized from readily available arylboronic acids. Ti0.97Pd0.03O1.97 powder catalyst is synthesized by solution combustion method and characterized by powder X-ray diffraction. The C–C bond formation reactions were carried out by catalyst cartridge method using Ti0.97Pd0.03O1.97 catalyst coated cordierite monolith. Coating of the catalyst on a cordierite monolith enhanced the applicability of the catalyst and made handling and recycling of the catalyst very easy. Catalyst was recovered and recycled for eight times in both homocoupling and oxidative Heck coupling reactions. The turnover number for both the reactions found to be 443 and 424, respectively. Graphic Abstract: [Figure not available: see fulltext.].
- Bhat, Shrikanth K.,Prasanna,Dasappa, Jagadeesh Prasad,Hegde
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p. 2911 - 2927
(2020/03/31)
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- Sodium pyruvate as a peroxide scavenger in aerobic oxidation under carbene catalysis
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NHC-Catalyzed aerobic oxidative reactions of imines and aldehydes have been developed by using sodium pyruvate as a novel and efficient peroxide scavenger. A structurally diverse set of imidates and amidines has been prepared from imines using this strategy. This general and efficient strategy features the use of sodium pyruvate as a novel and efficient peroxide scavenger and ambient air as the sole oxidant to efficiently control the NHC-catalyzed aerobic reaction pathway (selective realization of the oxidative pathway) under mild and green conditions. This journal is
- Fu, Zhenqian,Hong, Xianfang,Huang, Wei,Wang, Guanjie,Wei, Chenlong
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supporting information
p. 6819 - 6826
(2020/11/09)
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- Highly Regio- A nd Enantioselective Hydrogenation of Conjugated α-Substituted Dienoic Acids
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Highly regio- A nd enantioselective hydrogenation of conjugated α-substituted dienoic acids was realized for the first time using Trifer-Rh complex, providing a straightforward method for the synthesis of chiral α-substituted ?,?′-unsaturated acids. DFT calculations revealed N+H-O hydrogen bonding interaction is formed to stabilize the transition state and the coordination of 4,5-double bond to Rh(III) center would facilitate the reductive elimination process. This hydrogenation provided a gram-scale synthesis of the precursor of sacubitril.
- Liu, Xian,Liu, Song,Wang, Quanjun,Zhou, Gang,Yao, Lin,Ouyang, Qin,Jiang, Ru,Lan, Yu,Chen, Weiping
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supporting information
p. 3149 - 3154
(2020/04/09)
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- Synthesis and characterization of mesoporous organosilica supported palladium (SBA-Pr-NCQ-Pd) as an efficient nanocatalyst in the Mizoroki–Heck coupling reaction
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In the present study, the modification of a mesoporous organosilica nanocomposite SBA-15 (Santa Barbara Amorphous 15) was carried out in two steps, first through the surface functionalization of SBA-Pr-NH2 with 2-chloroquinoline-3-carbaldehyde to form SBA-Pr-NCQ, and then through a post-modification process with palladium ions. The target nanocompound structure of SBA-Pr-NCQ-Pd was characterized by different techniques (thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, Energy-dispersive X-ray spectroscopy (EDX), and Fourier transform infrared spectroscopy). The catalytic performance of the porous inorganic–organic hybrid nanocomposite (SBA-Pr-NCQ-Pd) in one of the most important carbon–carbon bond-forming processes, the Mizoroki–Heck coupling reaction of aryl halides and methacrylate in water/ethanol media, was examined. Compared to previous reports, this protocol afforded some advantages, such as high yields of products, short reaction times, catalyst stability without leaching, simple methodology, easy workup, and greener conditions. Also, the nanocatalyst can be easily separated from the reaction mixture and reused several times without a significant decrease in activity and promises economic as well as environmental benefits.
- Moradi, Razieh,Mohammadi Ziarani, Ghodsi,Badiei, Alireza,Mohajer, Fatemeh
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- PdII/Novel Chiral Cinchona Alkaloid Oxazoline-Catalyzed Enantioselective Oxidative Cyclization of Aromatic Alkenyl Amides
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A highly enantioselective PdII-catalyzed aza-Wacker oxidation tandem cyclization of aromatic nitrogen-containing dienes has been achieved in the presence of novel chiral cinchona alkaloid oxazoline ligands for the first time, affording chiral dihydroindole nitrogen-containing polycyclic compounds with good yields (up to 83 %), high diastereoselectivities (> 95:5 dr), and excellent enantioselectivities (up to 97 % ee).
- Tian, Qinqin,Liu, Yulong,Wang, Xiaoyun,Wang, Xie,He, Wei
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supporting information
p. 3850 - 3855
(2019/06/08)
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- Synthesis and discovery of 18β-glycyrrhetinic acid derivatives inhibiting cancer stem cell properties in ovarian cancer cells
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Despite advances in ovarian cancer treatment, the five-year overall survival rate is less than 30% with the presence of cancer stem cells (CSCs). To develop CSC-targeting therapy, a series of 18β-glycyrrhetinic acid (GA) derivatives containing cinnamamide moiety have been designed, synthesized, and screened for their antiproliferative activity in SKOV3 and OVCAR3 cells. Most of the compounds exhibited stronger antiproliferative activity than GA, and compound 7c was the most active one. Further biological studies showed that compound 7c could induce apoptosis and suppress migration. In addition, compound 7c could not only observably decrease the colony formation and sphere formation ability, but also significantly reduce the CD44+, CD133+, and ALDH+ subpopulation in SKOV3 and OVCAR3 cells. In conclusion, these results indicate that compound 7c is a promising anti-CSC agent for further anti-ovarian cancer studies.
- Li, Xiaojing,Liu, Yihua,Wang, Na,Liu, Yuyu,Wang, Shuai,Wang, Hongmin,Li, Aihua,Ren, Shaoda
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p. 27294 - 27304
(2019/09/12)
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- In situ synthesis of carbon nanotube-encapsulated cobalt nanoparticles by a novel and simple chemical treatment process: Efficient and green catalysts for the Heck reaction
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In this study, we present a novel, fast and easy method for supporting metal nanoparticles onto the internal surface of multi-walled CNTs; these CNT-encapsulated nanoparticles as heterogeneous, efficient, inexpensive and green catalysts promote the Heck cross-coupling of a large library of functional substrates under mild and sustainable conditions. Remarkably, the introduced catalytic system could be reused for at least nine successive runs without a discernible decrease in its catalytic activity.
- Hajipour, Abdol R.,Khorsandi, Zahra,Farrokhpour, Hossein
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supporting information
p. 8215 - 8219
(2019/06/07)
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- Palladium-melamine complex anchored on magnetic nanoparticles: A novel promoter for C-C cross coupling reaction
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A palladium-melamine complex deposited on Fe3O4@SiO2 nanoparticles (MNPs-Mel-Pd) was considered as an effective catalyst for C-C cross-coupling (Mirozoki-Heck) reaction. Surface and magnetic properties of the prepared core-shell hybrid nanocatalyst was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, energy-dispersive X-ray, vibrating sample magnetometry, transmission and scanning electron microscopy techniques and ICP/OES analysis. It was found that the heterogeneous nanocatalyst could be recovered simply and reused numerous times without loss of its catalytic activity. The advantages of this new methodology are: isolation of highly pure products without chromatography techniques, reusability of the catalyst using a magnet, easy workup procedure and negligible leaching of palladium.
- Bodaghifard, Mohammad Ali
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- Phenanthroline-based microporous organic polymer as a platform for an immobilized palladium catalyst for organic transformations
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Porous organic polymers have attracted significant attention owing to their large specific surface area, excellent chemical and thermal stability, and controllable skeletons. phenanthroline-based microporous organic polymer (Phen-MOP) has been synthesized via a cost-effective method based on the Scholl reaction. The Phen-MOP polymer exhibits high surface area and good stability. Owing to the phenanthroline skeleton embedding into the microporous polymer framework, the Phen-MOP can serve as a platform to support a transition metal catalyst. After being post-modified with palladium acetate, the synthesized Phen-Pd-MOP framework can serve as a highly efficient heterogeneous catalyst for the Suzuki-Miyaura coupling reaction and the Heck coupling reaction. Moreover, the Phen-Pd-MOP catalyst could be reused at least 10-12 times without any significant loss of the catalytic activity.
- Wang, Chang-An,Nie, Kun,Song, Guo-Dong,Li, Yan-Wei,Han, Yin-Feng
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p. 8239 - 8245
(2019/03/21)
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- Recyclable Pd ionic catalyst coated on cordierite monolith for high TOF Heck coupling reaction
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Abstract : Pd 2 + ionic catalyst, Ti 0.97Pd 0.03O 1.97 was coated over cordierite monolith by solution combustion method. The catalyst coated on the cordierite is nano-crystalline as seen from XRD studies. Coated catalyst was used for Heck coupling reactions with different substrates of aryl halides and olefins. Thus handling nano-crystalline catalyst powder is avoided by fixing it on a solid catalyst cartridge. Heck coupled products were characterized using 1H NMR, 13C NMR, Mass and FTIR spectroscopy. This catalyst showed high selectivity towards Heck coupling reaction. Turnover frequencies (TOF) for each of the reactions were found to be very high. The catalyst was recycled up to 7 times with total TOF 3017 h - 1, which is found to be a new green technique in the Heck coupling reaction. Graphical abstract: Ti 0.97Pd 0.03O 1.97 catalyst is coated on cordierite monolith honeycomb (HC) by solution combustion method and it is used in the Heck coupling reaction. Reactions are done in a specially designed flask. Catalyst is recycled for 7 times. The total turnover frequency (TOF) after 7 cycles was 3017 h - 1. [Figure not available: see fulltext.].
- Bhat, Shrikanth K,Prasad, Jagadeesh D,Hegde
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- Synthesis and antibacterial evaluation of novel 11-O-aralkylcarbamoyl-3-O-descladinosylclarithromycin derivatives
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A series of novel 11-O-aralkylcarbamoyl-3-O-descladinosylclarithromycin derivatives were designed, synthesized and evaluated for their in vitro antibacterial activity. The results showed that the majority of the target compounds displayed potent activity against erythromycin-susceptible S. pyogenes, erythromycin-resistant S. pneumoniae A22072 expressing the mef gene and S. pneumoniae AB11 expressing the mef and erm genes. Besides, most of the target compounds exhibited moderate activity against erythromycin-susceptible S. aureus ATCC25923 and B. subtilis ATCC9372. In particular, compounds 11a, 11b, 11c, 11e, 11f and 11h were found to exert favorable antibacterial activity against erythromycin-susceptible S. pyogenes with the MIC values of 0.015–0.125 μg/mL. Furthermore, compounds 10e, 11a, 11b and 11c showed superior activity against erythromycin-resistant S. pneumoniae A22072 with the MIC values of 0.25–0.5 μg/mL. Additionally, compound 11c was the most effective against all the erythromycin-resistant S. pneumoniae strains (A22072, B1 and AB11), exhibiting 8-, 8- and 32-fold more potent activity than clarithromycin, respectively.
- Jia, Li,Wang, Yinhu,Wang, Yanxia,Qin, Yinhui,Hu, Chaoyu,Sheng, Juzheng,Ma, Shutao
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supporting information
p. 2471 - 2476
(2018/06/06)
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- Highly efficient and green esterification of carboxylic acids in deep eutectic solvents without any other additives
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A protocol that carboxylic acids esterifies with the quaternary ammonium salt of deep eutectic solvent (DES) is presented, which opens a new access to ester using DES as alkylating agent, solvent, and catalyst. The reaction runs smoothly in DES without any other additives. Substituted cinnamic acids, aromatic acids, and aliphatic acids can be esterified in moderate to good yields. The advantages of this reaction include excellent functional group compatibility and simple reaction procedure.
- Yasmin, Sumera,Sheng, Wen-Bing,Peng, Cai-Yun,Rahman, Atta-ur,Liao, Duan-Fang,Choudhary, M. Iqbal,Wanga, Wei
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supporting information
p. 68 - 75
(2017/12/26)
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- Fabrication of Pd/CuFe2O4 hybrid nanowires: A heterogeneous catalyst for Heck couplings
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The development of environmentally benign transformations is indispensable in organic synthesis. Herein, a hybrid heterogeneous catalyst, palladium(0) on copper ferrite nanowires, has been synthesized, characterized, and for the first time, employed in the Jeffrey Heck reaction between iodoarenes and allylic alcohols, and good to excellent yields have been obtained. In addition, the catalyst was found to be suitable for the usual Heck coupling. The nanocatalyst was recovered and reused up-to multiple runs without any noticeable loss of its catalytic activity.
- Lakshminarayana,Mahendar,Ghosal,Sreedhar,Satyanarayana,Subrahmanyam, Ch.
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p. 1646 - 1654
(2018/02/09)
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- Synthesis of some monosaccharide-related ester derivatives as insecticidal and acaricidal agents
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To develop natural-product-based pesticidal agents, a series of monosaccharide-related ester derivatives (17a–q and 18a–f), glucose (xylose)-piperic acid/piperic acid-like conjugates, were synthesized. Three-dimensional structures of compounds 17b, 17g, 17h, and 17n were unambiguously determined by single-crystal X-ray diffraction. Especially compounds 18e and 18f exhibited the most potent insecticidal and acaricidal activities against Mythimna separata and Tetranychus cinnabarinus. Their structure-activity relationships were also discussed.
- Huang, Xiaobo,Zhang, Bingchuan,Xu, Hui
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p. 4336 - 4340
(2017/09/12)
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- Novel cyclodextrin-modified h-BN@Pd(II) nanomaterial: An efficient and recoverable catalyst for ligand-free C-C cross-coupling reactions in water
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An environmentally friendly palladium(II) catalyst supported on cyclodextrin-modified h-BN was successfully prepared. The catalyst was characterized by FT-IR, SEM, TG, XRD and XPS, and the loading level of Pd in h-BN@β-CD@Pd(II) was measured to be 0.088?mmol g?1 by ICP. It exhibits excellent catalytic activity for the Suzuki and Heck reactions in water, and can be easily separated and consecutively reused for at least nine times. In addition, a series of pharmacologically interesting products were successfully synthesized using this catalyst to demonstrate its potential applications in pharmaceutical industries. Above all, this work opens up an interesting and attractive avenue for the use of cyclodextrin-functionalized h-BN as an efficient support for hydrophilic heterogeneous catalysts.
- Ma, Xiaojun,Lv, Guanghui,Cheng, Xu,Li, Weijian,Sang, Rui,Zhang, Yong,Wang, Qiantao,Hai, Li,Wu, Yong
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- An ionic liquid catalyzed probase method for one-pot synthesis of α,β-unsaturated esters from esters and aldehydes under mild conditions
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A one-pot synthesis of α,β-unsaturated esters from unactivated esters and aldehydes using strong bases, such as sodium alkoxide and potassium tert-butoxide, was reported. However, the ionic liquid (IL) catalyzed probase method for producing α,β-unsaturated esters was not reported until now. In this work, a series of ILs with fluoride anions were firstly prepared and used as catalysts in combination with the probase N,O-bis(trimethylsilyl) acetamide (BSA) for the α,β-unsaturated esters synthesis. This process could also be promoted through the introduction of another IL with Lewis acid sites. The yield and selectivity of the product could reach up to 84.2% and 95.0%, respectively, when [Bmim]F was used in combination with [Bmim]Cl/AlCl3 (the molar fraction of AlCl3 is 0.67). The mechanism investigation through GC-MS indicates that BSA would convert into onium amide, which acted as a strong base for α-H abstraction, with the catalysis of [Bmim]F. Meanwhile, [Bmim]Cl/AlCl3 played an important role in the condensation step between enolates and aldehydes. On the basis of mechanism insights, kinetic and thermodynamic studies were also carried out for a better understanding of this new route.
- Wang, Gang,Xu, Yiming,Zhang, Suojiang,Li, Zengxi,Li, Chunshan
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p. 4838 - 4848
(2017/10/23)
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- Self-assembled Pd nanoparticle-containing ionic liquid: Efficient and reusable catalyst for the Heck reaction in water
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A self-assembled Pd nanoparticle-containing ionic liquid as metal–organic polymer was successfully prepared. The structure of the catalyst was characterized using Fourier transform infrared and 1H NMR spectroscopies, scanning electron microscopy and elemental analysis. The catalyst was effectively employed in the palladium-catalyzed Heck reaction in water as a green solvent. Moreover, due to its stability the catalyst can be recovered simply and effectively and reused nine times without much loss of activity.
- Zong, Yingxiao,Wang, Junke,An, Pengli,Yue, Guoren,Pan, Yi,Wang, Xicun
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p. 2389 - 2396
(2017/09/30)
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- Methionine-functionalized chitosan–Pd(0) complex: A novel magnetically separable catalyst for Heck reaction of aryl iodides and aryl bromides at room temperature in water as only solvent
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We report a novel catalyst system with an immobilized palladium metal-containing magnetic nanoparticle core (ImmPd(0)-MNPs) for the Heck reaction. ImmPd(0)-MNPs was found to be an exceptionally mild and versatile catalyst for the Heck reaction of aryl iodides and bromides at room temperature. The catalyst was simply recovered using an external magnet from the reaction mixture and recycled six times. The results showed that the catalyst was very active and stable. Moreover, the reaction was carried out in water as a green and environmentally acceptable solvent. In terms of scope and mildness, ImmPd(0)-MNPs is an improvement over previously reported catalysts for Heck coupling methods.
- Hajipour, Abdol R.,Tavangar-Rizi, Zeinab
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- Aminophosphine Palladium(0) Complex Supported on ZrO2 Nanoparticles (ZrO2@AEPH2-PPh2-Pd(0)) as an Efficient Heterogeneous Catalyst for Suzuki–Miyaura and Heck–Mizoroki Reactions in Green Media
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Abstract: A new aminophosphine palladium(0) complex supported on ZrO2nanoparticles (ZrO2@AEPH2-PPh2-Pd(0)) was successfully synthesized and characterized using FT-IR, XRD, XPS, SEM, TEM, EDS, TGA and ICP techniques. Characterization results revealed that the synthesized catalyst had tetragonal and monoclinic structure with spherical morphology. The prepared nanocatalyst was showed excellent reactivity in the Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. Moreover, this nanocatalyst can be easily recovered and reused for at least six cycles without deterioration in catalytic activity. Graphical Abstract: [Figure not available: see fulltext.]
- Razavi, Nasrin,Akhlaghinia, Batool,Jahanshahi, Roya
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p. 360 - 373
(2017/02/18)
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- Thiophene Methanimine–Palladium Schiff Base Complex Anchored on Magnetic Nanoparticles: A Novel, Highly Efficient and Recoverable Nanocatalyst for Cross-Coupling Reactions in Mild and Aqueous Media: Γ-Fe2O3/AEPH2-TC-Pd Catalyzed Suzuki–Miyaura and Heck–Mizoroki Reactions
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Abstract: In this study, a novel thiophene methanimine–palladium Schiff base complex anchored on decorated γ-Fe2O3 with 2-aminoethyl dihydrogen phosphate (γ-Fe2O3/AEPH2-TC-Pd) was synthesized as a new magnetically separable nanocatalyst. Characterization of the new designed nanocatalyst was performed successfully using different techniques such as FT-IR, XRD, XPS, TEM, TGA, VSM, ICP and elemental analysis. This nanocatalyst presented a superb catalytic activity for Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. The most important features of the prepared catalytic system which makes the current protocol more beneficial from both industrial and environmental viewpoints are its ease of recovery and reusability up to nine cycles without appreciable loss of the catalytic performance, as well as accomplishing the reactions under mild conditions in aqueous media which is a great challenge in some cross-coupling reactions. Graphical Abstract: [Figure not available: see fulltext.].
- Jahanshahi, Roya,Akhlaghinia, Batool
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p. 2640 - 2655
(2017/09/06)
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- Palladium nanoparticles immobilized on amphiphilic and hyperbranched polymer-functionalized magnetic nanoparticles: An efficient semi-heterogeneous catalyst for Heck reaction
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To address the obstacles facing the use of palladium-based homogeneous and heterogeneous catalysts in C─C cross-coupling reactions, a novel semi-heterogeneous support was developed based on hyperbranched poly(ethylene glycol)-block-poly(citric acid)-functionalized Fe3O4 magnetic nanoparticles (Fe3O4@PCA-b-PEG). Because of the surface modification of the Fe3O4 nanoparticles with amphiphilic and hyperbranched polymers (PCA-b-PEG), these hybrid materials are not only soluble in a wide range of solvents (e.g. water, ethanol and dimethylformamide) but also are able to trap Pd2+ ions via complex formation of free carboxyl groups of the PCA dendrimer with metal ions. The reduction of trapped palladium ions in the dendritic shell of Fe3O4@PCA-b-PEG leads to immobilized palladium nanoparticles. The morphology and structural features of the catalyst were characterized using various microscopic and spectroscopic techniques. The catalyst was effectively used in the palladium-catalysed Mizoroki–Heck coupling reaction in water as a green solvent. In addition, the catalyst can be easily recovered from the reaction mixture by applying an external magnetic field and reused for more than ten consecutive cycles without much loss in activity, exhibiting an example of a sustainable and green methodology.
- Tabatabaei Rezaei, Seyed Jamal,Shamseddin, Azin,Ramazani, Ali,Mashhadi Malekzadeh, Asemeh,Azimzadeh Asiabi, Pegah
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- Ligand-Free C–C Coupling Reactions Promoted by Hexagonal Boron Nitride-Supported Palladium(II) Catalyst in Water
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A micron-scale palladium(II) material has been successfully prepared using Schiff base-modified hexagonal boron nitride as a support and used for the first time as an efficient and recyclable catalyst in organic synthesis. The morphology, composition, metal loading and thermal stability of the catalyst were studied using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), infrared spectroscopy (FT-IR), inductively coupled plasma (ICP) and thermogravimetric (TG) analyses. Then, the micron material was tested in various C–C cross-coupling reactions and exhibited excellent catalytic activities in the Suzuki and Heck reactions. Moreover, the catalyst could be easily recovered by simple filtration and reused at least ten times without significant loss of its catalytic activity. In general, this work demonstrates the possibility of using Schiff-base@hexagonal boron nitride as an efficient support for heterogeneous catalysts. (Figure presented.).
- Cheng, Xu,Li, Weijian,Nie, Ruifang,Ma, Xiaojun,Sang, Rui,Guo, Li,Wu, Yong
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supporting information
p. 454 - 466
(2017/02/10)
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- Magnetic nanoparticle-supported tetrazole-functionalized palladium catalyst: synthesis, DFT study and application for Sonogashira and Heck cross-coupling reactions
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Abstract: A novel magnetic catalyst-immobilized nano-palladium was efficiently prepared via a (2?+?3) cycloaddition pathway and characterized with different analyses, including FT-IR, FE-SEM, EDS, XRD, TEM and VSM methods. Also, topological and NBO analysis of a simple model of the catalyst with the M06/6-311?g(d,p)-LANL2DZ model chemistry have been introduced. In addition, the catalytic pursuit of this novel magnetic nanocatalyst was successfully evaluated in Sonogashira and Heck cross-coupling reactions. Furthermore, the catalyst could be easily separated by a conventional method using a permanent magnet and reused repeatedly in the model reaction without noteworthy loss of its catalytic activity.
- Elhampour, Ali,Nemati, Firouzeh,Nahzomi, Hossein Taherpour,Mohagheghi, Vahid
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p. 6737 - 6761
(2017/10/06)
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- Hydrogen Peroxide Promoted Mizoroki-Heck Reactions of Phenyldiazenes with Acrylates, Acrylamides, and Styrenes
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Mizoroki-Heck reactions, which are well-known for aryldiazonium salts and which have recently been described for arylhydrazines, have now been extended to phenyldiazenes. In situ generation of phenyldiazenes from azocarboxylates allowed clean and selective reactions with styrenes, acrylates, and acrylamides using palladium(II) acetate in the presence of silver(I) acetate or hydrogen peroxide as oxidant. Hydrogen peroxide was thereby shown to be a cheap and broadly applicable alternative for the established palladium-silver(I) system.
- Lasch, Roman,Fehler, Stefanie K.,Heinrich, Markus R.
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supporting information
p. 1586 - 1589
(2016/05/02)
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- Attractive aerobic access to the α,β-unsaturated acyl azolium intermediate: Oxidative NHC catalysis via multistep electron transfer
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To replace high molecular weight oxidants with air (O2) we introduce multistep electron transfer NHC catalysis. The method provides a general and selective oxidation of the α,β-unsaturated aldehyde derived homoenolate to the synthetically useful α,β-unsaturated acyl azolium intermediate. Several independent oxidative NHC-catalyzed reactions are viable with this strategy and the products can be isolated in high to excellent yields.
- Ta,Axelsson,Sundén
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supporting information
p. 686 - 690
(2016/02/12)
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- Magnetic iron oxide nanoparticles–N-heterocyclic carbene–palladium(II): a new, efficient and robust recyclable catalyst for Mizoroki–Heck and Suzuki–Miyaura coupling reactions
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A new and efficient nanoparticle–N-heterocyclic carbene–palladium complex was synthesized and characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, transmission electron microscopy, elemental analysis, inductively coupled plasma analysis and vibrating sample magnetometry. This catalytic system was found to be a highly active catalyst in the Mizoroki–Heck and Suzuki–Miyaura cross-coupling reactions. These reactions were best performed in dimethylformamide and water, respectively, in the presence of only 0.054 mol% of palladium under mild conditions. Moreover, the catalyst could be recovered easily and reused at least ten times without any considerable loss of its catalytic activity. Copyright
- Hajipour, Abdol R.,Tadayoni, Nayereh S.,Khorsandi, Zahra
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p. 590 - 595
(2016/07/16)
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- Regioselective Heck reaction catalyzed by Pd nanoparticles immobilized on DNA-modified MWCNTs
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This is the first report of regioselective Heck reaction of aryl iodides with 2,3-dihydrofuran using heterogonous nanocatalyst. Herein, palladium nanoparticles is immobilized on DNA-modified multi walled carbon nanotubes and characterized by FT-IR spectroscopy, UV-vis spectroscopy, field emission scanning electron microscopy, X-ray diffraction, transmission electron microscopy, inductively coupled plasma and elemental analysis. DNA as a well-defined structure and biodegradable natural polymer generate the palladium catalyst which showed high activity in common and regioselective Heck reaction in excellent yields and good selectivity under ligand-free and mild reaction conditions. Moreover, the catalyst could be recovered and reused at least nine times without any considerable loss of its catalytic activity.
- Hajipour, Abdol R.,Khorsandi, Zahra,Farrokhpour, Hossein
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p. 59124 - 59130
(2016/07/06)
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- Multi walled carbon nanotubes supported N-heterocyclic carbene-cobalt (II) as a novel, efficient and inexpensive catalyst for the Mizoroki-Heck reaction
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In this paper, an N-heterocyclic carbene-cobalt complex (NHC-Co2+) was immobilized onto the surface of multi-walled carbon nanotubes (MWCNTs) via direct grafting amination approach for the first time. The resultant composite (Co - NHC@MWCNTs) was characterized by FT-IR, TGA, XRD, ICP-OES, FE-SEM, TEM and CHN analyses. It was demonstrated that Co-NHC@MWCNTs can act as an efficient and inexpensive catalyst for Heck reactions in normal conditions which provided the corresponding products in moderate to good yields. More importantly, this phosphine and palladium-free catalyst can be reused for at least six successive runs without any discernible decrease in its catalytic activity and no remarkable changes were observed in catalyst structure.
- Hajipour, Abdol R.,Khorsandi, Zahra
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- Catalytic asymmetric bromochlorination of aromatic allylic alcohols promoted by multifunctional Schiff base ligands
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It was found that the tridentate O,N,O-type Schiff base ligand bearing suitable substituents was a highly effective promoter in the catalytic asymmetric bromochlorination reaction, in which the corresponding aromatic bromochloroalcohols with vicinal halogen-bearing stereocenters were formed with perfect regioselectivity, with moderate to excellent enantioselectivities (up to 93% ee), and with good yields and chemoselectivities.
- Huang, Wei-Sheng,Chen, Li,Zheng, Zhan-Jiang,Yang, Ke-Fang,Xu, Zheng,Cui, Yu-Ming,Xu, Li-Wen
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supporting information
p. 7927 - 7932
(2016/08/30)
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- Aerobic Copper-Catalyzed O-Methylation with Methylboronic Acid
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The oxidative coupling of alkylboronic acids with oxygen nucleophiles offers a strategy for replacing toxic, electrophilic alkylating reagents. Although the Chan-Lam reaction has been widely applied in the arylation of heteroatom nucleophiles, O-alkylation with boronic acids is rare. We report a Cu-catalyzed nondecarboxylative methylation of carboxylic acids with methylboronic acid that proceeds in air with no additional oxidant. An isotope-labeling study supports an oxidative cross-coupling mechanism, in analogy to that proposed for Chan-Lam arylation.
- Jacobson, Clare E.,Martinez-Mu?oz, Noelia,Gorin, David J.
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p. 7305 - 7310
(2015/07/28)
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- Chemical assembly systems: Layered control for divergent, continuous, multistep syntheses of active pharmaceutical ingredients
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While continuous chemical processes have attracted both academic and industrial interest, virtually all active pharmaceutical ingredients (APIs) are still produced by using multiple distinct batch processes. To date, methods for the divergent multistep continuous production of customizable small molecules are not available. A chemical assembly system was developed, in which flow-reaction modules are linked together in an interchangeable fashion to give access to a wide breadth of chemical space. Control at three different levels - choice of starting material, reagent, or order of reaction modules - enables the synthesis of five APIs that represent three different structural classes (γ-amino acids, γ-lactams, β-amino acids), including the blockbuster drugs Lyrica and Gabapentin, in good overall yields (49-75%).
- Ghislieri, Diego,Gilmore, Kerry,Seeberger, Peter H.
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supporting information
p. 678 - 682
(2015/03/04)
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- Infrared irradiation assisted both the synthesis of (Z)-(aminomethyl)(aryl)phenylhydrazones via the Mannich coupling reaction and their application to the palladium-catalyzed Heck reaction
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The Mannich coupling reaction between arylhydrazones, formaldehyde and a secondary amine to generate the (Z)-(aminomethyl)(aryl)phenylhydrazones 1a-h assisted by infrared irradiation (IR) under solvent-free conditions is herein reported, and the catalytic potential of compounds 1a-h in the palladium-catalyzed and IR-assisted Heck coupling reaction is also evaluated. Coupling products are obtained in high yields and short reaction times. We show the advantages of this new alternative to promote both Mannich and Heck coupling reactions.
- Ortega-Jiménez, Fernando,Penieres-Carrillo, José Guillermo,Lagunas-Rivera, Selene,López-Cortés, José G.,álvarez-Toledano, Cecilio,Ortega-Alfaro, M. Carmen
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p. 80911 - 80918
(2015/10/06)
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- Highly efficient direct aerobic oxidative esterification of cinnamyl alcohol with alkyl alcohols catalysed by gold nanoparticles incarcerated in a nanoporous polymer matrix: A tool for investigating the role of the polymer host
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The selective aerobic oxidation of cinnamyl alcohol to cinnamaldehyde, as well as direct oxidative esterification of this alcohol with primary and secondary aliphatic alcohols, were achieved with high chemoselectivity by using gold nanoparticles supported in a nanoporous semicrystalline multi-block copolymer matrix, which consisted of syndiotactic polystyrene-co-cis-1,4- polybutadiene. The cascade reaction that leads to the alkyl cinnamates occurs through two oxidation steps: the selective oxidation of cinnamyl alcohol to cinnamaldehyde, followed by oxidation of the hemiacetal that results from the base-catalysed reaction of cinnamaldehyde with an aliphatic alcohol. The rate constants for the two steps were evaluated in the temperature range 10-45 °C. The cinnamyl alcohol oxidation is faster than the oxidative esterification of cinnamaldehyde with methanol, ethanol, 2-propanol, 1-butanol, 1-hexanol or 1-octanol. The rate constants of the latter reaction are pseudo-zero order with respect to the aliphatic alcohol and decrease as the bulkiness of the alcohol is increased. The activation energy (Ea) for the two oxidation steps was calculated for esterification of cinnamyl alcohol with 1-butanol (Ea=57.8±11.5 and 62.7±16.7 kJ mol -1 for the first and second step, respectively). The oxidative esterification of cinnamyl alcohol with 2-phenylethanol follows pseudo-first-order kinetics with respect to 2-phenylethanol and is faster than observed for other alcohols because of fast diffusion of the aromatic alcohol in the crystalline phase of the support. The kinetic investigation allowed us to assess the role of the polymer support in the determination of both high activity and selectivity in the title reaction. Golden boost to the esterification: The highly efficient and selective aerobic oxidation of cinnamyl alcohols, catalysed by gold nanoparticles supported in a nanoporous polymer matrix, in the presence of primary and secondary alkyl alcohols afforded alkyl cinnamates (see figure). The active role of the host-polymer matrix was investigated.
- Buonerba, Antonio,Noschese, Annarita,Grassi, Alfonso
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p. 5478 - 5486
(2014/05/20)
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- Ti/Ni-mediated inter- and intramolecular conjugate addition of aryl and alkenyl halides and triflates
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In this work, we show that the unique combination of a nickel catalyst and Cp2TiCl allows the direct conjugate addition of aryl and alkenyl iodides, bromides, and to a lesser extent, chlorides and triflates to α,β-unsaturated carbonyls at room temperature, without requiring the previous formation of an organometallic nucleophile. The reaction proceeds inter- and intramolecularly with good functional group compatibility, which is key for the development of free protecting group methodologies. Carbo- and heterocycles of five- and six-membered rings are obtained in good yields. Moreover, some insights about the mechanism involved have been obtained from cyclic voltammetry, UV-vis, and HRTEM measurements.
- Marquez, Irene R.,Miguel, Delia,Millan, Alba,Marcos, M. Luisa,De Cienfuegos, Luis Alvarez,Campana, Araceli G.,Cuerva, Juan M.
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p. 1529 - 1541
(2014/03/21)
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- Proline-catalyzed asymmetric Diels-Alder reactions of an o-quinodimethane
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Catalytic asymmetric Diels-Alder reaction of α-amino-o-quinodimethane with α,β-unsaturated aldehydes was achieved with high diastereo- and enantioselectivities in the presence of l-proline, which acts as a promoter to generate the quinodimethane from the corresponding precursor as well as a chiral catalyst for the enantioselective Diels-Alder reaction.
- Shirakawa, Hidenori,Sano, Hiroshi
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supporting information
p. 4095 - 4097
(2014/07/22)
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- Simultaneous immobilization of a matrix containing palladium and phase transfer catalyst on silica nanoparticles: Application as a recoverable catalyst for the Heck reaction in neat water
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Simultaneous covalent anchoring of a phosphonium-palladium complex/phase transfer catalyst matrix on the surface of silica nanoparticles and the application of the resulting catalyst in the Heck reaction of a variety of different haloarenes in neat aqueous media is described. This journal is the Partner Organisations 2014.
- Hajipour, Abdol R.,Azizi, Ghobad
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p. 20704 - 20708
(2014/06/09)
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- Synthesis and characterization of the 2-methylaminopyridine-functionalized polystyrene resin-supported Pd(II) catalyst for the mizoroki-heck and sonogashira reactions in water
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A new polystyrene-anchored Pd(II) pyridine complex is synthesized and characterized. This Pd(II) pyridine complex behaves as a very efficient heterogeneous catalyst in the Heck reaction of methyl acrylate with aryl halides and the Sonogashira reaction of terminal alkynes with aryl halides in water. Furthermore, the catalyst shows good thermal stability and recyclability. This polymer-supported Pd(II) catalyst could easily be recovered by simple filtration of the reaction mixture and reused for more than five consecutive trials without a significant loss in its catalytic activity. The present Pd(II) pyridine complex behaves as a very efficient heterogeneous catalyst in the Heck reaction of methyl acrylate with aryl halides and Sonogashira reaction of terminal alkynes with aryl iodides and bromides in water. Furthermore, the catalyst has shown good thermal stability and recyclability. Copyright
- Bakherad, Mohammad,Amin, Amir Hosein,Gholipoor, Farzaneh
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p. 279 - 284
(2014/05/06)
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- Poly(vinyl chloride)-supported Pd(II) complex as an efficient catalyst for Heck and Cu-free Sonogashira reactions under aerobic conditions
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A novel poly(vinyl chloride)-supported Pd complex was found to be a highly active catalyst for the Heck and Sonogashira reactions of aryl halides under aerobic conditions. The complex is thermally stable, and can be easily recovered and reused. The catalyst was recycled for the Heck and Sonogashira reactions for five runs without appreciable loss of its catalytic activity, and with negligible metal leaching.
- Bakherad, Mohammad,Keivanloo, Ali,Samangooei, Shahrzad
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p. 324 - 328
(2014/04/03)
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- Iron-catalyzed cross-coupling reaction: Recyclable heterogeneous iron catalyst for selective olefination of aryl iodides in poly(ethylene glycol) medium
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An environmentally friendly iron-based catalyst supported on acac-functionalized silica was successfully prepared and evaluated as a heterogeneous catalyst for Mizoroki-Heck reaction of aryl iodides and olefins. Our catalytic system showed good activities that were comparable to that of palladium catalysts. The catalyst was simply recovered from the reaction mixture and recycled five times. Furthermore, the reaction was carried out in poly(ethylene glycol) as a green solvent. Interestingly, using this catalyst, aryl iodides were selectively olefinated in the presence of aryl bromides.
- Hajipour, Abdol Reza,Azizi, Ghobad
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p. 1030 - 1034
(2013/07/26)
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- Catalytic asymmetric cross-dehydrogenative coupling: Activation of C-H bonds by a cooperative bimetallic catalyst system
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A cooperative bimetallic catalyst system was applied in the catalytic asymmetric cross-dehydrogenative coupling of β-ketoesters and xanthene. Various optically active xanthene derivatives bearing a quaternary stereogenic carbon center were obtained in moderate to good yields (up to 90%) with excellent enantioselectivities (up to 99% ee). Meanwhile, a transition-state model was proposed to explain the origin of the asymmetric induction.
- Cao, Weidi,Liu, Xiaohua,Peng, Ruixue,He, Peng,Lin, Lili,Feng, Xiaoming
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supporting information
p. 3470 - 3472
(2013/05/23)
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- Suzuki, Heck, and copper-free Sonogashira reactions catalyzed by 4-amino-5-methyl-3-thio-1,2,4-triazole-functionalized polystyrene resin-supported Pd(II) under aerobic conditions in water
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4-amino-5-methyl-3-thio-1,2,4-triazole-functionalized polystyrene resin-supported Pd(II) complex was found to be an efficient catalyst in the palladium-catalyzed Suzuki-Miyaura coupling reactions of aryliodides and bromides, Mizoroki-Heck reactions of aryliodides and bromides, and copper-free Sonogashira reactions of aryliodides and bromides in water. Under appropriate conditions, all of these reactions give the desired products in moderate to excellent yields. The catalyst is air-stable and easily available. The palladium catalyst is easily separated, and can be reused for several times without a significant loss in its catalytic activity.
- Bakherad, Mohammad,Keivanloo, Ali,Bahramian, Bahram,Jajarmi, Saeideh
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p. 206 - 212
(2013/03/13)
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- A dithizone-functionalized polystyrene resin-supported Pd(II) complex as an effective catalyst for Suzuki, Heck, and copper-free Sonogashira reactions under aerobic conditions in water
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A novel polystyrene-supported palladium(II) dithizone complex is found to be a highly active catalyst for the Suzuki, Heck, and Sonogashira reactions of aryl halides in water. By this protocol, aryl halides, coupled with phenyl boronic acid (Suzuki reaction), alkenes (Heck reaction) or terminal alkyne (Sonogashira reaction), smoothly affords the corresponding cross-coupling products in good to excellent yields. Furthermore, the catalyst shows good thermal stability and recyclability. The catalyst was recycled for the Suzuki, Heck, and Sonogashira reactions for five runs without appreciable loss of its catalytic activity and negligible metal leaching.
- Bakherad, Mohammad,Jajarmi, Saeideh
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p. 152 - 159
(2013/04/24)
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- Chiral magnesium(II) binaphtholates as cooperative bronsted/lewis acid-base catalysts for the highly enantioselective addition of phosphorus nucleophiles to α,β-unsaturated esters and ketones
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A little cooperation goes a long way: The cooperative Bronsted/Lewis acid-base supramolecular catalysts formed in situ from simple chiral magnesium(II) binaphtholate aqua complexes promoted the highly enantioselective 1,4-hydrophosphinylation of α,β-unsaturated esters with diaryl phosphine oxides and 1,2-hydrophosphonylation of α,β-unsaturated ketones with dialkyl phosphites (see scheme). Copyright
- Hatano, Manabu,Horibe, Takahiro,Ishihara, Kazuaki
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supporting information
p. 4549 - 4553
(2013/06/04)
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- Solvent-free Heck and copper-free Sonogashira cross-coupling reactions catalyzed by a polystyrene-anchored Pd(II) phenyldithiocarbazate complex
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A new polystyrene-anchored Pd(II) phenyldithiocarbazate complex is synthesized and characterized. This Pd-complex behaves as an efficient heterogeneous catalyst in the Heck coupling and copper-free Sonogashira coupling reactions under aerobic conditions. Furthermore, the catalyst shows good thermal stability and recyclability.
- Bakherad, Mohammad,Keivanloo, Ali,Samangooei, Shahrzad
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p. 5773 - 5776
(2012/10/29)
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- Highly effective recyclable palladium-catalyzed ligand-free heck reactions under aerobic conditions
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An effective protocol was developed for the Heck coupling reactions between various aryl halides and olefins. In the presence of 2 mol% of Pd(OAc) 2, the desired products could be obtained in good yields under ligand-free and aerobic conditions. The catalytic system could be easily recycled for five times with high efficiency. Georg Thieme Verlag Stuttgart. New York.
- Sun, Peng,Qu, Xiaoming,Li, Tingyi,Zhu, Yan,Yang, Hailong,Xing, Zeyong,Mao, Jincheng
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supporting information; experimental part
p. 150 - 154
(2012/02/04)
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- Phosphine-free polystyrene-supported palladium(II) complex as an efficient catalyst for the Heck and Suzuki coupling reactions in water
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A palladium complex, 1-phenyl-1,2-propanedione-2-oxime thiosemi-carbazone- functionalized polystyrene resin supported Pd(II), is found to be a highly active catalyst for the Heck reaction of methyl acrylate with aryl halides and Suzuki reaction of phenylboronic acid with aryl iodides and bromides, giving excellent yields. The reactions were performed under phosphine-free conditions in an air atmosphere. The palladium catalyst is easily separated, and can be reused for several times without a significant loss in its catalytic activity.
- Bakherad, Mohammad,Keivanloo, Ali,Amin, Amir H.,Jajarmi, Saeideh
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p. 945 - 949
(2013/02/22)
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- Stereoselective synthesis of unsymmetrical β,β-diarylacrylates by a heck-matsuda reaction: Versatile building blocks for asymmetric synthesis of β,β-diphenylpropanoates, 3-Aryl-indole, and 4-Aryl-3,4-dihydro- quinolin-2-one and formal synthesis of (-)-indatraline
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β,β-Disubstituted R,β-unsaturated esters may serve as valuable derivatives for the preparation of other highly functionalized systems found in many natural products and marketed drugs. The stereoselective synthesis of unsymmetrical β,β-diarylacrylate compounds possessing two similar aromatic groups remains a substantial challenge. A simple and convenient stereoselective protocol for the preparation of β,β- disubstituted acrylates via a Heck-Matsuda reaction is reported. Good to high yields were accomplished by a "ligand-free" Pd-catalyzed arylation reaction of cinnamate esters with arenediazonium tetrafluoroborates. Both electron-deficient and electron-rich arenediazonium salts could be employed as arylating reagents, and cinnamate esters were generally more reactive when substituted with an electron-donating group. The overall methodology is highly stereoselective, and this attribute was taken advantage of in the asymmetric Cu-catalyzed 1,4 reduction reaction to provide β,β-diarylpropanoates in high enantioselectivities. The synthesis of a 3-aryl indole and a chiral 4-aryl-2-quinolone from β,β-diarylacrylates was achieved by cyclization in the presence of a diphosphine ligated CuH catalyst. A convenient route for the asymmetric formal synthesis of the psychoactive compound (-)-Indatraline is also presented.
- Taylor, Jason G.,Correia, Carlos Roque D.
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supporting information; scheme or table
p. 857 - 869
(2011/04/18)
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