24980-41-4Relevant articles and documents
Baeyer-Villiger oxidation of ketones catalysed by rhenium complexes bearing N- or oxo-ligands
Alegria, Elisabete C.B.A.,Martins, Luísa M.D.R.S.,Kirillova, Marina V.,Pombeiro, Armando J.L.
, p. 27 - 32 (2012)
Rhenium (I, III-V or VII) complexes bearing N-donor or oxo-ligands catalyse the Baeyer-Villiger oxidation of cyclic and linear ketones (e.g. 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone and 3,3-dimethyl-2-butanone) into the corresponding lactones or esters, in the presence of aqueous H2O2 (30%). The effects of various reaction parameters are studied allowing to achieve yields up to 54%.
Oxaziridine-mediated catalytic hydroxylation of unactivated 3° C-H bonds using hydrogen peroxide
Brodsky, Benjamin H.,Du Bois
, p. 15391 - 15393 (2005)
The design, structural characterization, and evaluation of a unique class of 1,2,3-benzoxathiazine-based oxaziridines as potent O-atom transfer agents for catalytic C-H hydroxylation and alkene epoxidation are described. Turnover of this reaction is made possible by employing a diaryl diselenide cocatalyst and urea·H2O2 as the terminal oxidant. Oxidation of saturated hydrocarbons is strongly biased toward 3° C-H bonds even in systems possessing a significantly greater number of methylene groups. In addition, the benzoxathiazine catalyst is effective for epoxidation of terminal and electron-deficient olefins. Collectively, these findings represent an important first step toward the advancement of general methodology for selective C-H oxidation. Copyright
Kinetics and enantioselectivity of the Baeyer-Villiger oxidation of cyclohexanones by chiral tetrapyridyl oxoiron(IV) complex
Turcas, Ramona,Lakk-Bogáth, Dóra,Speier, Gábor,Kaizer, József
, p. 141 - 144 (2018)
The previously reported oxoiron(IV) complex, [FeIV(asN4Py)(O)]2+ with chiral pentadentate ligand, asN4Py (asN4Py = N,N?bis(2?pyridylmethyl)?1,2?di(2?pyridyl)ethylamine), is effective for the Baeyer-Villiger oxidation of cyclohexanone derivatives. The reaction is shown to be first order in both cyclohexanone and the oxoiron(IV) species. The second order rate constant is smaller by one order of magnitude than that obtained for the related achiral [FeIV(N4Py)(O)]2+ complex. Oxidation of 4-substituted cyclohexanone derivatives by the chiral oxoiron(IV) complex attains moderate enantioselectivities up to 45% enantiomeric excess (ee).
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Friess
, p. 2571,2572 (1949)
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Kinetics Modeling of a Convergent Cascade Catalyzed by Monooxygenase-Alcohol Dehydrogenase Coupled Enzymes
Bornscheuer, Uwe T.,Engel, Jennifer,Kara, Selin
, p. 411 - 420 (2021)
A convergent cascade reaction coupling a cyclohexanone monooxygenase variant and an alcohol dehydrogenase to make ?-caprolactone from cyclohexanone and 1,6-hexanediol was characterized via progress curve analysis with two kinetic models developed iteratively. A chemical side reaction occurring with the utilized Tris buffer and consequent byproduct formations were considered in Model 2, which reduced the root-mean-square error (RMSE) values by half, compared to Model 1 (RMSE values of 13%-40%). The optimized model, Model 2, led us to simulate the cascade reaction including 22 kinetic parameters with a maximum RMSE value in the range of 10%-21%.
The Baeyer-Villiger oxidation of ketones with bis(trimethylsilyl) peroxide in the presence of ionic liquids as the solvent and catalyst
Baj, Stefan,Chrobok, Anna,Slupska, Roksana
, p. 279 - 282 (2009)
A new method for lactone synthesis with bis(trimethylsilyl) peroxide as the oxidant and ionic liquids as solvents is reported. We propose two possibilities for the Baeyer-Villiger reaction course. The first of these is based on simply exchanging dichloromethane, the classical solvent for Baeyer-Villiger oxidation, for the ionic liquid bmimNTf2, which results in increased product yields. The second possibility is the elimination of the Baeyer-Villiger reaction catalyst and use of 1-butyl-3-methylimidazolium trifluoromethanesulfonate as both the solvent and catalyst. This method gives lactones in high yields with the possibility of ionic liquid recycling.
One-pot conversion of cycloalkanes to lactones
Pennec, Aliz,Hollmann, Frank,Smit, Martha S.,Opperman, Diederik J.
, p. 236 - 239 (2015)
The one-pot conversion of cycloalkanes to their corresponding lactones was achieved through the use of a synthetic pathway consisting of a cytochrome P450 monooxygenase (CYP450) for initial oxyfunctionalization of the cycloalkane, an alcohol dehydrogenase for ketone production and a Baeyer-Villiger monooxygenase for lactone formation. Through variation of the cofactor dependence of the biocatalysts and the cofactor regeneration system, final product concentrations of nearly 3 g L-1 enantholactone (2-oxocanone) from cycloheptane was reached within 12 h with a total turnover number (TTN) of 4185 with respect to the CYP450.
Baeyer-Villiger oxidations with a difference: Molecular sieve redox catalysts for the low-temperature conversion of ketones to lactones
Raja, Robert,Thomas, John Meurig,Sankar, Gopinathan
, p. 525 - 526 (1999)
Redox molecular sieve catalysts MA1PO-36 (M = Mn or Co) convert cyclopentanone, cyclohexanone, 2-methylcyclohexanone and adamantan-2-one to their corresponding lactones with high efficiency (selectivities in excess of 90%, conversions in the range 50 to 85%), in the presence of O2 and PhCHO as sacrificial oxidant.
Baeyer-Villiger oxidation of cyclohexanone with molecular oxygen in the presence of benzaldehyde
Li, Xuegeng,Wang, Fan,Zhang, Hao,Wang, Chen,Song, Guoqiang
, p. 1613 - 1616 (1996)
The metal-catalyzed Baeyer-Villiger oxidation of cyclohexanone with molecular oxygen (1atm) in the presence of benzaldehyde gives ε-caprolactone in high yield. The same oxidation in the absence of metal catalysts is also studied. Additives to the system can improve the reaction highly efficiently.
The chemo-enzymatic Baeyer-Villiger oxidation of cyclic ketones with an efficient silica-supported lipase as a biocatalyst
Drozdz,Chrobok,Baj,Szymańska,Mrowiec-Bia?on?,Jarz?bski
, p. 163 - 170 (2013)
The synthesis and characterisation of new, silica-supported lipase biocatalysts and studies of their performance in Baeyer-Villiger oxidation (BVO) of cyclic ketones to lactones were described. Biocatalysts were obtained by immobilisation of Candida Antarctica lipase B onto siliceous materials with multimodal pore structure (MH) and also on typical SBA-15, chemically modified with organosilanes terminated with methyl, octyl and hexadecyl group. Biocatalysts structure was characterised by nitrogen adsorption and TEM/SEM imaging. The lipase presence was confirmed by FTIR spectroscopy, whereas protein loads were obtained from thermogravimetric data. They appeared to be notably larger for MH catalysts than SBA-15s and correlated with surface hydrophobicity of supports which decreased in the order Hd > Oc > Me, from 198 to 80 mg/g, for MH-Hd-L and MH-Me-L biocatalysts, respectively. Investigation of the biocatalysts performance (activity, stability, reusability) in BVO of cyclic ketones, using urea hydrogen peroxide as oxidant and ethyl acetate as both the peracid precursor and solvent, clearly demonstrated very large activity of MH biocatalysts. For the same lipase load activity decreased in the order MH-Me-L > MH-Oc-L > MH-Hd-L, with that of least active (MH-Hd-L) catalysts being even trice larger than of Novozyme-435 under equal mass basis. The biocatalysts showed good stability, even in the presence of 60% aq. hydrogen peroxide, and facile reuse. On this basis we proposed a general chemo-enzymatic BVO method for oxidation of cyclohexanones and cyclobutanone to obtain adequate lactones with high yields (80-98%).
Structural and synthetic studies on the retrofractamides-amide constituents of Piper retrofractum
Banerji, Avijit,Bandyopadhyay, Debabrata,Sarkar, Manjusha,K. Siddhanta, Arup,C. Pal, Sudhir,Ghosh, Somnath,Abraham, Koshy,N. Shoolery, James
, p. 279 - 284 (1985)
Two new unsaturated amides, retrofractamides A and C, were isolated from the total above-ground parts of Piper retrofractum. Retrofractamide A was shown to be N-isobutyl-9(3′,4′-methylenedioxyphenyl)2E,4E,8E-nonatrienamide from spectroscopic and chemical investigations. The structure 6 for retrofractamide C was suggested from spectroscopic and chemical studies and was confirmed by a total stereoselective synthesis. The presence of sesamin and 3,4,5-trimethoxydihydrocinnamic acid as well as two higher homologues of retrofractamide A, viz. pipericide (retrofractamide B) and retrofractamide D was demonstrated. The synthesis of pipericide was also achieved.
N-Hydroxyphthalimide (NHPI) Promoted Aerobic Baeyer-Villiger Oxidation in the Presence of Aldehydes
Wang, Lingyao,Wang, Yongtao,Du, Renfeng,Dao, Rina,Yuan, Haoran,Liang, Cheng,Yao, Jia,Li, Haoran
, p. 4961 - 4966 (2018)
Metal-free aerobic Baeyer-Villiger (BV) oxidation of ketones to lactones or esters in the presence of aldehydes promoted by N-hydroxyphthalimide (NHPI) has been developed. The reaction proceeded under mild conditions with excellent selectivity and high yields. Compared with the methods that use metal complexes as catalysts, this strategy not only showed good environmental advantages, but also increased aldehyde efficiency up to 84 %. Control experiments indicated that NHPI accelerated the oxidation of aldehydes to peroxy acids but did not improve the BV oxidation while peroxy acids were already generated. Peroxy acids generated from aldehydes in situ were the key intermediates, and the phthalimide-N-oxyl radical (PINO) contributed to high aldehyde efficiency by stabilizing the radical species, which are necessary for the chain propagation reactions. This study may offer some useful strategies for new transition metal-free catalytic aerobic oxidation reactions in which aldehydes act as sacrificial agents.
Efficient Preparation of 1,2,4,5-Tetroxanes from Bis(trimethylsilyl) Peroxide and Carbonyl Compounds
Jefford, Charles W.,Boukouvalas, Amer Jaber John
, p. 391 - 393 (1988)
Symmetrically 3,6-disubstituted and 3,3,6,6-tetrasubstituted 1,2,4,5-tetroxanes are prepared in good yields by the condensation of bis(trimethylsilyl) peroxide with aldehydes and ketones in the presence of trimethylsilyl trifluoromethanesulfonate.
Study on Synthesis of Acid-Washed Illite Supported Fe3O4 Nanometer Catalyst and Baeyer–Villiger Oxidation Reaction of Cyclohexanone
Yang, Yong,Guan, Dongdong,Liu, Yu,Chen, Shuang,Meng, Wan,Jiang, Nanzhe
, p. 1111 - 1117 (2019)
Baeyer–Villiger oxidation allows for effective control of the stereochemical structure of the product, which is a significant feature for functional group conversion and ring expansion in organic synthesis. In this study, Fe3O4 nanoparticles were loaded on acid-washed porous illite silicon slag (I-SR) using an in situ hydrothermal method to obtain the magnetic composite Fe3O4@I-SR. This composite was characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, N2 adsorption–desorption isotherm measurements, vibrating sample magnetometer analysis, etc. The results indicated that the Fe3O4 nanoparticles had a face-centered cubic lattice geometry with an average size of about 10?nm; the nanoparticles were uniformly dispersed on the surface of the carrier (I-SR) and exhibited strong paramagnetism. Fe3O4@I-SR composite was found to be a promising and efficient catalyst with high activity (> 99% cyclohexanone conversion and > 99% ε-caprolactone selectivity) for the Baeyer–Villiger of cyclohexanone to ε-caprolactone. The catalyst could be easily separated from the reaction mixture and reused many times. Thus, Fe3O4@I-SR is an attractive multiphase catalyst that is easy to handle and recycle under environmentally friendly reaction conditions. Graphical Abstract: [Figure not available: see fulltext.].
A Bi-enzymatic Convergent Cascade for ε-Caprolactone Synthesis Employing 1,6-Hexanediol as a 'Double-Smart Cosubstrate'
Bornadel, Amin,Hatti-Kaul, Rajni,Hollmann, Frank,Kara, Selin
, p. 2442 - 2445 (2015)
A bi-enzymatic cascade consisting of a Baeyer-Villiger monooxygenase and an alcohol dehydrogenase (ADH) was designed in a convergent fashion to utilise two molar equivalents of cyclohexanone (CHO) and one equivalent of 1,6-hexanediol as a 'double-smart cosubstrate' to produce ε-caprolactone (ECL) with water as sole by-product. The convergent enzymatic cascade reaction reported herein, is performed at ambient conditions in water, is self-sufficient with respect to cofactor, and incorporates all starting materials into the desired product, ECL. Among different enzymes explored, the reaction catalysed by cyclohexanone monooxygenase from Acinetobacter sp. NCIMB 9871 coupled with ADH from Thermoanaerobacter ethanolicus showed the best results, reaching 91 % conversion of CHO after 24 h with a product titre of 2 g L-1. Scale-up of the coupled system (50 mL) performed better than the small-scale reactions and >99 % conversion of CHO and ECL concentration of 20 mM were achieved within 18 h.
Fluoride-induced Activation of Molybdenum Hexacarbonyl: Formation of Esters and Lactones from Alkyl Iodides
Imbeaux, Michele,Mestdagh, Helene,Moughamir, Khadija,Rolando, Christian
, p. 1678 - 1679 (1992)
In the presence of fluoride ion, alkyl iodides RI are carbonylated by molybdenum hexacarbonyl to esters RCO2R, and diiodides lead to good yields of the corresponding lactones.
Useful application of acidic ionic liquids as solvents in Baeyer-Villiger oxidation with hydrogen peroxide for the synthesis of lactones
Baj, Stefan,Chrobok, Anna
, p. 2385 - 2391 (2008)
Cyclic ketones have been efficiently oxidized with hydrogen peroxide using acidic ionic liquids (ILs) as solvents. This is a new method for the synthesis of lactones with high yields that does not utilize any additional catalysts and enables ILs to be recycled. Copyright Taylor & Francis Group, LLC.
Fabrication of Ag/WO3 nanobars for Baeyer-Villiger oxidation using hydrogen peroxide
Ghosh, Shilpi,Acharyya, Shankha Shubhra,Singh, Raghuvir,Gupta, Piyush,Bal, Rajaram
, p. 33 - 37 (2015)
We report the preparation of Ag/WO3 nanobars, mediated by cationic surfactant CTAB through hydrothermal route. XRD revealed the formation of metallic Ag supported on monoclinic WO3 phase and TEM diagram showed the formation of bar-like structure, where supported Ag nanoparticles are in the range between 2 and 7 nm. The catalyst exhibited high activity for selective oxidation of cyclohexanone to caprolactone with H2O2. A cyclohexanone conversion of 97% with 99% caprolactone selectivity was achieved over this catalyst at 80°C temperature. Moreover, the catalyst did not show any significant activity loss even after 5 reuses and proved its efficiency in the oxidation of other cycloalkanones also.
A tetranuclear diphenyltin(IV) complex and its catalytic activity in the aerobic Baeyer-Villiger oxidation of cyclohexanone
Hazra, Susanta,Martins, Nuno M.R.,Mahmudov, Kamran,Zubkov, Fedor I.,Guedes da Silva, M. Fátima C.,Pombeiro, Armando J.L.
, p. 193 - 200 (2018)
The synthesis and crystal structure of the new tetranuclear diphenyltin(IV) compound [{SnPh2}{SnPh2(OCOMe)}(μ2-OMe)(μ3-O)]2 (1), generated from the reaction of [SnPh2Cl2] and NaOCOMe, are described. Single crystal X-ray diffraction revealed that 1 is a tetranuclear complex with four diphenyltin(IV) units which are inter-connected by μ3-oxido and μ2-methoxido bridges leading to a ladder-like Sn4O4 cluster. Structural comparison with related compounds found in crystallographic data base (CSD) attests that such tetranuclear systems are more abundant than related oxido bridged dimers or trimers. Complex 1 efficiently catalyzes the aerobic Baeyer-Villiger oxidation of cyclohexanone to ε-caprolactone, under mild conditions. With the sacrificial benzaldehyde method, quantitative conversion was observed in just 30 min with a remarkable selectivity.
Green Oxidation of Ketones to Lactones with Oxone in Water
Bertolini, Valentina,Appiani, Rebecca,Pallavicini, Marco,Bolchi, Cristiano
, p. 15712 - 15716 (2021/11/01)
Cyclic ketones were quickly and quantitatively converted to 5-, 6-, and 7-membered lactones, very important synthons, by treatment with Oxone, a cheap, stable, and nonpollutant oxidizing reagent, in 1 M NaH2PO4/Na2HPO4 water solution (pH 7). Under such simple and green conditions, no hydroxyacid was formed, thus making the adoption of more complex and non-eco-friendly procedures previously developed to avoid lactone hydrolysis unnecessary. With some changes, the method was successfully applied also to water-insoluble ketones such as adamantanone, acetophenone, 2-indanone, and the challenging cycloheptanone.
Selective Aerobic Oxidation of Secondary C (sp3)-H Bonds with NHPI/CAN Catalytic System
Wang, Lingyao,Zhang, Yuanbin,Yuan, Haoran,Du, Renfeng,Yao, Jia,Li, Haoran
, p. 1663 - 1669 (2020/10/21)
Abstract: The direct aerobic oxidation of secondarty C(sp3)-H bonds was achieved in the presence of N-hydroxyphthalimide (NHPI) and cerium ammonium nitrate (CAN) under mild conditions. Various benzylic methylenes could be oxidized to carbonyl compounds in satisfied selectivity while saturated cyclic alkanes could be further oxidized to the corresponding lactones with the catalytic system. Remarkably, 25% of isochroman was converted to corresponding ketone with a selectivity of 96%. The reaction was initiated by hydrogen atom abstraction from NHPI by cerium and nitrates under oxygen atmosphere to form PINO radicals. 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO) addition experiments showed that the oxidation proceeded via a complex radical chain mechanism and an ion pathway. Graphic Abstract: [Figure not available: see fulltext.]
Aliphatic C–H hydroxylation activity and durability of a nickel complex catalyst according to the molecular structure of the bis(oxazoline) ligands
Hikichi, Shiro,Izumi, Takashi,Matsuba, Naki,Nakazawa, Jun
, (2021/07/13)
Applicability of the oxazoline-based compounds, bis(2-oxazolynyl)methane (BOX) and 2,6-bis(2-oxazolynyl)pyridine (PyBOX), as supporting ligands of nickel(II) complexes for the catalysis of aliphatic C–H hydroxylation with m-CPBA (meta-chloroperoxybenzoic acid) was explored. Substituent groups at the fourth and fifth positions of oxazoline rings and the bridgehead carbon atom of the BOX derivatives affected the catalytic performances toward cyclohexane hydroxylation. Presence of dioxygen led to a reduced catalytic performance of the nickel complexes, except in the case of a fully substituted BOX ligand complex.
