294634-40-5Relevant academic research and scientific papers
Total Synthesis of (-)-Xishacorene B from (R)-Carvone Using a C-C Activation Strategy
Kerschgens, Isabel,Rovira, Alexander R.,Sarpong, Richmond
, p. 9810 - 9813 (2018)
The activation of C-C bonds that are traditionally viewed as unreactive, when coupled with other bond-forming processes, can offer new approaches to the synthesis of complex molecular scaffolds. In this Communication, we demonstrate the conversion of carv
Oxidation of olefins with H2O2 catalyzed by gallium(III) nitrate and aluminum(III) nitrate in solution
Mandelli, Dalmo,Kozlov, Yuriy N.,da Silva, Cezar A.R.,Carvalho, Wagner A.,Pescarmona, Paolo P.,Cella, Daniele de A.,de Paiva, Polyana T.,Shul'pin, Georgiy B.
, p. 216 - 220 (2016/09/19)
Soluble gallium and aluminum nitrates (simple salts of non-transition metals) are good catalysts for the epoxidation of olefins (cyclooctene, dec-1-ene) including terpenes (carvone, limonene) with hydrogen peroxide in ethyl acetate or tetrahydrofurane (THF). Typically, the gallium salt is more efficient in comparison with the aluminum derivative. Products are formed in yields up to 93%, turnover numbers (TONs) attained 40. Addition of trifluoroacetic acid or pyrazine-2-carboxylic acid (PCA) accelerates the reaction and improves the yield. In striking contrast, added 2,2′-bipyridine or phenanthroline dramatically inhibit the oxidation.
Hydrotalcite catalysis for the synthesis of new chiral building blocks
Rodilla, Jesus M.,Neves, Patricia P.,Pombal, Sofia,Rives, Vicente,Trujillano, Raquel,Díez, David
, p. 834 - 840 (2016/03/19)
The use of hydrotalcites for the synthesis of two chiral building blocks in a simple way is described as a new and green methodology. The synthesis of these compounds implies a regioselective Baeyer-Villiger reaction in a very selective way with ulterior
Regioselective Cleavage of Electron-Rich Double Bonds in Dienes to Carbonyl Compounds with [Fe(OTf)2(mix-BPBP)] and a Combination of H2O2 and NaIO4
Spannring, Peter,Yazerski, Vital A.,Chen, Jianming,Otte, Matthias,Weckhuysen, Bert M.,Bruijnincx, Pieter C. A.,Klein Gebbink, Robertus J. M.
, p. 3462 - 3466 (2015/08/06)
A method for the regioselective transformation of dienes to carbonyl compounds has been developed. Electron-rich olefins react selectively to yield valuable aldehydes and ketones. The method is based on the catalyst [Fe(OTf)2(mix-BPBP)] with an oxidant combination of H2O2 (1.0 equiv.) and NaIO4 (1.5 equiv.); it uses mild conditions and short reaction times, and it outperforms other olefin cleavage methodologies. The combination of an Fe-based catalyst, [Fe(OTf)2(mix-BPBP)], and the oxidants H2O2 and NaIO4 can discriminate between electronically different double bonds and oxidatively cleave the electron-rich bond in dienes to yield aldehydes and ketones in a regioselective manner. The reaction requires mild conditions (0-50 C) and short reaction times (70 min).
Non-heme iron catalysis in CC, C-H, and CH2 oxidation reactions. Oxidative transformations on terpenoids catalyzed by Fe(bpmen)(OTf)2
Clemente-Tejeda, David,López-Moreno, Alejandro,Bermejo, Francisco A.
, p. 2977 - 2986 (2013/03/29)
The oxidation of terpene olefins with hydrogen peroxide in the presence of the non-hemo catalyst 5a afforded mixtures of epoxides whose composition was dependent upon the oxidation protocol used in each case. With terpenoid enones, the mixtures obtained evolved from clean epoxidation of α-ionone 23 to the clean allylic oxidation of damascone 28 due to the progressive deactivation of the electron density on the double bonds present in this series. The oxidation of bicyclic and tricyclic terpenoids afforded oxidation products coming from epoxidation, to olefin degradation, methyne and methylene activation products. Probably, the most attractive result was the synthesis of the Magnus lactone 46, from the tricyclic ether 45, with 88% yield and 100% conversion.
MnII complexes with tetradentate N4 ligands: Highly efficient catalysts for the epoxidation of olefins with H2O 2
Yu, Songjie,Miao, Cheng-Xia,Wang, Daqi,Wang, Shoufeng,Xia, Chungu,Sun, Wei
experimental part, p. 185 - 191 (2012/03/10)
A series of Mn-complexes with tetradentate N4 ligands, introducing aromatic groups into 2-pyridylmethyl positions of N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)ethane-1,2-diamine (mep), N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)cyclohexane-trans-diamine (mcp), have been synthesized and applied for epoxidation of olefins using H 2O2 as the oxidant. The Mn-complexes still possessed an octahedral mononuclear structure in a cis-α topology. These complexes showed good regioselectivity, high yields and turnover frequency (even up to 228,000 h-1) with low catalyst loading (0.1-0.01 mol%) for epoxidation of a family of olefins (including internal aromatic olefins, internal and terminal aliphatic olefins and diolefins).
Efficient epoxidation of electron-deficient alkenes with hydrogen peroxide catalyzed by [γ-PW10O38V2(μ-OH) 2]3-
Kamata, Keigo,Sugahara, Kosei,Yonehara, Kazuhiro,Ishimoto, Ryo,Mizuno, Noritaka
scheme or table, p. 7549 - 7559 (2011/08/03)
A divanadium-substituted phosphotungstate, [γ-PW10O 38V2(μ-OH)2]3- (I), showed the highest catalytic activity for the H2O2-based epoxidation of allyl acetate among vanadium and tungsten complexes with a turnover number of 210. In the presence of I, various kinds of electron-deficient alkenes with acetate, ether, carbonyl, and chloro groups at the allylic positions could chemoselectively be oxidized to the corresponding epoxides in high yields with only an equimolar amount of H2O2 with respect to the substrates. Even acrylonitrile and methacrylonitrile could be epoxidized without formation of the corresponding amides. In addition, I could rapidly (min) catalyze epoxidation of various kinds of terminal, internal, and cyclic alkenes with H;bsubesubbsubesub& under the stoichiometric conditions. The mechanistic, spectroscopic, and kinetic studies showed that the I-catalyzed epoxidation consists of the following three steps: 1) The reaction of I with H;bsubesubbsubesub& leads to reversible formation of a hydroperoxo species [I;circbsubesubbsubesubbsubesubcirccircbsupesup& (II), 2) the successive dehydration of II forms an active oxygen species with a peroxo group [ 2:2-O2)]3- (III), and 3) III reacts with alkene to form the corresponding epoxide. The kinetic studies showed that the present epoxidation proceeds via III. Catalytic activities of divanadium-substituted polyoxotungstates for epoxidation with H 2O2 were dependent on the different kinds of the heteroatoms (i.e., Si or P) in the catalyst and I was more active than [γ-SiW10O38V2(μ-OH)2] 4-. On the basis of the kinetic, spectroscopic, and computational results, including those of [γ-SiW10O38V 2(μ-OH)2]4-, the acidity of the hydroperoxo species in II would play an important role in the dehydration reactivity (i.e., k3). The largest k3 value of I leads to a significant increase in the catalytic activity of I under the more concentrated conditions. Copyright
Oxidation of (1S,5R,7R,S)-(4,7-Dimethyl-6-oxabicyclo[3.2.1]oct-3-en-7-yl) methanol with pyridinium chlorochromate
Torosyan,Gimalova,Valeev,Miftakhov
experimental part, p. 682 - 686 (2011/08/22)
The oxidation of (1S,5R,7R,S)-(4,7-dimethyl-6-oxabicyclo[3.2.1]oct-3-en-7- yl)methanol epimeric at the C7 atom resulted in scalemic (5R)-5-acetyl-2- methylcyclohex-2-en-1-one. Pleiades Publishing, Ltd., 2011.
Epoxidation of olefins by β-bromoalkoxydimethylsulfonium ylides
Majetich, George,Shimkus, Joel,Li, Yang
supporting information; experimental part, p. 6830 - 6834 (2011/03/18)
Olefins can be converted to their respective epoxides in a one-pot procedure by dissolving the olefin in anhydrous DMSO, adding NBS to the reaction mixture to generate a β-bromoalkoxydimethylsulfonium ylide, and then adding DBU to the reaction mixture. A large variety of alkenes were successfully epoxi-dized with yields largely dependent on the structure of the alkene. Most importantly, the facial selectivity of this one-pot process is the opposite of that observed when using traditional epoxidizing reagents. Electron-poor alkenes are not epoxidized under these conditions.
Convenient, mild catalytic deprotection of oximes to carbonyl compounds with hydrogen peroxide and iodine catalyst in aqueous acetonitrile
Ganguly, Nemai C.,Nayek, Subhasis,Barik, Sujoy Kumar
experimental part, p. 4053 - 4061 (2009/12/24)
A clean, mild, and efficient catalytic deoximation procedure compatible with several common functional groups has been developed using 30% hydrogen peroxide activated by iodine catalyst in aqueous acetonitrile under essentially neutral conditions. The mechanistic features of an iodonium ion-driven nucleophilic cleavage of oximic C=N have been revealed.
