104-57-4Relevant articles and documents
Autorecycling System for Reduction of Carbonyl Compounds to Alcohols by 1,5-Dihydro-5-deazaflavins
Yoneda, Fumio,Kuroda, Kazunori,Kamishimoto, Mutsuko
, p. 1160 - 1162 (1981)
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.
Aryl Cations: Searching for and Assigning Structures to + Isomers
Bissonnette, Martine C.,George, M.,Holmes John, L.
, p. 1019 - 1022 (1991)
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.
Silica sulfuric acid and AI(HSO4)3: As efficient catalysts for the formylation of alcohols by using ethyl formate under heterogeneous conditions
Zolfigol, Mohammad Ali,Chehardoli, Gholamabbas,Dehghanian, Mina,Niknam, Khodabakhsh,Shirini, Farhad,Khoramabadi-Zad, Ahmad
, p. 885 - 889 (2008)
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.
Conversion of alkyl halides into alcohols via formyloxylation reaction with DMF catalyzed by silver salts
Abad, Antonio,Agullo, Consuelo,Cunat, Ana C.,Navarro, Ismael
, p. 3355 - 3361 (2005)
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.
Lewis Base Promoted Reduction of CO2 with BH3NH3 into Boryl Formates: CO2 as a Carbon Source in Organic Synthesis Under Mild Conditions
Zhang, Bo,Du, Gaixia,Hang, Wei,Wang, Sheng,Xi, Chanjuan
, p. 1739 - 1743 (2018)
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.
Operando systems chemistry reaction catalysis (OSCR-Cat) for visible light driven CO2conversion
Das, Kousik,De, Ratnadip,Roy, Soumyajit,Verpoort, Francis
, p. 13355 - 13365 (2021/06/16)
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.
Substituted 9-Anthraldehydes from Dibenzocycloheptanol Epoxides via Acid-Catalyzed Epoxide Opening/Semipinacol Rearrangement
Phumjan, Tanawat,Songthammawat, Poramate,Jongcharoenkamol, Jira,Batsomboon, Paratchata,Ruchirawat, Somsak,Ploypradith, Poonsakdi
, p. 13322 - 13349 (2021/09/13)
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.
Chemoselective: O -formyl and O -acyl protection of alkanolamines, phenoxyethanols and alcohols catalyzed by nickel(ii) and copper(ii)-catalysts
Sonawane, Rahul B.,Sonawane, Swapnali R.,Rasal, Nishant K.,Jagtap, Sangeeta V.
supporting information, p. 3186 - 3195 (2020/06/19)
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.
Ionic liquid-stabilized vanadium oxo-clusters catalyzing alkane oxidation by regulating oligovanadates
Ding, Bingjie,Gong, Xueqing,Hou, Zhenshan,Li, Difan,Yao, Yefeng,Zhang, Ran,Zheng, Anna,Zhou, Qingqing
, p. 7601 - 7612 (2020/11/27)
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.
One-Pot Conversion of Cinnamaldehyde to 2-Phenylethanol via a Biosynthetic Cascade Reaction
Vorster, Amanda,Smit, Martha S.,Opperman, Diederik J.
supporting information, p. 7024 - 7027 (2019/09/12)
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.
