- Carbanionic displacement reactions at phosphorus: Diethyl (2-pyridyl)methylphosphonate synthesis
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We describe the formation and reactions of the α-lithiated (2-pyridyl)methylphosphonate 1. The lithiated α-picoline is obtained by metallation in THF at low temperature with LDA (lithium diisopropylamide) (2 equiv.). This is then condensed with diethyl ch
- Carran, John,Waschbuesch, Rachel,Savignac, Philippe
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- A new insight into the push-pull effect of substituents via the stilbene-like model compounds
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In this paper, authors report on 1-pyridyl-2-arylethenes, 1-furyl-2-arylethylenes, 1,2-diphenylpropylenes and substituted cinnamyl anilines as stilbene-like model compounds to investigate the factors dominating the push-pull effect of substituents via usi
- Cao, Chaotun,Cao, Chenzhong,Zeng, Zhao
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- A new Pd(II)-supported catalyst on magnetic SBA-15 for C-C bond formation via the Heck and Hiyama cross-coupling reactions
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Magnetic mesoporous silica composite (MNP@SiO2-SBA) was obtained via embedding magnetite nanoparticles between SBA-15 channels. It was silylated with N-(3-(trimethoxysilyl)propyl)picolinamide (TMS-PCA) and then complexed with Pd(II). The obtained supported Pd(II) catalyst (MNP@SiO2-SBA-PCA) was characterized by conventional methods. The prepared magnetic catalyst showed high activity in the Heck and Hiyama reactions under optimal reaction conditions, including solvent, amount of catalyst, base, and temperature. Aryl bromides and iodides showed better results than aryl chlorides, and the catalyst exhibited noticeable stability and reused several times.
- Rahimi, Leila,Mansoori, Yagoub,Nuri, Ayat,Koohi-Zargar, Behzad,Esquivel, Dolores
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- A New Nitrogen Pd(II) Complex Immobilized on Magnetic Mesoporous Silica: A Retrievable Catalyst for C–C Bond Formation
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Abstract: A new nitrogen ligand, i.e. 1,3-di-(o-aminophenoxy)-2-propyl propargyl ether (DPPE), has been synthesized and characterized. Magnetic mesoporous silica composite (MNP@SiO2-SBA) was obtained via embedding magnetite nano-particles (MNPs) between SBA-15 channels. DPPE palladium dichloride (MNP@SiO2-SBA-DPPE-Pd(II)) was then prepared via click chemistry and fully characterized. The activity and recyclability of supported magnetic Pd(II) catalyst were evaluated in Heck coupling reaction after optimizing the optimal reaction conditions including solvent, amount of catalyst, base and temperature. Aryl iodides and aryl bromides showed enhanced activity compared to those of aryl chlorides in the Heck reaction. The catalyst was easily separated magnetically, reused in five runs sequentially, and no significant loss of activity was observed. Graphic Abstract: [Figure not available: see fulltext.]
- Mousavi, Samira,Mansoori, Yagoub,Nuri, Ayat,Koohi-Zargar, Behzad
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p. 1923 - 1936
(2020/11/30)
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- Determination and application of the excited-state substituent constants of pyridyl and substituted phenyl groups
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Thirty six 1-pyridyl-2-arylethenes XCH=CHArY (abbreviated XAEY) were synthesized, in which, X is 2-pyridyl, 3-pyridyl and 4-pyridyl and Y is OMe, Me, H, Br, Cl, F, CF3, and CN. Their ultraviolet absorption spectra were measured in anhydrous ethanol, and their wavelengths of absorption maximum λmax were recorded. Also, the 234 λmax values of 1-substituted phenyl-2-arylethylene compounds (XAEY, where X is substituted phenyl) were collected. The excited-state substituent constants (Formula presented.) of three pyridyl groups and 23 substituted phenyl groups (total of 26) were obtained by means of curve-fitting method. Taking the λmax values of 358 samples of bi-arylethene derivatives as a data set and 126 samples of bi-aryl Schiff bases (including nine compounds synthesized by this work) as another data set, quantitative correlation analyses were performed by employing the obtained (Formula presented.) as a parameter, and good results were obtained for the two data sets. The reliability of the obtained (Formula presented.) values was verified. The results of this paper can provide excited-state substituent constants for the study and application of optical properties of conjugated organic compounds containing aryl groups.
- Cao, Chao-Tun,Yan, Lu,Cao, Chenzhong
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supporting information
(2021/05/21)
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- [2+2] Photodimerization of Stilbazoles Promoted by Oxalic Acid in Suspension
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In this study, a very simple technique to perform efficiently photodimerization of some vinylpyridines is reported. By irradiating a stirred mixture of several stilbazoles with solid oxalic acid dihydrate dispersed in a nonpolar (i.e., cyclohexane) or moderately polar (benzene, dichloromethane, dioxane) solvent, the corresponding dimeric cyclobutane adducts were obtained in high yields and excellent regio- and stereoselectivities. The strategy could also be applied successfully to oily, waxy, or even insoluble stilbazoles. Moreover, the oxalic acid loading could be lowered to substoichiometric amounts. When further optimizations were needed, our strategy was found to be highly flexible to identify other oligocarboxylic acids as alternative additives to improve, or even overturn, the regioselectivity. Oxalic acid and other oligocarboxylic acids were found to be capable of orienting more than 50 stilbazoles toward photodimerization under these conditions.
- Nguyen, Thanh Binh,Nguyen, Tuan Minh,Retailleau, Pascal
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supporting information
p. 4682 - 4689
(2020/04/15)
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- N-heterocyclic carbene–palladium(II) complex supported on magnetic mesoporous silica for Heck cross-coupling reaction
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Magnetic mesoporous silica was prepared via embedding magnetite nanoparticles between channels of mesoporous silica (SBA-15). The prepared composite (Fe3O4@SiO2-SBA) was then reacted with 3-chloropropyltriethoxysilane, sodium imidazolide and 2-bromopyridine to give 3-(pyridin-2-yl)-1H-imidazol-3-iumpropyl-functionalized Fe3O4@SiO2-SBA as a supported pincer ligand for Pd(II). The functionalized magnetic mesoporous silica was further reacted with [PdCl2(SMe2)2] to produce a supported N-heterocyclic carbene–Pd(II) complex. The obtained catalyst was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, vibrating sample magnetometry, Brunauer–Emmett–Teller surface area measurement and X-ray diffraction. The amount of the loaded complex was 80.3?mg?g?1, as calculated through thermogravimetric analysis. The formation of the ordered mesoporous structure of SBA-15 was confirmed using low-angle X-ray diffraction and transmission electron microscopy. Also, X-ray photoelectron spectroscopy confirmed the presence of the Pd(II) complex on the magnetic support. The prepared magnetic catalyst was then effectively used in the coupling reaction of olefins with aryl halides, i.e. the Heck reaction, in the presence of a base. The reaction parameters, such as solvent, base, temperature, amount of catalyst and reactant ratio, were optimized by choosing the coupling reaction of 1-bromonaphthalene and styrene as a model Heck reaction. N-Methylpyrrolidone as solvent, 0.25?mol% catalyst, K2CO3 as base, reaction temperature of 120°C and ultrasonication of the catalyst for 10?min before use provided the best conditions for the Heck cross-coupling reaction. The best results were observed for aryl bromides and iodides while aryl chlorides were found to be less reactive. The catalyst exhibited noticeable stability and reusability.
- Nuri, Ayat,Mansoori, Yagoub,Bezaatpour, Abolfazl
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- Palladium(ii) ligated with a selenated (Se, CNHC, N-)-type pincer ligand: An efficient catalyst for Mizoroki-Heck and Suzuki-Miyaura coupling in water
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A new 1-[N-benzylacetamido]-3-[1-(2-phenylselenylethyl)]benzimidazolium chloride (L), the precursor of a novel (Se, CNHC, N-)-type pincer ligand (L) was synthesised in high yield through a sequence of consecutive reactions of 1H-benzimidazole with ethylene dichloride, sodium selenophenolate, and N-benzyl-2-chloroacetamide. The palladium-promoted reaction of L with PdCl2 resulted in a moisture- and air-insensitive complex [Pd(L-H2Cl)Cl] (1), which demonstrated outstanding catalytic potential for Mizoroki-Heck coupling of aromatic bromides and chlorides (with yields up to 94% and 70%, respectively) at very low catalyst loading (0.2 mol%) and under mild reaction conditions in water. The complex (1) was also investigated for Suzuki-Miyaura coupling and found to be selectively efficient (yields up to 94%) for Suzuki-Miyaura coupling of aromatic bromides at 0.01 mol% of 1 in water. All coupling reactions were carried out in the green and economical solvent, water, which is highly desirable for bulk synthesis of complex molecules in industry. During the catalytic process, complex 1 converted into PdSe nanoparticles (NPs, size range 5-6 nm) in situ. The morphology and composition of these NPs were analysed through high-resolution transmission electron microscopy and transmission electron microscopy-energy dispersive X-ray spectroscopy, respectively. The core-level, X-ray photoelectron spectroscopy analysis confirmed the presence of stable Pd0 and Pd2+ oxidation states in these PdSe NPs. Based on further experimental investigations, these nanoparticles were found to work as a stock of true catalytic species. The hot filtration test, as well as the two-phase test, confirmed the largely homogeneous nature of the catalytic process, which probably proceeds by leaching of solution-phase Pd species from these NPs.
- Sharma, Kamal Nayan,Satrawala, Naveen,Srivastava, Avinash Kumar,Ali, Munsaf,Joshi, Raj Kumar
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p. 8969 - 8976
(2019/10/28)
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- Direct Wittig Olefination of Alcohols
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A base-promoted transition metal-free approach to substituted alkenes using alcohols under aerobic conditions using air as the inexpensive and clean oxidant is described. Aldehydes are relatively difficult to handle compared to corresponding alcohols due to their volatility and penchant to polymerize and autoxidize. Wittig ylides are easily oxidized to aldehydes and consequently form homo-olefination products. By the strategy of simultaneously in situ generation of ylides and aldehydes, for the first time, alcohols are directly transferred to olefins with no need of prepreparation of either aldehydes or ylides. Thus, the di/monocontrollable olefination of diols is accomplished. This synthetically practical method has been applied in the gram-scale synthesis of pharmaceuticals, such as DMU-212 and resveratrol from alcohols.
- Li, Qiang-Qiang,Shah, Zaher,Qu, Jian-Ping,Kang, Yan-Biao
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p. 296 - 302
(2018/02/19)
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- Br?nsted acid-catalysed conjugate addition of photochemically generated α-amino radicals to alkenylpyridines
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The conjugate addition of α-amino radicals to alkenylpyridines has been accomplished by the synergistic merger of Br?nsted acid and visible light photoredox catalysis. Key to reaction development was the protonation of the alkenylpyridines that transientl
- Hepburn, Hamish B.,Melchiorre, Paolo
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supporting information
p. 3520 - 3523
(2016/03/04)
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- Preparation of Vinyl Arenes by Nickel-Catalyzed Reductive Coupling of Aryl Halides with Vinyl Bromides
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This work emphasizes the synthesis of substituted vinyl arenes by reductive coupling of aryl halides with vinyl bromides under mild and easy-to-operate nickel-catalyzed reaction conditions. A broad range of aryl halides, including heteroaromatics, and vinyl bromides were employed to yielding products in moderate to excellent yields with high functional-group tolerance. The nickel-catalytic system displays good chemoselectivity between the two C(sp2)-halide coupling partners, thus demonstrating a mechanistic pathway distinct from other stepwise protocols.
- Liu, Jiandong,Ren, Qinghua,Zhang, Xinghua,Gong, Hegui
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p. 15544 - 15548
(2016/12/09)
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- Palladium-Catalyzed Oxidative Heck Coupling of Vinyl Pyridines with Aryl Boronic Acids
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An efficient methodology has been developed for the oxidative cross-coupling of vinyl pyridine with various boronic acids catalyzed by palladium. In this reaction, vinyl pyridines reacted with various aryl boronic acids in the presence of 10 mol% palladium(II) trifluoroacetate, 10 mol% 1,10- phenanthroline, and 1 equivalent silver(I) oxide, to give the corresponding aryl vinyl pyridine products as a single stereoisomer, with N,N-dimethylformamide as the solvent and under 1 atmosphere of oxygen gas. The aryl vinyl pyridine products were obtained in moderate to good yields after 24 hours. A mechanism for the reaction is proposed.
- Chen, Shanshan,Zhang, Xiuli,Chu, Mingjie,Gan, Xiaoping,Lv, Xianhai,Yu, Jie
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supporting information
p. 791 - 796
(2015/03/30)
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- Lewis-acid-catalyzed benzylic reactions of 2-methylazaarenes with aldehydes
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Lewis-acid-catalyzed benzylic reactions of 2-methylazaarenes with aldehydes have been investigated. Series of azaarene derivatives were afforded by this reaction. 2-(Pyridin-2-yl)ethanols with common substituents were formed through the LiNTf2-promoted aldol reaction for the first time. 2-Alkenylpyridines, exclusively in the form of the E isomers, were synthesized in the presence of LiNTf2 cooperated with H2NTf. In the presence of La(Pfb)3 as catalysis, 2-alkenylquinolines were obtained in high yields through the reactions between 2-methylquinolines and aldehydes under air.
- Mao, Dan,Hong, Gang,Wu, Shengying,Liu, Xin,Yu, Jianjun,Wang, Limin
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p. 3009 - 3019
(2014/05/20)
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- Heck cross-coupling of vinyl heteroaromatic compounds with aryl and heteroaryl halides using Pd(II) complex under phosphine-free conditions
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The palladium-catalyzed cross-coupling reaction of vinyl heteroaromatic compounds with aryl bromides and heteroaryl bromides is described using air and moisture stable N,N′,N″,O-tetrafunctional Pd catalyst under phosphine-free conditions. As a result a variety of trans-1,2-disubstituted vinyl heterocycles were obtained in high to good yields.
- Annapurna, Manne,Vishnuvardhan Reddy,Singh, Surya Prakash,Kantam, Mannepalli Lakshmi
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p. 10940 - 10945
(2014/01/06)
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- 1,2,3-Triazol-5-ylidene-palladium complex catalyzed Mizoroki-Heck and Sonogashira coupling reactions
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The bis-1,4-dimesityl-1,2,3-triazol-5-ylidene-palladium complex (1a) successfully catalyzes the Mizoroki-Heck and Sonogashira coupling reactions with aryl bromides to give the corresponding alkenes and alkynes, respectively, in good to excellent yields. In the Mizoroki-Heck reaction, electron-rich, electron-poor, and functionalized aryl bromides and alkenes are tolerated, while the substrates are limited to electron-poor aryl halides in the Sonogashira coupling reaction. The palladium complex also catalyzes cross-coupling reactions with aryl chlorides to give higher yields of products than does the bis-IMes-Pd complex analogue (2), under specific conditions.
- Inomata, Sayuri,Hiroki, Hidekatsu,Terashima, Takahiro,Ogata, Kenichi,Fukuzawa, Shin-Ichi
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experimental part
p. 7263 - 7267
(2011/10/08)
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- Ruthenium-mediated regio- and stereoselective alkenylation of pyridine
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A novel alkenylation reaction of pyridine is developed. Heating a cationic ruthenium vinylidene complex [CpRu(C=C=HR)(PPh3)2]PF6 in pyridine at 100-125 °C for 24 h affords (E)-2-alkenylpyridine. Initially, pyridine coordinates to ruthenium by displacement of one of the phosphine ligands. Then, [2 + 2] heterocycloaddition occurs to form a four-membered ruthenacyclic complex. Deprotonation of the β-hydrogen affords a neutral π-azaallyl complex. Protonolysis furnishes the product. As a result, a vinylidene group is inserted into the α C-H bond of pyridine. The alkenylation reaction is made catalytic in ruthenium by the use of (alkyn-1-yl)silane as the vinylidene source. Treatment of (alkyn-1-yl)trimethylsilane with pyridine in the presence of a cationic ruthenium complex [CpRu(PPh3)2]PF6 affords the corresponding (E)-2-alkenylpyridine in good yield in a regio- and stereoselective manner. Copyright
- Murakami, Masahiro,Hori, Seiji
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p. 4720 - 4721
(2007/10/03)
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- Trans-Selective Olefination of Carbonyl Compounds by Low-Valent Titanium-Mediated Dehydroxybenzotriazolylation
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Lithiation with n-butyllithium of a variety of benzotriazole derivatives 1a-f and 5a-d, all containing a proton α to the benzotriazolyl moiety, gave anions which underwent addition to aliphatic, aromatic, and α,β-unsaturated aldehydes and cyclic and acyclic ketones. The resultant N-(β-hydroxyalkyl)benzotriazole derivatives 3a-m, 6a-g, 9a-d, and 10a were dehydroxybenzotriazolylated when treated with low-valent titanium to give alkenes 4a-m, dienes 7a- j, and triene 11a, with selectivity for the trans isomers without separation of diastereoisomeric intermediates. This method offers an alternative to the three most frequently used methods for the formation of alkenes from carbonyl compounds-the Wittig, Peterson, and Julia reactions-especially in the formation of tri- and tetrasubstituted alkenes.
- Katritzky, Alan R.,Cheng, Dai,Henderson, Scott A.,Li, Jianqing
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p. 6704 - 6709
(2007/10/03)
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- Anil-Synthese. 22 Mitteilung. Ueber die Herstellung von Styryl und Distyryl-Derivaten des Pyridins
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2,4-, 2,5- and 2,6-Dimethylpyridines react with anils of aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide to yield the corresponding distyrylpyridines ('anil synthesis').Under the same reaction conditions (4-methylstyryl)pyridines are converted to (stilbenylvinyl)pyridines.Similarly, the Schiff's base derived from pyridine-3-carbaldehyde and chloranile on treatment with methyl- and p-tolyl-substituted aromatic hetericycles gives the corresponding (heteroaryl-styryl)pyridines, whereas with the Schiff's bases derived from pyridine-2= and -4-carbaldehyde side reactions, such as dimerization followed by disproportionation predominate.
- Siegrist, Adolf Emil,Meyer, Hans Rudolf,Gassmann, Peter,Moss, Serge
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p. 1311 - 1334
(2007/10/02)
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- Hypoglycemic stilbazolte derivatives
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Stilbazole derivatives in which the phenyl ring is substituted with a carboxylic acid group at the para position or a group convertible in the body to a carboxylic acid group, are useful as hypoglycemic agents.
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