60047-17-8Relevant academic research and scientific papers
One-pot synthesis at room temperature of epoxides and linalool derivative pyrans in monolacunary Na7PW11O39-catalyzed oxidation reactions by hydrogen peroxide
Da Silva, Márcio J.,Teixeira, Milena Galdino,Vilanculo, Castelo B.,Villarreal, Jesus Avendano
, p. 7691 - 7697 (2020/03/10)
In this work, we describe a new one-pot synthesis route of valuable linalool oxidation derivatives (i.e., 2-(5-methyl-5-vinyltetrahydrofuran-2-yl propan-2-ol) (1a)), 2,2,6-trimethyl-6-vinyltetrahydro-2H-pyran-3-ol (1b) and diepoxide (1c), using a green oxidant (i.e., hydrogen peroxide) under mild conditions (i.e., room temperature). Lacunar Keggin heteropolyacid salts were the catalysts investigated in this reaction. Among them, Na7PW11O39 was the most active and selective toward oxidation products. All the catalysts were characterized by FT-IR, TG/DSC, BET, XRD analyses and potentiometric titration. The main reaction parameters were assessed. Special attention was dedicated to correlating the composition and properties of the catalysts and their activity.
Enantioselective Bio-Hydrolysis of Geranyl-Derived rac-Epoxides: A Chemoenzymatic Route to trans-Furanoid Linalool Oxide
van Lint, Matthijs J.,Gümüs, Aysegül,Ruijter, Eelco,Faber, Kurt,Orru, Romano V. A.,Hall, Mélanie
, p. 813 - 825 (2019/01/04)
In contrast to many chemical dihydroxylation methods, enzymatic epoxide hydrolysis provides an environmentally benign route to vicinal diols, which are important intermediates in the synthesis of fine chemicals and pharmaceuticals. Using epoxide hydrolases, enantiopure diols are accessible under mild conditions. In order to assess the selectivity of epoxide hydrolases on geraniol-derived oxiranes, a range of derivatives were screened against a large variety of enzyme preparations. For nearly all substrates, a matching hydrolase with excellent enantioselectivity (≥95% ee) could be found. In addition, a chemoenzymatic approach for the stereoselective synthesis of furanoid linalool oxide was developed. Combination of enzymatic enantioselective hydrolysis with stereoselective Tsuji-Trost reaction granted diastereoselective access to trans-(2R,5R)-configured linalool oxide with high diastereomeric and enantiomeric excess (97% de and 97% ee). (Figure presented.).
Asymmetric synthesis and structure-activity studies of the fungal metabolites colletorin A, colletochlorin A and their halogenates analogues
Marsico, Giulia,Pignataro, Barbara A.,Masi, Marco,Evidente, Antonio,Casella, Francesca,Zonno, Maria Chiara,Tak, Jun-Hyung,Bloomquist, Jeffrey R.,Superchi, Stefano,Scafato, Patrizia
, p. 3912 - 3923 (2018/06/08)
The first asymmetric total synthesis of both enantiomers of the natural products colletorin A and colletochlorin A is presented. The proposed methodology is based on the coupling reaction between highly substituted aromatic Gilman cuprates and optically active allyl bromides, in turn obtained by Sharpless asymmetric dihydroxylation. The latter ensured a high degree of regio- and stereocontrol in the enantioselective step of the synthesis. The same synthetic strategy has been also applied for the preparation of differently halogenated synthetic analogues of colletochlorin A in high enantiomeric purity. The enantioselective synthesis of colletorin A and colletochlorin A allows to reliably assign their absolute configuration. Preliminary assessment of their herbicidal and insecticidal properties evidence the possibility to modulate the bioactivity of these compounds, highlighting its dependence on both the absolute stereochemistry and the halogen nature.
Catalytic homogeneous oxidation of monoterpenes and cyclooctene with hydrogen peroxide in the presence of sandwich-type tungstophosphates [M4(H2O)2(PW9O34)2]n?, M = CoII, MnII and FeIII
Santos, Isabel C.M.S.,Gamelas, José A.F.,Duarte, Tiago A.G.,Sim?es, Mário M.Q.,Neves, M. Gra?a P.M.S.,Cavaleiro, José A.S.,Cavaleiro, Ana M.V.
, p. 593 - 599 (2016/12/16)
Catalytic efficiency of tetrabutylammonium salts of sandwich tungstophosphates B‐α‐[M4(H2O)2(PW9O34)2]n?, M = CoII, MnII, FeIII, was studied in the oxidation of (R)-(+)-limonene, geraniol, linalool, linalyl acetate, carveol, and cis-cyclooctene with hydrogen peroxide, in acetonitrile. Oxidation of (R)-(+)-limonene gave limonene-1,2-diol as main product. Epoxidation of linalool takes place preferentially at the more substituted 6,7-double bond, the corresponding 6,7-epoxide reacting further, yielding furano- and pyrano-oxides, via intramolecular cyclization. Oxidation of linalyl acetate occurred preferentially at the more substituted 6,7-double bond for Mn4(PW9)2, affording 6,7-epoxide at 82% selectivity. Linalyl acetate 1,2-epoxide was the major product with 51% and 77% selectivity for Co4(PW9)2 and Fe4(PW9)2, respectively. Oxidation of carveol occurred with very good conversions in the presence of Mn4(PW9)2, Co4(PW9)2 and Fe4(PW9)2, yielding carvone and carveol 1,2-epoxide in similar amounts. Oxidation of cis-cyclooctene gave only the epoxide, while oxidation of geraniol at room temperature afforded 2,3-epoxygeraniol as the major product.
Method for preparing furan-type oxidized linalool
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Paragraph 0030-0057, (2017/09/13)
The invention discloses a method for preparing furan-type oxidized linalool. The method specifically comprises the following steps: firstly, at the room temperature, mixing and stirring 4H-5-(1-hydroxyl-1-methyl ethyl)-2-methyl-2-furan ethanol, paratoluensulfonyl chloride and alkali to implement reaction, after the reaction is completed, adjusting the pH value to be neutral by using an acid solution, extracting, drying and filtering; performing evaporation concentration on the filtrate so as to obtain sulfonate; adding potassium tert-butoxide and tertiary butanol into the sulfonate, and performing reaction at 70-80 DEG C so as to obtain a crude product; and performing purification treatment on the crude product, thereby obtaining the furan-type oxidized linalool. The method disclosed by the invention is easy in raw material obtaining, simple in preparation process, convenient to operate, relatively low in production cost and applicable to industrial production.
UTL titanosilicate: An extra-large pore epoxidation catalyst with tunable textural properties
P?ech, Jan,?ejka, Ji?í
, p. 2 - 8 (2016/10/03)
The UTL titanosilicate was prepared together with related lamellar Ti-IPC-1PISi material and zeolites Ti-IPC-2 (OKO) and Ti-IPC-4 (PCR) via top-down synthesis. The titanium can be incorporated to the UTL framework by conventional hydrothermal synthesis and it does not affect the so-called ADOR chemistry of the UTL material. Silica-titania pillaring concept was successfully applied providing very active Ti-IPC-1PITi catalyst for bulky molecules epoxidation with hydrogen peroxide. The textural properties of catalysts prepared can be tuned widely keeping the same crystalline titanosilicate active phase. All the materials were characterised by XRD, nitrogen sorption measurement, SEM, and DR-UV/vis spectroscopy. Ti-IPC-1PITi was the most active catalyst in cyclooctene, norbornene, and linalool epoxidation due to the lowest diffusion constraints and sufficient titanium content. Ti-UTL showed activity similar to Ti-BEA in epoxidation of cyclooctene and it provided different products than other titanosilicates in oxidation of linalool with hydrogen peroxide.
Unusually Broad Substrate Profile of Self-Sufficient Cytochrome P450 Monooxygenase CYP116B4 from Labrenzia aggregata
Yin, Yue-Cai,Yu, Hui-Lei,Luan, Zheng-Jiao,Li, Ren-Jie,Ouyang, Peng-Fei,Liu, Jing,Xu, Jian-He
, p. 2443 - 2449 (2015/03/03)
A new member of the CYP116B subfamily - P450LaMO - was discovered in Labrenzia aggregata by genomic data mining. It was successfully overexpressed in Escherichia coli, purified, and subsequently characterized spectroscopically, and its catalytic properties were assessed. Substrate profiling of the P450LaMO revealed that it was a versatile catalyst, exhibiting hydroxylation and epoxidation activities as well as O-dealkylation and asymmetric sulfoxidation activities. Diverse compounds, including alkylbenzenes, aromatic bicyclic molecules, and terpenoids, were shown to be hydroxylated by P450LaMO. Such diverse catalytic activities are uncommon for the bacterial P450s, and the P450LaMO -mediated stereoselective hydroxylation of inactivated C - H bonds - ubiquitous and relatively unreactive in organic molecules - is particularly unusual. The self-sufficient nature of P450LaMO, coupled with its broad substrate range, highlights it as an ideal template for directed evolution towards various applications.
Unusually Broad Substrate Profile of Self-Sufficient Cytochrome P450 Monooxygenase CYP116B4 from Labrenzia aggregata
Yin, Yue-Cai,Yu, Hui-Lei,Luan, Zheng-Jiao,Li, Ren-Jie,Ouyang, Peng-Fei,Liu, Jing,Xu, Jian-He
, p. 2443 - 2449 (2015/08/24)
A new member of the CYP116B subfamily - P450LaMO - was discovered in Labrenzia aggregata by genomic data mining. It was successfully overexpressed in Escherichia coli, purified, and subsequently characterized spectroscopically, and its catalytic properties were assessed. Substrate profiling of the P450LaMO revealed that it was a versatile catalyst, exhibiting hydroxylation and epoxidation activities as well as O-dealkylation and asymmetric sulfoxidation activities. Diverse compounds, including alkylbenzenes, aromatic bicyclic molecules, and terpenoids, were shown to be hydroxylated by P450LaMO. Such diverse catalytic activities are uncommon for the bacterial P450s, and the P450LaMO -mediated stereoselective hydroxylation of inactivated C-H bonds - ubiquitous and relatively unreactive in organic molecules - is particularly unusual. The self-sufficient nature of P450LaMO, coupled with its broad substrate range, highlights it as an ideal template for directed evolution towards various applications.
Catalytic performance of a boron peroxotungstate complex under homogeneous and heterogeneous conditions
Santos, Isabel C.M.S.,Balula, Salete S.,Sim?es, Mário M.Q.,Cunha-Silva, Luís,Neves, M. Gra?a P.M.S.,De Castro, Baltazar,Cavaleiro, Ana M.V.,Cavaleiro, José A.S.
, p. 87 - 94 (2013/08/24)
The preparation and characterization (FT-IR, FT-Raman, 11B MAS NMR, diffuse reflectance, elemental analysis) of a novel boron peroxotungstate (BTBA)4H[BW4O24] (BTBA = benzyltributylammonium) is reported, along with its use in the homogeneous oxidation of cis-cyclooctene, geraniol, linalool and (-)-carveol with H 2O2 as oxidant and acetonitrile as solvent. High catalytic activity was registered for all the substrates studied under homogeneous conditions, namely 99% of conversion of geraniol after 2 h, 93% for linalool after 5 h, 74% for cis-cyclooctene after 6 h, and 100% for (-)-carveol after 2 h of reaction. Some oxidation studies were carried out with the Venturello complex, [PW4O24]3-, in the same conditions. Furthermore, the boron peroxotungstate (BW4) was immobilized using two different strategies: (a) BW4 anchored into a functionalized silica (aptesSiO2) giving BW4@aptesSiO2 and (b) BW4 encapsulated on a metal organic framework, commonly referred as MIL-101, giving BW4@MIL-101. The catalytic activity of both heterogeneous materials was investigated for geraniol oxidation and the results were compared with those obtained with BW4 under homogeneous conditions. The encapsulated boron peroxotungstate (BW4@MIL-101) gave rise to the best results, reaching complete conversion of geraniol after 3 h of reaction and 78% selectivity for 2,3-epoxygeraniol. Additionally, this heterogeneous catalyst could be reused without appreciable loss of catalytic activity, affording similar 2,3-epoxygeraniol selectivity. The heterogeneous catalysts' stability was also investigated after the oxidation reactions by different characterization techniques.
Vanadyl arsenates as catalysts for selective oxidation of organic sulfides and alkenes
Berrocal, Teresa,Larrea, Edurne S.,Iglesias, Marta,Arriortua, Maria I.
scheme or table, p. 176 - 182 (2011/03/23)
Two vanadyl arsenates templated with ethylendiamonium (EnVAs) and piperazonium (PipVAs) were evaluated as catalysts for the oxidation of thioethers and alkenes, using H2O2 and t-butyl hydroperoxide (TBHP) as oxidants. The intrinsic activity of EnVAs was higher than that of PipVAs for the oxidation of sulfides. Similar results were obtained when using either H2O2 or TBHP as oxidants. However, the sterical effects were enhanced when TBHP was used and higher selectivities towards sulfoxides were achieved with this oxidant. The catalytic activity of the V-based materials in the epoxidation of simple alkenes and allylic alcohols was assessed. Upon reuse, both materials show no significant decrease in their catalytic properties.
