- Autorecycling System for Reduction of Carbonyl Compounds to Alcohols by 1,5-Dihydro-5-deazaflavins
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An effective recycling system for the reduction of carbonyl compounds to alcohols was constructed for the first time using 5-deazaflavins and formic acid, in such a way that each mol of the compound catalyses the reduction, by formic acid, of up to 25 mol of benzaldehyde.
- Yoneda, Fumio,Kuroda, Kazunori,Kamishimoto, Mutsuko
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- Aryl Cations: Searching for and Assigning Structures to + Isomers
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The energetics and mass spectral characteristics of a number of + ions have been examined.No compelling evidence could be found to show that the 2-cyclopropaphenyl cation was produced by loss of bromine from the ionized 2-bromo derivative.It was proposed that the ethynylcyclopentadienyl cation may be the global minimum on the + hypersurface.
- Bissonnette, Martine C.,George, M.,Holmes John, L.
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Read Online
- Silica sulfuric acid and AI(HSO4)3: As efficient catalysts for the formylation of alcohols by using ethyl formate under heterogeneous conditions
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A mixture of ethyl formate and a catalytic amount of silica sulfuric acid or Al(HSO4)3 as suitable formylating systems can formylate various alcohols to their corresponding formate ester derivatives under mild, nearly neutral and heterogeneous conditions at room temperature with good to excellent yields.
- Zolfigol, Mohammad Ali,Chehardoli, Gholamabbas,Dehghanian, Mina,Niknam, Khodabakhsh,Shirini, Farhad,Khoramabadi-Zad, Ahmad
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- Conversion of alkyl halides into alcohols via formyloxylation reaction with DMF catalyzed by silver salts
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The transformation of alkyl halides into alcohols via a two-step process based on the reaction with DMF catalyzed by Ag(I) salts followed by acid or basic hydrolysis of the intermediate formate ester has been evaluated. The results show that a large variety of primary and some secondary alkyl halides can be transformed efficiently into the corresponding alcohols, making this alkyl halide to alcohol interconversion a valuable alternative to the existing procedures, particularly in molecules with labile functional groups that are generally involved in multistep synthesis. Georg Thieme Verlag Stuttgart.
- Abad, Antonio,Agullo, Consuelo,Cunat, Ana C.,Navarro, Ismael
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- Lewis Base Promoted Reduction of CO2 with BH3NH3 into Boryl Formates: CO2 as a Carbon Source in Organic Synthesis Under Mild Conditions
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Lewis base promoted selective reduction of CO2 into boryl formates by using BH3NH3 as a reductant under mild conditions has been reported. The boryl formates, generated in situ, were shown to be reactive and versatile sources of formyl compounds to create new C–N, C–O, and C–C bonds. The reactivity of the boryl formates to yield formic acid, formamides, formates, secondary alcohols, and benzoheterocyclic rings was investigated.
- Zhang, Bo,Du, Gaixia,Hang, Wei,Wang, Sheng,Xi, Chanjuan
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Read Online
- Operando systems chemistry reaction catalysis (OSCR-Cat) for visible light driven CO2conversion
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A systems chemistry approach is taken for compartmentalization of a continuous reaction medium (water and CO2) with induced creation of micro-heterogeneity in the medium by using a SOM (soft-oxometalate) catalyst. The first step involves compartmentalization of an assembled catalyst-photosensitizer duo catalysing the reduction of CO2into formic acid in two reaction spaces: the interior of the compartment and the exterior of the compartment. The exterior compartment obeys typical surface activity driven nanocatalysis principles where the perturbation of the catalyst surface area inversely varies with product yield. The second step of disassembly to disrupt the SOM-catalyst, induced by addition of a base, releases the interior reaction product with total disappearance of the catalyst system. The assembly-disassembly cascade demonstrates the application of systems chemistry principles in perturbation, compartmentalization, catalysis and release of products with well-defined externally controlled stimuli such as concentration, light, and pH. The OSCR-catalyst reported here is an attempt to emulate Golgi bodies in the context of cellular chemistry on a functional level.
- Das, Kousik,De, Ratnadip,Roy, Soumyajit,Verpoort, Francis
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p. 13355 - 13365
(2021/06/16)
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- Substituted 9-Anthraldehydes from Dibenzocycloheptanol Epoxides via Acid-Catalyzed Epoxide Opening/Semipinacol Rearrangement
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Starting from benzaldehyde derivatives, the corresponding dibenzocycloheptenol could be prepared in five steps. Under both substrate (secondary vs tertiary alcohol and the substituents on the aromatic ring(s)) and condition control, the subsequent epoxidation and acid-catalyzed epoxide opening/semipinacol rearrangement/aromatization afforded the corresponding 9-anthraldehydes in good yields, up to 88% over two steps. The presence of the electron-withdrawing group(s) on the aromatic ring(s) suppressed the rate of the epoxidation while the subsequent semipinacol rearrangement step required heating; the presence of the electron-donating group(s), on the other hand, frequently led to the decomposition during the epoxidation. From the mechanistic studies, the semipinacol rearrangement of the epoxide could precede the ionization at the bisbenzylic position, yielding the aldehyde intermediate. The ensuing dehydrative aromatization led to the formation of 9-anthraldehyde. Conversely, nucleophilic addition to the aldehyde and dehydrative aromatization with concomitant loss of formic acid led to anthracene.
- Phumjan, Tanawat,Songthammawat, Poramate,Jongcharoenkamol, Jira,Batsomboon, Paratchata,Ruchirawat, Somsak,Ploypradith, Poonsakdi
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p. 13322 - 13349
(2021/09/13)
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- Chemoselective: O -formyl and O -acyl protection of alkanolamines, phenoxyethanols and alcohols catalyzed by nickel(ii) and copper(ii)-catalysts
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Achieving chemoselectivity is always crucial and challenging for bi-functional compounds, such as alkanolamines, that have both amines and alcohols as reactive functional groups. Achieving 100% selectivity for O-formyl and O-acyl protection of alkanolamines is one of the examples of such reactions. To avoid protection and deprotection steps and overcome this problem, a novel chemoselective, efficient, and simple protocol for functional group protection as O-formylation and O-acylation of alkanolamines and phenoxyethanols and competitive O-selectivity between alcohols and amines, catalyzed by Ni(ii) and Cu(ii) complexes with 8-hydroxyquinoline at a catalyst loading of only 5 mol% in a homogeneous medium has been presented here. Good to excellent yields are achieved in the absence of a solvent for O-formylation at room temperature with formic acid as the formyl source and O-acylation at 70 °C with acetic acid as the acyl source. In addition, minimal effluent and waste are generated during this reaction, as the corresponding sodium salts of acids could be recovered during the process and can be reused. This chemistry readily tolerates a variety of functional groups, as demonstrated by 20 examples with 100% chemoselectivity for O-formylation and O-acylation of alkanolamines and 30 examples of O-formylation and O-acylation of phenoxyethanols and alcohols in the presence of amines which have been synthesized successfully.
- Sonawane, Rahul B.,Sonawane, Swapnali R.,Rasal, Nishant K.,Jagtap, Sangeeta V.
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supporting information
p. 3186 - 3195
(2020/06/19)
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- Ionic liquid-stabilized vanadium oxo-clusters catalyzing alkane oxidation by regulating oligovanadates
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Alkane oxidation under mild conditions occupies an important position in the chemical industry. Herein, we have designed a novel class of ionic liquid ([TBA][Pic])-stabilized vanadium oxo-clusters (TBA = tetrabutylammonium; Pic = picolinate ions), in which the molar ratio of the IL to V atoms can be tuned facilely to obtain V-OC?IL-0.5, V-OC?IL-1 and V-OC?IL-2, respectively. The as-synthesized vanadium oxo-clusters have been characterized by elemental analysis, FT-IR, UV-vis, XRD, TGA, EPR, NMR and MS. These vanadium oxo-clusters were catalytically active for catalyzing the oxidation of cyclohexane with H2O2 as an oxidant. In particular, the oxo-cluster V-OC?IL-1 (where IL/V is 1.0) can provide an approximately 30% total yield of KA oil (cyclohexanol and cyclohexanone) without adding any co-catalyst at 50 °C within 1.0 h. Moreover, the present vanadium oxo-cluster was recyclable owing to the modification of the IL and it can also be extended to the oxidation of the sp2 hybrid aromatic ring. The further characterization results demonstrated that the oligovanadate anions were strongly dependent on the molar ratio of the IL to V atoms. The vanadium oxo-clusters with the appropriate molar ratio of IL/V could exist in the form of a trimer and a dimer due to the presence of the TBA cation and the coordination of picolinate. Notably, the oligovanadate anions are highly active species for the C-H oxidation but the mononuclear vanadate afforded a very poor activity according to the activity assessment and the identification of vanadium species from the 51V NMR spectra and MS spectra. The annihilation reaction of free radicals and EPR characterization suggested that the vanadium oxo-clusters operated via a mechanism of the HO radical in the oxidation reaction.
- Ding, Bingjie,Gong, Xueqing,Hou, Zhenshan,Li, Difan,Yao, Yefeng,Zhang, Ran,Zheng, Anna,Zhou, Qingqing
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p. 7601 - 7612
(2020/11/27)
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- Efficient Enzymatic Preparation of Flavor Esters in Water
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A straightforward biocatalytic method for the enzymatic preparation of different flavor esters starting from primary alcohols (e.g., isoamyl, n-hexyl, geranyl, cinnamyl, 2-phenethyl, and benzyl alcohols) and naturally available ethyl esters (e.g., formate, acetate, propionate, and butyrate) was developed. The biotransformations are catalyzed by an acyltransferase from Mycobacterium smegmatis (MsAcT) and proceeded with excellent yields (80-97%) and short reaction times (30-120 min), even when high substrate concentrations (up to 0.5 M) were used. This enzymatic strategy represents an efficient alternative to the application of lipases in organic solvents and a significant improvement compared with already known methods in terms of reduced use of organic solvents, paving the way to sustainable and efficient preparation of natural flavoring agents.
- Perdomo, Igor Chiarelli,Gianolio, Stefania,Pinto, Andrea,Romano, Diego,Contente, Martina Letizia,Paradisi, Francesca,Molinari, Francesco
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p. 6517 - 6522
(2019/06/20)
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- One-Pot Conversion of Cinnamaldehyde to 2-Phenylethanol via a Biosynthetic Cascade Reaction
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A novel biosynthetic pathway for the production of natural 2-phenylethanol from cinnamaldehyde is reported. An ene-reductase (OYE)-mediated selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde is followed by a regioselective Baeyer-Villiger oxidation (BVMO) to produce the corresponding formate ester that either spontaneously hydrolyzes to 2-phenylethanol in water or is assisted by a formate dehydrogenase (FDH). This cascade reaction is performed in a one-pot fashion at ambient temperature and pressure. High selectivity and complete conversion were achieved.
- Vorster, Amanda,Smit, Martha S.,Opperman, Diederik J.
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supporting information
p. 7024 - 7027
(2019/09/12)
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- Photocatalytic Chemical CO2 Fixation by Cu-BDC Nanosheet?Macroporous-Mesoporous-TiO2 under Mild Conditions
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Growing greenhouse gas CO2 is driving the research on the chemical fixation of CO2. Here, the organic reaction of CO2 with benzyl halogen for chemical CO2 fixation under ambient conditions with irradiation of ultraviolet light is successfully catalyzed by Cu-BDC nanosheet?macroporous-mesoporous-TiO2 (Cu-BDC?macro-meso-TiO2), which shows high photocatalytic activity for both benzyl chloride and bromide reacting with CO2. Meanwhile, the prepared Cu-BDC?macro-meso-TiO2 possesses a three-scale porous structure, including macropores, mesopores, and micropores. In the uniform hierarchical structure, the microporous Cu-BDC nanosheet is confined in the macropore of macroporous-mesoporous-TiO2, while the ordered mesoporous structure is in the macroporous walls. This multilevel porous distribution can significantly improve the active surface areas and mass transfer efficiency of Cu-BDC?macro-meso-TiO2. Therefore, this finding has opened a field of research on photocatalytic chemical CO2 fixation.
- Li, Zhenxing,Chu, Junmei,Meng, Dong,Wen, Yangyang,Xing, Xiaofei,Miao, He,Hu, Mingliang,Yu, Chengcheng,Wei, Zhiting,Yang, Yang,Li, Yongle
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p. 8659 - 8668
(2019/09/30)
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- Sustainable Co-Synthesis of Glycolic Acid, Formamides and Formates from 1,3-Dihydroxyacetone by a Cu/Al2O3 Catalyst with a Single Active Sites
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Glycolic acid (GA), as important building block of biodegradable polymers, has been synthesized for the first time in excellent yields at room temperature by selective oxidation of 1,3-dihyroxyacetone (DHA) using a cheap supported Cu/Al2O3 catalyst with single active CuII species. By combining EPR spin-trapping and operando ATR-IR experiments, different mechanisms for the co-synthesis of GA, formates, and formamides have been derived, in which .OH radicals formed from H2O2 by a Fenton-like reaction play a key role.
- Dai, Xingchao,Adomeit, Sven,Rabeah, Jabor,Kreyenschulte, Carsten,Brückner, Angelika,Wang, Hongli,Shi, Feng
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supporting information
p. 5251 - 5255
(2019/03/07)
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- Making Carbonyls of Amides Nucleophilic and Hydroxyls of Alcohols Electrophilic Mediated by SO2F2 for Synthesis of Esters from Amides
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We discovered that with the promotion of sulfuryl fluoride, the carbonyl groups of amides performed as nucleophiles while the hydroxyl groups of alcohols were activated to functionalize as electrophiles. This study displayed that the amide C-N bonds could be easily cleaved with delicate nucleophiles to form the ester C-O bonds at room temperature without using transition metals. The broad substrate scope and excellent functional group compatibility were proved with 44 examples in up to 99% yields.
- Fang, Wan-Yin,Zha, Gao-Feng,Qin, Hua-Li
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supporting information
p. 8657 - 8661
(2019/10/17)
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- A phase transfer catalysis synthesis method of benzyl (by machine translation)
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The invention relates to a phase transfer catalysis synthesis of benzyl method, this method to the alkene is solid graphite oxide carries ji anyan as catalyst, in order to [...] and carboxylate as raw materials, water as a solvent, in the 80 - 120 °C conditions can be achieved under the benzyl ester high efficient synthesis, [...] conversion is higher than 99%, benzyl ester selectivity higher than 97%. The method is simple in operation, process green, catalyst is easy to recover and duplicate using of good performance, after treatment of the product is simple, the production cost is low. (by machine translation)
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Paragraph 0028-0031
(2018/04/01)
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- A General, Activator-Free Palladium-Catalyzed Synthesis of Arylacetic and Benzoic Acids from Formic Acid
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A new catalyst for the carboxylative synthesis of arylacetic and benzoic acids using formic acid (HCOOH) as the CO surrogate was developed. In an improvement over previous work, CO is generated in situ without the need for any additional activators. Key to success was the use of a specific system consisting of palladium acetate and 1,2-bis((tert-butyl(2-pyridinyl)phosphinyl)methyl)benzene. The generality of this method is demonstrated by the synthesis of more than 30 carboxylic acids, including non-steroidal anti-inflammatory drugs (NSAIDs), under mild conditions in good yields.
- Wang, Lin,Neumann, Helfried,Beller, Matthias
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supporting information
p. 6910 - 6914
(2018/06/04)
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- Method for preparing formate-type compound
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The invention discloses a method for preparing a formate-type compound. The method comprises the following steps of: adopting an alcohol-type compound and 1,3-dihydroxyacetone as reaction raw materials, and under the existence of a composite catalyst and an oxidant, reacting for 2-48 hours in a reaction medium in a reactor at a reaction temperature of 25-100 DEG C so as to obtain the formate-typecompound. The method disclosed by the invention is simple, and is mild in reaction condition, and by the method, a target product can be obtained by low cost and high yield; the used catalyst has highcatalytic activity, and is easily separated from a reaction system to be repeatedly used; the whole process is environment-friendly, and the reaction raw material (1,3-dihydroxyacetone) is easily converted from a side product (glycerol) of biodiesel, so that the utilization of the glycerol is promoted.
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Paragraph 0039; 0047; 0048
(2018/07/30)
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- Purified mCPBA, a Useful Reagent for the Oxidation of Aldehydes
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Purified mCPBA is a useful reagent for the oxidation of several classes of aldehyde. Although linear unbranched aliphatic aldehydes are oxidized to the corresponding carboxylic acids, α-branched ones undergo Baeyer–Villiger oxidation to formates. α-Branched α,β-unsaturated aldehydes provide enolformates and/or epoxides, which can be saponified to α-hydroxy ketones with shortening of the carbon chain by 1 carbon. Unbranched α,β-unsaturated aldehydes undergo an interesting Baeyer–Villiger oxidation/epoxidation/formate migration/BV oxidation cascade, which results in formyl-protected hydrates with an overall loss of two carbon atoms.
- Horn, Alexander,Kazmaier, Uli
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p. 2531 - 2536
(2018/03/21)
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- An alternative route to tethered Ru(II) transfer hydrogenation catalysts
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A new route towards a series of tethered η6-arene/Ru(II) catalysts for use in the transfer and pressure hydrogenation of ketones and aldehydes to alcohols is reported. The route proceeds through the formation of an amide from the diamine precursor, followed by reduction, rather than the direct alkylation of the diamine. This has the advantage that dialkylation of the amine is avoided during the synthesis. Through this new route, both racemic and enantiomerically-pure η6-arene/Ru(II) tethered catalysts can be prepared in high yield.
- Hodgkinson, Roy,Jur?ík, Václav,Nedden, Hans,Blackaby, Andrew,Wills, Martin
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supporting information
p. 930 - 933
(2018/02/12)
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- Fe-catalyzed esterification of amides via C-N bond activation
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An efficient Fe-catalyzed esterification of primary, secondary, and tertiary amides with various alcohols for the preparation of esters was performed. The esterification process was accomplished with FeCl3$6H2O, which is a stable, inexpensive, environmentally friendly catalyst with high functional group tolerance.
- Chen, Xiuling,Hu, Siying,Chen, Rongxing,Wang, Jian,Wu, Minghu,Guo, Haibin,Sun, Shaofa
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p. 4571 - 4576
(2018/02/09)
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- Application of polydopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles (Fe3O4@PDA-SO3H) as a heterogeneous and recyclable nanocatalyst for the formylation of alcohols and amines under solvent-free conditions
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Herein, formylation of structurally different amines and alcohols with ethyl formate was carried out in the presence of a catalytic proportion of sulfonic acid supported on polydopamine (PDA)-encapsulated Fe3O4 nanoparticles as a heterogeneous, recyclable, and greatly efficient catalyst; this method provided the corresponding N-formyl compounds in good to excellent yields under solvent-free conditions. The magnetically catalytic system was recovered, by-passing the time-consuming filtration operation using an external magnet device. This procedure also increases the purity of the product and promises economic and ecological advantages. Furthermore, the recovery and reuse of the catalyst was demonstrated five times without detectable loss in the activity.
- Taheri, Sepideh,Veisi, Hojat,Hekmati, Malak
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p. 5075 - 5081
(2017/07/11)
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- Kinetics and DFT Studies of Photoredox Carbon-Carbon Bond Cleavage Reactions by Molecular Vanadium Catalysts under Ambient Conditions
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Visible light assisted photocatalytic organic reactions have recently received intense attention as a versatile approach to achieve selective chemical transformations, including C-C and several C-X (X = N, O, S) bond formations under mild reaction conditions. The light harvesters in previous reports predominantly comprise ruthenium or iridium photosensitizers. In contrast, selective, photocatalytic aliphatic C-C bond cleavage reactions are scarce. The present study focuses on rationally designing VV oxo complexes as molecular, photoredox catalysts toward the selective activation and cleavage of a C-C bond adjacent to the alcohol group in aliphatic alcoholic substrates. We have employed kinetics measurements and DFT calculations to develop a candidate for the catalytic C-C bond activation reaction that is up to 7 times faster than our original vanadium complex. We have also identified a substrate where the C-C bond cleaves at rates 2.5-17 times faster, depending on the catalyst used. In order to better understand the effects of ligand modification on the thermodynamics and catalysis, DFT calculations were employed to reveal the orbital energies, the electronic transitions during the C-C bond cleavage, and the activation barriers. Our combined kinetics and computational studies indicate that the incorporation of electron-withdrawing groups at select sites of the ligand is essential for the development of active and stable vanadium photocatalysts for our C-C bond cleavage reactions.
- Gazi, Sarifuddin,Doki?, Milo?,Moeljadi, Adhitya Mangala Putra,Ganguly, Rakesh,Hirao, Hajime,Soo, Han Sen
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p. 4682 - 4691
(2017/07/24)
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- N-Heterocyclic Carbene Catalyzed Transformylation
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The N-heterocyclic carbene (NHC) catalyzed transformylation has been developed for the conversion of 1°, 2°, and 3° alcohols to the corresponding formates. The reaction employs low catalyst loadings and methyl formate as the formyl transfer reagent. The scope of the reaction is broad with 23 examples reported with good yields (59-96%). The reaction is insensitive to common nitrogen and oxygen protecting groups and can be achieved in the presence of a number of heterocycles.
- Fernando, Jared E. M.,Levens, Alison,Moock, Daniel,Lupton, David W.
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p. 3505 - 3510
(2017/07/27)
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- Heteroleptic 1D coordination polymers: 5-Coordinated zinc(II) polymer as an efficient transesterification catalyst
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The synthesis of three 1D coordination polymers (CPs), [Zn(TPPZ)(HCCB)]n·DMF·H2O (1) [Cd(TPPZ)(HCCB)]n(2) and [Co(TPPZ)(HCCB)]n(3), based on the N,N,N-chelating κ3-2,3,5,6-tetrakis(2-pyridyl)pyrazine (TPPZ) and polymerizing carboxylate (–COO?) 3-(carboxy-methylamino)-4-chlorobenzoic acid (H3CCB) ligands, using a solvothermal method, have been described. The CPs have been adequately characterized by satisfactory elemental analyses, FT-IR, UV–vis, emission, TGA and PXRD analysis. The structure of 1 has been verified by single crystal X-ray diffraction analysis. The structural data revealed the 5-coordinated heteroleptic polymeric framework is exclusively extended through the H3CCB carboxylate group and strong N,N,N-chelating TPPZ ligand acts as a branch terminating site. Notably, the structure of 1 is comprised of one unit of each H2O and DMF solvent in its crystal lattice. In contrast, 2 and 3 exclude lattice solvents, as suggested by PXRD studies, after thermal desolvation of 1. Furthermore, 1 with 5-coordinated Zn(II) centers exhibited an efficient catalytic performance for transesterification reactions, with remarkable stability and good reusability.
- Wani, Manzoor A.,Kumar, Ashish,Pandey, Mrituanjay D.,Pandey, Rampal
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supporting information
p. 142 - 149
(2017/02/19)
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- Acidic ionic liquid immobilized on nanoporous Na+-montmorillonite as an efficient and reusable catalyst for the formylation of amines and alcohols
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In this work, nanoporous sodium montmorillonite clay (Na+-MMT) was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The Na+-MMT chemical modification ([Na+-MMT-[pmim]HSO4) was confirmed by a variety of techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy and potentiometric titration. The catalytic performance of this immobilized acidic ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent-free conditions. This reagent is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also, this catalyst can be reused ten times without loss of its catalytic activity.
- Shirini, Farhad,Mazloumi, Masoumeh,Seddighi, Mohadeseh
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p. 1759 - 1776
(2016/03/16)
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- TiCl4/Et3N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates
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A methodology to build (E)-β-alkoxy- and (E)-β-aryloxyacrylate moieties from acetate and formate esters promoted by the TiCl4/Et3N system is presented. The reaction is compatible with a broad range of structural skeletons and elapses through an unusual condensation pathway. Taking into account the obtained results, we propose a plausible mechanism involving a bimetallic titanium intermediate for this type of transformation.
- álvarez-Calero, José María,Jorge, Zacarías D.,Massanet, Guillermo M.
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supporting information
p. 6344 - 6347
(2016/12/23)
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- Deep eutectic solvent choline chloride·2CrCl3·6H2O: An efficient catalyst for esterification of formic and acetic acid at room temperature
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A highly efficient and selective method for esterification of formic and acetic acid with alcohols has been achieved at room temperature, with the choline chloride (ChCl)/chromium(iii) chloride hexahydrate (CrCl3·6H2O) deep eutectic solvent as a catalyst. High yields and good selectivities of organic esters are obtained using DES [ChCl][CrCl3·6H2O]2 with the molar ratio 5:1 (carboxylic acids:alcohols) at room temperature in 24 h. The ease of recovery and reusability of DES with high catalytic activity makes this method efficient and practical.
- Cao, Jin,Qi, Bin,Liu, Jun,Shang, Yuhan,Liu, Huiwen,Wang, Wenjing,Lv, Jia,Chen, Zhiyan,Zhang, Haibo,Zhou, Xiaohai
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p. 21612 - 21616
(2016/03/08)
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- METAL CATALYZED PROCESS FOR REDUCTION OF CO2 TO SODIUM FORMATE AND FORMIC ACID
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The patent discloses a one step, one pot metal catalyzed process for synthesis of formic acid or sodium formate from CO2 in the presence of reducing agent and a catalyst or without catalyst at moderate temperature and atmospheric pressure with high yields.
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Paragraph 080; 081
(2016/02/29)
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- Ruthenium-Catalyzed Synthesis of Dialkoxymethane Ethers Utilizing Carbon Dioxide and Molecular Hydrogen
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The synthesis of dimethoxymethane (DMM) by a multistep reaction of methanol with carbon dioxide and molecular hydrogen is reported. Using the molecular catalyst [Ru(triphos)(tmm)] in combination with the Lewis acid Al(OTf)3resulted in a versatile catalytic system for the synthesis of various dialkoxymethane ethers. This new catalytic reaction provides the first synthetic example for the selective conversion of carbon dioxide and hydrogen into a formaldehyde oxidation level, thus opening access to new molecular structures using this important C1source.
- Thenert, Katharina,Beydoun, Kassem,Wiesenthal, Jan,Leitner, Walter,Klankermayer, Jürgen
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supporting information
p. 12266 - 12269
(2016/10/13)
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- ZINC COMPLEX
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A zinc complex characterized in exhibiting an octahedral structure and being configured from repeating units represented by general formula (I): wherein L represents a linker region, and R1 represents a C1-4 alkyl group, which can have a halogen atom.
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- Cu(ii)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds
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A novel Cu(ii)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.
- Ma, Ran,He, Liang-Nian,Liu, An-Hua,Song, Qing-Wen
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supporting information
p. 2145 - 2148
(2016/02/09)
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- Tribromoisocyanuric acid (TBCA) as a mild and metal free catalyst for the acetylation and formylation of hydroxyl groups under solvent free conditions
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A convenient approach for acetylation and formylation of various types of alcohols and phenols with acetic anhydride and formic acid in the presence of Tribromoisocyanuric acid (TBCA) as catalyst is reported. The reactions were carried out under solvent-free condition and in good to high yields at room temperature. This present method is featured with relatively mild reaction conditions, simple operation, broad substrate scope, clean work-up, short reaction times, good to high yields, excellent selectivity and also avoids tedious purifications and the use of toxic reagents.
- Hekmatian, Zahra,Khazaei, Ardeshir
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p. 1565 - 1570
(2016/01/26)
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- Method of manufacturing imidoyl diazidosulfochloride compd. various compd. and manufacturing method of using the same
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PROBLEM TO BE SOLVED: To provide a new production method for synthesizing an imidoyl chloride compound dispensing with chlorination agents having poor handleability, to provide a method for producing various compounds in high yield and purity by using the imidoyl chloride compound, and to provide a method for isolating the imidoyl chloride compound in high efficiency and purity from a mixture of the imidoyl chloride compound and a phthalic anhydride compound.SOLUTION: The method for producing the imidoyl chloride compound comprises reaction of a specific amide compound with a specific phthaloyl chloride compound to produce a specific imidoyl chloride compound.
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Paragraph 0056
(2016/12/16)
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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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- Br?nsted acidic ionic liquid supported on rice husk ash (RHA-[pmim]HSO4): A highly efficient and reusable catalyst for the formylation of amines and alcohols
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In this work, rice husk ash (RHA), as a natural source of amorphous silica, was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The immobilized acidic ionic liquid was characterized with a variety of techniques including infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and pH analysis. The catalytic performance of this heterogeneous ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent free conditions. It is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also this catalyst can be reused ten times without loss of its catalytic activity.
- Shirini, Farhad,Seddighi, Mohadeseh,Mamaghani, Manouchehr
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p. 50631 - 50638
(2014/12/10)
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- An eco-benign and highly efficient procedure for N-acylation catalyzed by heteropolyanion-based ionic liquids using carboxylic acid under solvent-free conditions
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An eco-benign and highly efficient route for N-acylation of amines has been developed by treating amines with corresponding carboxylic acids in the presence of 2 mol % of heteropolyanion-based ionic liquids as catalysts under solvent-free conditions. This practical reaction could tolerate a wide range of substrates. Thus, various N-acylation products including N-acyl α-amino acid derivatives were obtained in moderate to excellent yields at 70 C to 120 C. Moreover, recycling studies revealed that heteropolyanion-based ionic liquids were easily reusable for this N-acylation. This method provides a green and much improved protocol over the existing methods.
- Chen, Zhikai,Fu, Renzhong,Chai, Wen,Zheng, Hao,Sun, Lin,Lu, Qiang,Yuan, Rongxin
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p. 2237 - 2245
(2014/03/21)
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- MONOMER, POLYMER, RESIST COMPOSITION, AND PATTERNING PROCESS
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A polymer comprising recurring units derived from a (meth)acrylate monomer of tertiary ester type having branched alkyl on alicycle is used to form a resist composition. When subjected to exposure, PEB and organic solvent development, the resist composition is improved in dissolution contrast.
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- Convenient esterification of carboxylic acids by SN2 reaction promoted by a protic ionic-liquid system formed in situ in solvent-free conditions
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The reaction of esterification of benzoic acid with benzyl chloride was chosen as a model reaction to study the esterification by SN2 promoted by tertiary amine as deprotonating agent. The use of ionic liquid (IL) 1,3-dimethylimidazolium methanesulfonate [MMIm][OMs] as reaction medium has proven to give quantitative yield of the ester, but interestingly the reaction does occur even in solvent-free conditions, where the acid + the amine form a liquid system (a protic IL) in situ. This last methodology was extended to several carboxylic acids in conditions of atom economy (i.e., without excess of any reagent), giving moderately good yields of esters (54-78%) recovered by weight in pure form.
- Cardellini, Fabio,Brinchi, Lucia,Germani, Raimondo,Tiecco, Matteo
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p. 3248 - 3256
(2015/10/06)
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- Non-heme iron hydroperoxo species in superoxide reductase as a catalyst for oxidation reactions
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The non-heme high-spin ferric iron hydroperoxo species formed in superoxide reductase catalyzes oxidative aldehyde deformylation through its nucleophilic character. This species also acts as an electrophile to catalyze oxygen atom transfer in sulfoxidation reactions, highlighting the oxidation potential of non-heme iron hydroperoxo species. This journal is
- Rat,Mnage,Thomas,Nivire
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supporting information
p. 14213 - 14216
(2015/02/19)
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- Formylation of amines catalysed by protic ionic liquids under solvent-free condition
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A fast, efficient and simple route for the N-formylation of amines has been developed by treating amines with 85% formic acid at 70°C in the presence of 5 mol % of protic ionic liquid as catalyst under solvent-free condition. This method provides a green and much improved protocol over the existing methods.
- Majumdar, Swapan,De, Jhinuk,Hossain, Jewel,Basak, Ajoy
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p. 262 - 266
(2013/02/22)
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- Application of Sulfonic Acid Functionalised Hybrid Silicas Obtained by Oxidative Cleavage of Tetrasulfide Bridges as Catalysts in Esterification Reactions
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Hybrid materials with tetrasulfide bridges were synthesised by co-condensation between bis[3-(triethoxysilyl)propyl]tetrasulfide and either tetraethyl orthosilicate or 1,4-bis(triethoxysilyl)benzene under acidic conditions in the presence of Brij-76 as a structure-directing agent. They were post-modified by treatment with H2O2 for 3h or 24h. A progressive loss of the mesostructure in the resulting materials was observed upon increasing the S content in the synthesis mixtures. Thus, only those samples with the lowest tetrasulfide content could be considered as periodic mesoporous organosilicas. This effect was even more pronounced upon oxidation. The oxidised materials exhibited a considerable acidity, particularly those with the two precursors in approximately equal amounts. All sulfonic acid functionalised materials were used as catalysts in the esterification of acetic acid with ethanol, and they exhibited a comparable or very similar activity to that of Amberlyst-15. Several mesoporous and microporous hybrid materials were selected and compared to this commercial resin in the transformation of more hydrophobic substrates. Some of these hybrid materials were especially attractive for the transformation of benzyl alcohol and various secondary alcohols.
- Lopez, Maria Isabel,Esquivel, Dolores,Jimenez-Sanchidrian, Cesar,Romero-Salguero, Francisco Jose
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p. 1002 - 1010
(2013/05/09)
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- Nickel-catalyzed hydrosilylation of CO2 in the Presence of Et3B for the synthesis of formic acid and related formates
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The reaction of CO2 with Et3SiH catalyzed by the nickel complex [(dippe)Ni(μ-H)]2 (1) afforded the reduction products Et3SiOCH2OSiEt3 (12%), Et 3SiOCH3 (3%), and CO, which were characterized by standard spectroscopic methods. Part of the generated CO was found as the complex [(dippe)Ni(CO)]2 (2), which was characterized by single-crystal X-ray diffraction. When the same reaction was carried out in the presence of a Lewis acid, such as Et3B, the hydrosilylation of CO2 efficiently proceeded to give the silyl formate (Et3SiOC(O)H) in high yields (85-89%), at 80 C for 1 h. Further reactivity of the silyl formate to yield formic acid, formamides, and alkyl formates was also investigated.
- Gonzalez-Sebastian, Lucero,Flores-Alamo, Marcos,Garcia, Juventino J.
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p. 7186 - 7194
(2014/01/06)
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- Nanocatalysis in continuous flow: Supported iron oxide nanoparticles for the heterogeneous aerobic oxidation of benzyl alcohol
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Investigations on heterogeneous iron catalysis in the selective aerobic oxidation of a primary alcohol are presented. Continuous flow technology was used in combination with an iron oxide nanoparticle catalyst stabilized in a mesoporous aluminosilicate support ( flow nanocatalysis ) as a process intensification tool to maximize catalyst efficiency. Using 5 mol% 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a co-catalyst, up to 42% benzyl alcohol as a simple model substrate was selectively converted to benzaldehyde in a single pass of the reactor. Full conversion was achieved by continuous recirculation, simulating an extension of the catalyst bed. ICPMS analysis indicated that the catalyst is highly stable and does not leach under the investigated conditions, providing solid evidence for the participation of a heterogeneous iron species in the catalytic cycle.
- Obermayer, David,Balu, Alina M.,Romero, Antonio A.,Goessler, Walter,Luque, Rafael,Kappe, C. Oliver
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p. 1530 - 1537
(2013/09/24)
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- Palladium-catalyzed carbonylation of aryl, alkenyl, and allyl halides with phenyl formate
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Highly efficient palladium-catalyzed carbonylation of aryl, alkenyl, and allyl halides with phenyl formate is reported. This procedure does not use carbon monoxide and affords one-carbon-elongated carboxylic acid phenyl esters in excellent yields. The reaction proceeds smoothly under mild conditions and tolerates a wide range of functional groups including aldehyde, ether, ketone, ester, and cyano groups. Furthermore, a variety of heteroaromatic bromides can be converted to the corresponding phenyl esters in high yields.
- Ueda, Tsuyoshi,Konishi, Hideyuki,Manabe, Kei
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supporting information; experimental part
p. 3100 - 3103
(2012/07/27)
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- Origin of the selectivity in the gold-mediated oxidation of benzyl alcohol
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Benzyl alcohol has received substantial attention as a probe molecule to test the selectivity and efficiency of novel metallic gold catalysts. Herein, the mechanisms of benzyl alcohol oxidation on a gold surface covered with atomic oxygen are elucidated; the results show direct correspondence to the reaction on gold-based catalysts. The selective, partial oxidation of benzyl alcohol to benzaldehyde is achieved with low oxygen surface concentrations and takes place through dehydrogenation of the alcohol to form benzaldehyde via a benzyloxy (C6H5-CH2O) intermediate. While in this case atomic oxygen plays solely a dehydrogenating role, at higher concentrations it leads to the formation of intermediates from benzaldehyde, producing benzoic acid and CO2. Facile ester (benzyl benzoate) formation also occurs at low oxygen concentrations, which indicates that benzoic acid is not a precursor of further oxidation of the ester; instead, the ester is produced by the coupling of adsorbed benzyloxy and benzaldehyde. Key to the high selectivity seen at low oxygen concentrations is the fact that the production of the aldehyde (and esters) is kinetically favored over the production of benzoic acid.
- Rodríguez-Reyes, Juan Carlos F.,Friend, Cynthia M.,Madix, Robert J.
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experimental part
p. 1129 - 1134
(2012/08/08)
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- Formylation of amines and alcohols using aminopropylated mesoporous SBA-15 silica (APMS) as an efficient and recyclable catalyst
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Aminopropylated mesoporous SBA-15 silica (APMS) is introduced as a new, recyclable and efficient catalyst for the formylation of a variety of amines and alcohols by using readily available formic acid under solvent-free conditions.
- Malakooti, Reihaneh,Sobhani, Sara,Razavi, Nasrin,Shafiei, Soheila,Mokhtari, Rezvan
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experimental part
p. 1979 - 1990
(2012/04/17)
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- Selective oxidations of organoboron compounds catalyzed by Baeyer-Villiger monooxygenases
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The applicability of Baeyer-Villiger monooxygenases (BVMOs) in organoboron chemistry has been explored through testing chemo- and enantioselective oxidations of a variety of boron-containing aromatic and vinylic compounds. Several BVMOs, namely: phenylacetone monooxygenase (PAMO), M446G PAMO mutant, 4-hydroxyacetophenone monooxygenase (HAPMO) and cyclohexanone monooxygenase (CHMO) were used in this study. The degree of chemoselectivity depends on the type of BVMO employed, in which the biocatalysts prefer boron-carbon oxidation over Baeyer-Villiger oxidation or epoxidation. Interestingly, it was discovered that PAMO can be used to perform kinetic resolution of boron-containing compounds with good enantioselectivities. These findings extend the known biocatalytic repertoire of BVMOs by showing a new family of compounds that can be oxidized by these enzymes. Copyright
- Brondani, Patricia B.,De Gonzalo, Gonzalo,Fraaije, Marco W.,Andrade, Leandro H.
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supporting information; experimental part
p. 2169 - 2173
(2011/10/31)
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- Photoionization mass spectrometry: A useful method to evaluate the pyrolysis process of glycoside flavor precursor
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The thermal decomposition behavior and the pyrolysis products of benzyl-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (BGLU) were studied with synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry at temperatures of 300, 500 and 700 °C at 0.062 Pa. Several pyrolysis products and intermediates were identified by the measurement of photoionization mass spectra at different photon energies. The results indicated that the primary decomposition reaction was the cleavage of O-glycosidic bond of the glycoside at low temperature, proven by the discoveries of benzyloxy radical (m/z = 107) and glycon radical (m/z = 331) in mass spectra. As pyrolysis temperature increased from 300 to 700 °C, two possible pyrolytic modes were observed. This work reported an application of synchrotron VUV photoionization mass spectrometry in the study of the thermal decomposition of glycoside flavor precursor, which was expected to help understand the thermal decomposition mechanism of this type of compound. The possibility of this glycoside to be used as a flavor precursor in high temperature process was evaluated.
- Ding, Yu,Cai, Ji-Bao,Qi, Fei,Su, Qing-De
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experimental part
p. 290 - 295
(2011/10/13)
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- Silica-bonded N-propyl sulfamic acid as an efficient catalyst for the formylation and acetylation of alcohols and amines under heterogeneous conditions
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A simple and efficient procedure for the preparation of silica-bonded N-propyl sulfamic acid (SBNPSA) by the reaction of 3-aminopropylsilica (1) and chlorosulfonic acid in chloroform is described. This solid acid is employed as a new catalyst for the formylation of alcohols and amines with ethyl formate under mild and heterogeneous conditions at room temperature with good to excellent yields. Also, SBNPSA catalyzed acetylation of various alcohols and amines with acetic anhydride at room temperature.
- Niknam, Khodabakhsh,Saberi, Dariush
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experimental part
p. 5210 - 5214
(2009/12/06)
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- Highly efficient formylation of alcohols, thiols and aniline derivatives by a heterogeneous (HCOOH/SiO2) system under microwave irradiation and solvent-free conditions
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A simple, rapid and efficient microwave-assisted procedure for the formylation of aniline derivatives and alcohols, using a heterogeneous (HCOOH/SiO2) system under solvent-free conditions is reported. The method is applied to a set of amines, alcohols and thiols and short reaction times (10 min) with high yields are reported. This protocol introduces a practical and viable green technology of solvent-free and catalyst-free reactions.
- Ghorbani-Vaghei, Ramin,Veisi, Hojat,Amiri, Mostafa,Chegini, Mohammad,Karimi, Mehdi,Dadamahaleh, Somayeh Akbari,Sedrpoushan, Alireza
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experimental part
p. 39 - 43
(2010/09/03)
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- Dual behavior of alcohols in iodine-catalyzed esterification under solvent-free reaction conditions
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The dual behavior phenomenon of alcohols in iodine-catalyzed esterification under solvent-free reaction conditions (SFRCs) is described; the governing factor is the stability of the carbonium ion generated from the alcohol; high concentration reaction conditions (HCRCs) or dilute solutions are much less suitable. In the case of benzylic alcohols, loss of optical activity was noted, whereas alkyl alcohols furnished a product with retention of stereochemistry.
- Jereb, Marjan,Vra?i?, Dejan,Zupan, Marko
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scheme or table
p. 2347 - 2352
(2009/09/06)
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- Formate ester synthesis via reaction of 2-bromoethylamines with dimethylformamide
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2-Bromoethylamines are converted to the corresponding formate esters in the presence of DMF. Both primary and secondary bromides are smoothly transformed to the esters in satisfactory yields. The reaction mechanism involves the formation of an aziridinium ion, which upon reaction with DMF forms a Vilsmeier-type intermediate that is further hydrolyzed to the corresponding formates. Participation of the β-amino group appears to control not only the regioselectivity but also the stereoselectivity of the reaction. Application of the reaction conditions to chiral substrates indicated that non-rearranged products are formed with retention of configuration at the reacting center.
- Dakanali, Marianna,Tsikalas, George K.,Krautscheid, Harald,Katerinopoulos, Haralambos E.
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p. 1648 - 1651
(2008/09/19)
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- Didecyldimethylammonium bromide (DDAB): a universal, robust, and highly potent phase-transfer catalyst for diverse organic transformations
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Didecyldimethylammonium bromide (DDAB) has been scrutinized in comparison with traditional phase-transfer catalysts in variety of liquid-liquid reactions. It was found to be an exceptionally comprehensive, durable, and highly efficient phase-transfer catalyst (PTC) in a number of representative organic transformations such as C- and N-alkylations, isomerization, esterification, elimination, cyanation, bromination, and oxidation under very mild conditions of temperature and mixing. It was confirmed that DDAB is an exceedingly accessible and concurrently a highly liphophilic phase-transfer catalyst. This unprecedented characteristic renders DDAB to be a multipurpose catalyst that functions effectively both in mass transfer controlled and chemically controlled phase-transfer reactions.
- Chidambaram, Mandan,Sonavane, Sachin U.,de la Zerda, Jaima,Sasson, Yoel
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p. 7696 - 7701
(2008/02/08)
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