- Supramolecular Catalysis of Acyl Transfer within Zinc Porphyrin-Based Metal-Organic Cages
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To illustrate the supramolecular catalysis process in molecular containers, two porphyrinatozinc(II)-faced cubic cages with different sizes were synthesized and used to catalyze acyl-transfer reactions between N-acetylimidazole (NAI) and various pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC). A systemic investigation of the supramolecular catalysis occurring within these two hosts was performed, in combination with a host-guest binding study and density functional theory calculations. Compared to the reaction in a bulk solvent, the results that the reaction of 2-PC was found to be highly efficient with high rate enhancements (kcat/kuncat = 283 for Zn-1 and 442 for Zn-2), as well as the different efficiencies of the reactions with various ortho-substituted 2-PC substrates and NAI derivates should be attributed to the cages having preconcentrated and preoriented substrates. The same cage displayed different catalytic activities toward different PC regioisomers, which should be mainly attributed to different binding affinities between the respective reactant and product with the cages. Furthermore, control experiments were carried out to learn the effect of varying reactant concentrations and product inhibition. The results all suggested that, besides the confinement effect caused by the inner microenvironment, substrate transfer, including the encapsulation of the reactant and the release of products, should be considered to be a quite important factor in supramolecular catalysis within a molecular container.
- Li, Lili,Yang, Linlin,Li, Xuezhao,Wang, Jing,Liu, Xin,He, Cheng
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supporting information
p. 8802 - 8810
(2021/06/28)
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- Proton-exchanged montmorillonite-mediated reactions of hetero-benzyl acetates: Application to the synthesis of Zafirlukast
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Proton-exchanged montmorillonite (H-mont) with outstanding surface characteristics can provide abundant acidic sites in the mesopores, and serve as an efficient heterogeneous catalyst for the synthesis of heterocycle-containing diarylmethanes via Friedel-Crafts-like alkylation of (hetero)arenes by heterobenzyl acetates under mild reaction conditions without requiring any additives or an inert atmosphere. Using this strategy, the gram-scale synthesis of indole-containing diarylmethane 13 has been accomplished in good yield for the preparation of Zafirlukast. In addition, H-mont can be applied to the nucleophilic substitution reactions of heterobenzyl acetate 5p with a variety of alcohols and 1,3-dicarbonyl compounds.
- Yang, Lei,Chen, Xuan,Ni, Kaidong,Li, Yuansheng,Wu, Jianhong,Chen, Weilin,Ji, Yin,Feng, Lili,Li, Fei,Chen, Dongyin
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supporting information
(2020/06/28)
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- A 3 - pyridine formaldehyde synthetic method
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The present invention relates to machine the chemical field, in particular to a 3 - pyridine formaldehyde synthetic method, comprises the following steps: 1, to 3 - methyl pyridine as raw materials, under acidic conditions, through the oxidation reaction
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Paragraph 0032; 0034; 0037; 0039; 0042; 0044
(2019/05/28)
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- Synthesis and characterization of MCM-41@XA@Ni(II) as versatile and heterogeneous catalyst for efficient oxidation of sulfides and acetylation of alcohols under solvent-free conditions
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Herein, Ni(II) immobilized on modified mesoporous silica MCM-41 was designed and synthesized via a facile sequential strategy. The structure of the catalyst was characterized by X-ray diffraction. The thermal property of the as-synthesized materials was studied using thermogravimetric-differential thermal analysis. The average particles size and morphology of MCM-41@XA@Ni(II) were investigated using scanning electron microscopy and transmission electron microscopy. This nanostructure catalyst was effective for the selective oxidation of sulfides and acetylation of alcohols in solvent-free conditions. The easy recyclability of the catalyst and their complete chemoselectivity toward the sulfur group of substrates in the oxidation of sulfides are important “green” attributes of this catalyst.
- Nazarzadeh, Somayeh,Ghorbani-Choghamarani, Arash,Tahanpesar, Elham
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p. 649 - 659
(2018/01/28)
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- Synthetic method of 3-pyridylaldehyde
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The invention relates to the field of organic chemistry, in particular to a synthetic method of 3-pyridylaldehyde. The synthetic method comprises the following steps: 1, taking 3-methyl pyridine as a raw material and obtaining 3-pyridine nitrogen oxide through oxidation reaction under an acidic condition; 2, synthesizing the 3-pyridine nitrogen oxide into acetic acid-3-pyridine methyl ester through acetic anhydride rearrangement; 3, hydrolyzing the acetic acid-3-pyridine methyl ester to obtain 3-pyridine methanol; 4, performing oxidation reaction on the 3-pyridine methanol to obtain 3-pyridylaldehyde. After the synthetic method is adopted, the 3-methyl pyridine is used as the raw material, and the 3-pyridine methanol is obtained through N-oxidation, rearrangement and hydrolyzation and is further oxidized to obtain the 3-pyridylaldehyde. The synthetic method provided by the invention is high in total yield, low in raw material price, short in reaction time, mild in condition, and simple in process operation.
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Paragraph 0032; 0034; 0039; 0044
(2017/11/18)
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- An Elastic Monolithic Catalyst: A Microporous Metalloporphyrin-Containing Framework-Wrapped Melamine Foam for Process-Intensified Acyl Transfer
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The advent of conjugated microporous polymers (CMPs) has had significant impact in catalysis. However, the presence of only micropores in these polymers often imposes diffusion limitations, which has resulted in the low utilization of CMPs in catalytic reactions. Herein, the preparation of a foam-supporting CMP composite with interconnective micropores and macropores and elastic properties is reported. Metalloporphyrin-based CMP organogels are synthesized within the melamine foam by a room-temperature oxidative homocoupling reaction of terminal alkynes. Upon drying, the CMP-based xerogels tightly wrap the framework skeletons of the foam, while the foam cells are still open to allow for the preservation of elasticity and macroporosity. Such a hierarchical structure is efficient for acyl transfer, facilitates substrate diffusion within interpenetrative macropores and micropores, and could be used to intensify catalytic processes.
- Wu, Keyi,Guo, Jia,Wang, Changchun
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supporting information
p. 6013 - 6017
(2016/05/19)
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- Pyridinium saccharinate salts as efficient recyclable acylation catalyst: A new bridge between heterogeneous and homogeneous catalysis
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It is important to find a way for separation of concerned chemicals from product mixture after reaction, in order to avoid spreading harmful chemicals to society. The homogeneous nature of DMAP-catalyzed acylation still suffers from the problems of catalyst separation and/or residual DMAP contamination. DMAP causes acute dermal toxicity, whereas the corresponding DMAP salt exhibits only slight irritation to the skin. Very recently, we found that the DMAP saccharinate salt is also great recyclable catalyst, whose acylation of alcohols has been successfully and effectively carried out 10 times without loss in activity. This report covers our comprehensive studies on using the pyridinium saccharinate salts as efficient recyclable acylation catalysts including 4-N,N-dimethylaminopyridinium saccharinate (A), 4-(1-pyrrolidinyl) pyridinium saccharinate (B), 2-N,N-dimethylaminopyridinium saccharinate (C), and pyridinium saccharinate (D). Their structure and reactivity have been studied. The salts A, C, and D contain very interesting seven-membered synthon showing multiple H-bonding interactions for pair of pyridinium cation and saccharinate anion in the solid state. The salt B exhibits H-bonding interaction of N(sac) ... H-N(py) in the solid state, instead of seven-membered synthon. The catalytic reactivity studies show that salts A and B are both very effective, with salt B even better in reactivity, and are both recyclable in the esterification of a variety of alcohols, under solvent-free and base-free conditions at room temperature.
- Lu, Norman,Chang, Wei-Hsuan,Wei, Rong-Jyun,Fang, Yung-Cheng,Han, Tu-Wen,Wang, Guo-Quan,Chang, Jia-Yaw,Wen, Yuh-Sheng,Liu, Ling-Kang
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p. 3468 - 3476
(2016/06/06)
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- An approach to heterodiarylmethanes via sp2-sp3 Suzuki-Miyaura cross-coupling
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The synthesis of a range of structurally diverse diarylmethanes via the Suzuki-Miyaura cross-coupling of aryl methane acetates and arylboronic acids is reported, including several challenging examples containing nitrogen, oxygen and sulfur heteroatoms in one or both coupling partners. A single set of optimized conditions was used to generate the diarylmethanes in 52-91% yield.
- Stewart, Gavin W.,Maligres, Peter E.,Baxter, Carl A.,Junker, Ellyn M.,Krska, Shane W.,Scott, Jeremy P.
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p. 3701 - 3706
(2016/06/06)
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- A basic germanodecatungstate with a - 7 charge: Efficient chemoselective acylation of primary alcohols
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The synthesis of highly negatively charged polyoxometalates with electrically and structurally controlled uniform basic sites can lead to the unique base catalysis. In this work, a γ-Keggin germanodecatungstate, [γ-HGeW10O36]7- (A), having a -7 charge was, for the first time, successfully synthesized by the reaction of [γ-H2GeW10O36]6- with one equivalent of [(n-C4H9)4N]OH under non-aqueous conditions. The activities of germanodecatungstates for base-catalyzed reactions dramatically increased with increase in the number negative charges from -6 to -7. In the presence of A, various combinations of acylating agents and primary alcohols including those with acid-sensitive functional groups chemoselectively gave the desired acylated products in high yields even under the stoichiometric conditions.
- Sugahara, Kosei,Satake, Naoto,Kamata, Keigo,Nakajima, Takahito,Mizuno, Noritaka
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supporting information
p. 13248 - 13252
(2015/01/09)
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- Base-catalyzed retro-Claisen condensation: A convenient esterification of alcohols via C-C bond cleavage of ketones to afford acylating sources
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The base-catalyzed esterification of alcohols via retro-Claisen condensation has been demonstrated for the first time. A variety of alcohols including aryl- and heteroaryl methanols as well as aliphatic ones underwent efficient acylation to give the ester products in reasonable to good yields upon isolation. Not only conventional 1,3-diketones but also strong electron-withdrawing group containing acetophenones could serve as the acylating suppliers. The synthetic protocol is operationally simple and adaptable to a broad substrate scope. It complements the existed esterification via the retro-Claisen condensation, and enlarges this benign synthetic methodology.
- Xie, Feng,Yan, Fengxia,Chen, Mengmeng,Zhang, Min
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p. 29502 - 29508
(2014/08/05)
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- Tribromo melamine as novel and versatile catalyst for the formylation and acetylation of alcohols
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Tribromo melamine has been found to be an efficient and green organocatalyst for the acetylation and formylation reactions of alcohols with acetic anhydride and ethyl formate at room temperature and under mild reaction conditions.
- Hajjami, Maryam,Ghorbani-Choghamarani, Arash,Karamshahi, Zahra,Norouzi, Masoomeh
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p. 260 - 263
(2014/03/21)
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- Cp*Rh-based heterometallic metallarectangles: Size-dependent borromean link structures and catalytic acyl transfer
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A series of CpRh-based functional metallarectangles have been synthesized from metallaligands. Enlargement of one linker leads to the isolation of two novel Borromean link architectures. All these complexes are intact in solution, as evident from ESI-MS spectroscopic analysis. Arising from the combination of open Cu centers and favorable cavity space, {(CpRh)4(bpe) 2[Cu(opba)·2MeOH]2}4(OTf)·6MeOH shows extraordinary catalytic abilities with high efficiency and wide substrate selectivity in the acyl-transfer reaction.
- Huang, Sheng-Li,Lin, Yue-Jian,Hor, T. S. Andy,Jin, Guo-Xin
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supporting information
p. 8125 - 8128
(2013/07/19)
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- A salt made of 4-N,N-dimethylaminopyridine (DMAP) and saccharin as an efficient recyclable acylation catalyst: A new bridge between heterogeneous and homogeneous catalysis
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Here, we report insights into the new recyclable catalyst 1, (DMAP·saccharin). The DMAP·saccharin-catalysed acylation of alcohols has been successfully carried out more than 8 times. Only 1 mol% of catalyst 1 efficiently promotes acylation with almost equimolar amounts of acid anhydrides, under both base-free and solvent-free conditions.
- Lu, Norman,Chang, Wei-Hsuan,Tu, Wen-Han,Li, Chieh-Keng
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supporting information; experimental part
p. 7227 - 7229
(2011/09/12)
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- Electron-deficient [TiIV(salophen)(OTf)2]: A new and highly efficient catalyst for the acetylation of alcohols and phenols with acetic anhydride
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In the present work, a highly efficient method for acetylation of alcohols and phenols with acetic anhydride catalyzed by high-valent [Ti IV(salophen)(OTf)2] is reported. Under these conditions, primary, secondary and tertiary alcohols as well as phenols were acetylated with short reaction times and high yields. The catalyst was reused several times without loss of its catalytic activity.
- Yadegari, Maryam,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj
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experimental part
p. 2237 - 2243
(2011/10/03)
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- Investigation of catalytic activity of high-valent vanadium(IV) tetraphenylporphyrin: A new, highly efficient and reusable catalyst for acetylation of alcohols and phenols with acetic anhydride
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In the present work, the catalytic activity of high-valent tetraphenylporphyrinatovanadium(IV) trifluoromethanesulfonate, [V IV(TPP)(OTf)2], in the acetylation of alcohols and phenols with Ac2O is reported. This new V(IV) catalyst was used as an efficient catalyst for not only primary alcohols (benzylic and aliphatic) but also sterically-hindered secondary and tertiary alcohols with acetic anhydride and the corresponding acetates were obtained in 85-99% yield and 0.5-15 min. Acetylation of phenols with acetic anhydride was also performed to afford the desired acetates in 88-99% and 1.5-20 min. This catalyst can be reused several times without loss of its catalytic activity.
- Taghavi, S. Abdolmanaf,Moghadam, Majid,Mohammadpoor-Baltork, Iraj,Tangestaninejad, Shahram,Mirkhani, Valiollah,Khosropour, Ahmad Reza
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experimental part
p. 159 - 164
(2011/12/16)
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- Synthesis of alkyl heteryl ethers from acetates under interphase catalysis conditions in a liquid/solid system
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The reaction of acetates of heterocyclic alcohols with alkyl halides in the two-phase catalytic system of solid KOH/C6H6/18-crown-6 at room temperature leads selectively to the formation of the corresponding heterocyclic ethers in 32-93% yield. 1998 Plenum Publishing Corporation.
- Abele,Abele,Gaukhman,Lukevics
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- Oxidation of substituted pyridines PyrCHRSiMe3 (R=H, Me, Ph) and substituted quinolines QnCH2SiMe3 with hypervalent iodine reagents
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Oxidation of a variety of substituted pyridines, PyrCHRSiMe3 (R = H, Me, Ph) and quinolines, QnCH2SiMe3 with hypervalent iodine reagents PIDA, (PhI(OCOCH3)2) and PIFA, (PhI(OCOCF3)2) has been studied. Oxy-desilylation with PIDA/TBAF gives low to moderate yields of PyrCHROR1 and QnCH2OR1 (R1 = H, Ac), while good yields of PyrCHROH and QnCH2OH are obtained when PIFA is used.
- Andrews, Ian P.,Lewis, Norman J.,McKillop, Alexander,Wells, Andrew S.
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p. 1151 - 1158
(2007/10/03)
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- The Mechanism of the Reaction of Nicotinic Acid 1-Oxide with Acetic Anhydride
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In order to elucidate the mechanism of the 2-acetylation in the reaction of nicotinic acid 1-oxide (2a) with boiling acetic anhydride, thermal reactions and reactions with hot acetic anhydride have been explored with 3-X-pyridine 1-oxides (2).The former reactions of 2d (X = CONHAc), 2f (X = CONMeAc), 2h (X = CH2OAc) and 2j result in recovery or decomposition.The latter reactions of 2c (X = CONH2), 2d, 2e (X = CONHMe), 2h and 2j bring about mainly deoxygenative α-acetoxylation, no 2-acetylation being noticed.However, the reaction of 2f with acetic anhydride affords 6,7-dihydro-6-methyl-7-methylene-5H-pyrrolopyridin-5-one 1-oxide (7) as an initial product, which further undergoes deoxygenative β-acetoxylation to give 7-acetoxy-7-acetoxymethyl-6,7-dihydro-6-methyl-5H-pyrrolopyridin-5-one (8) and 7-acetoxymethylene-6,7-dihydro-6-methyl-5H-pyrrolopyridin-5-one (9).On the basis of the results we propose a new electrophilic pathway for the 2-acetylation of 2a and 2f.Keywords - pyridine 1-oxide 3-substituted; nicotinic acid 1-oxide; nicotinamide 1-oxide N-acetyl-N-methyl; pyrrolopyridine; 2-acetylation; pyridone formation
- Nagano, Hiroyuki,Nawata, Yoshiharu,Hamana, Masatomo
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p. 4068 - 4077
(2007/10/02)
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