71697-84-2Relevant academic research and scientific papers
Chemo-enzymatic pathways toward pinene-based renewable materials
Stamm,Tengdelius,Schmidt,Engstr?m,Syrén,Fogelstr?m,Malmstr?m
, p. 2720 - 2731 (2019)
Sobrerol methacrylate (SobMA) was synthesized and subsequently polymerized using different chemical and enzymatic routes. Sobrerol was enzymatically converted from α-pinene in a small model scale by a Cytochrome P450 mutant from Bacillus megaterium. Conve
Biomimetic conversion of α-pinene with H2O2 to sobrerol over V2O5: Dihydroxylation by a peroxo vanadium peracid vectoring gentle synergistic oxidation
He, Huiting,Huang, Geng,Kirk, Steven Robert,Li, Hui,Liu, Jian,Liu, Qiang,Liu, Xianxiang,Mao, Liqiu,Su, Shengpei,Xu, Qiong,Yin, Dulin
, (2020/05/18)
In this communication, we report the gentle preparation of sobrerol from dihydroxylation of α-pinene synergistically catalyzed by V2O5-H2O2 under benign conditions. It was proposed that a “peroxo vanadium acid”, VVO(OH)(OOH), was formed by HOO? insertion and proton transfer between V2O5 and H2O2. Theoretical DFT calculations that using the dimer?vanadium peracid as a model of the catalytically active species revealed that peroxo vanadium acid exhibited bifunctional catalytic capabilities resembling epoxidation of α-pinene by peracetic acid and then open-ring hydration with an acetic media.
Hot water-promoted SN1 solvolysis reactions of allylic and benzylic alcohols
Xu, Zhao-Bing,Qu, Jin
supporting information, p. 314 - 323 (2013/03/13)
During the studies of hydrolysis of epoxides in water, we found that the hydrolysis of (-)-α-pinene oxide at 20 °C gave enantiomerically pure trans-(-)-sobrerol, whereas the same reaction in water heated at reflux unexpectedly gave a racemic mixture of trans- and cis-sobrerol (trans/cis=6:4). We have examined this remarkable difference in detail and found that hot water, whose behavior is quite different compared with room- or high-temperature water, could promote SN1 solvolysis reactions of allylic alcohols and thus caused the racemization of trans-(-)-sobrerol. The effect of reaction temperature, the addition of organic co-solvent, and the concentration of the solute on the rate of the racemization of trans-(-)-sobrerol were further examined to understand the role that hot water played in the reaction. It was proposed that the catalytic effects of hot water are owing to its mild acidic characteristic, thermal activation, high ionizing power, and better solubility of organic reactant. Further investigation showed that the racemization of other chiral allylic/benzylic alcohols could efficiently proceed in hot water.
Unique salt effect on highly selective synthesis of acid-labile terpene and styrene oxides with a tungsten/Hcatalytic system under acidic aqueous conditions
Hachiya, Houjin,Kon, Yoshihiro,Ono, Yutaka,Takumi, Kiyoshi,Sasagawa, Naoki,Ezaki, Yoichiro,Sato, Kazuhiko
experimental part, p. 1672 - 1678 (2012/07/16)
Acid-labile epoxides such as terpene and styrene oxides are effectively synthesized in high yields with good selectivities using tungsten-catalyzed hydrogen peroxide epoxidation in the presence of NaO The salt effect is thought to originate with the addition of a saturated amount of NaOto aqueous H this addition strongly inhibited the undesired hydrolysis of the acid-labile epoxy products, despite the biphasic conditions of substrate as oil phase and Has acidic aqueous phase.
Unique salt effect on the high yield synthesis of acid-labile terpene oxides using hydrogen peroxide under acidic aqueous conditions
Hachiya, Houjin,Kon, Yoshihiro,Ono, Yutaka,Takumi, Kiyoshi,Sasagawa, Naoki,Ezaki, Yoichiro,Sato, Kazuhiko
scheme or table, p. 2819 - 2822 (2012/01/02)
Acid-labile epoxides such as -pinene oxide are (effectively) synthesized in high yield from the epoxidation of terpenes with aqueous H2O 2 catalyzed by Na2WO4, [Me(n-C 8H17)3N]HSO4, and PhP(O)(OH) 2 in the presence of Na2SO4 as an auxiliary additive under organic solvent-free conditions at ambient temperature. Origin of the salt effect is considered that the addition of a saturated amount of Na2SO4 to aqueous H2O2 strongly inhibited the undesired hydrolysis of the acid-labile epoxide products, despite the highly acidic reaction conditions. Georg Thieme Verlag Stuttgart · New York.
Isomerization of α-pinene oxide over cerium and tin catalysts: Selective synthesis of trans-carveol and trans-sobrerol
Costa, Vinícius V.,Da Silva Rocha, Kelly A.,De Sousa, Líniker F.,Robles-Dutenhefner, Patricia A.,Gusevskaya, Elena V.
experimental part, p. 69 - 74 (2011/10/05)
A remarkable effect of the solvent nature on the acid catalyzed transformation of α-pinene oxide allowed direction of the reaction to either trans-carveol or trans-sobrerol. Each of these highly valuable compounds was obtained in nearly 70% yield using an appropriate polar solvent, whose basicity affected strongly the product distribution. In acetone, a weakly basic solvent, the reaction over heterogeneous sol-gel Sn/SiO2 or Ce/SiO2 catalysts gave mainly trans-sobrerol. No leaching of active components occurs under the reaction conditions and the catalysts can be recovered and reused. On the other hand, in more basic solvent, i.e., dimethylacetamide, the reaction was essentially directed to trans-carveol. Due to the leaching problems with Sn/SiO2 and Ce/SiO2 materials, the synthesis of trans-carveol was performed under homogeneous conditions using CeCl3 or SnCl2 as catalysts with a catalyst turnover number up to ca. 1200. The method represents one of the few examples of the synthesis of isomers from α-pinene oxide, other than campholenic aldehyde, with a sufficient for practical usage selectivity.
Novel α-pinene-derived mono- and bisphosphinite ligands: Synthesis and application in catalytic hydrogenation
Hobu?, Dennis,Hasenj?ger, Jens,Driessen-H?lscher, Birgit,Baro, Angelika,Axenov, Kirill V.,Laschat, Sabine,Frey, Wolfgang
scheme or table, p. 94 - 103 (2011/09/15)
Novel mono- and bisphosphinite (-)-pinane-based ligands have been synthesized from (-)-α-pinene. Mixed with [(COD)2Rh] +[BF4]-, these ligands displayed moderate up to high catalytic activity in hydrogenation of dimethyl itaconate with dihydrogen. It has been observed that the structure of the ligand, the reaction temperature and solvent are important to define productivity of the phosphinite-based Rh-catalysts. Bisphosphinite ligands in hydrogenation reactions suffered from an Arbuzov rearrangement, leading to fast deactivation of the hydrogenation catalyst. In contrast, monophosphinite-derived Rh-catalysts showed increased productivity as well as thermal stability. An almost quantitative conversion of dimethyl itaconate has been achieved at elevated temperatures in toluene. Alternatively, hydrogenation of dimethyl itaconate with monophosphinite ligands has been carried out in MeOH at room temperature or 40 °C and has led to a nearly quantitative conversion.
Phosphotungstic acid as a versatile catalyst for the synthesis of fragrance compounds by α-pinene oxide isomerization: Solvent-induced chemoselectivity
Da Silva Rocha, Kelly A.,Hoehne, Juliana L.,Gusevskaya, Elena V.
body text, p. 6166 - 6172 (2009/06/17)
The remarkable effect of the solvent on the catalytic performance of H 3PW12O40, the strongest heteropoly acid in the Keggin series, allows direction of the transformations of α-pinene oxide (1) to either campholenic aldehyde (2), trans-carveol (3), trans-sobrerol (4a), or pinol (5). Each of these expensive fragrance compounds was obtained in good to excellent yields by using an appropriate solvent. Solvent polarity and basicity strongly affect the reaction pathways: nonpolar nonbasic solvents favor the formation of aldehyde 2; polar basic solvents favor the formation of alcohol 3; whereas in polar weakly basic solvents, the major products are compounds 4a and 5. On the other hand, in 1,4-dioxane, which is a nonpolar basic solvent, both aldehyde 2 and alcohol 3 are formed in comparable amounts. The use of very low catalyst loading (0.005-1 mol%) and the possibility of catalyst recovery and recycling without neutralization are significant advantages of this simple, environmentally benign, and low-cost method. This method represents the first example of the synthesis of isomers from α-pinene oxide, other than campholenic aldehyde, with a selectivity that is sufficient for practical usage.
Formation of trans-verbenol and verbenone from α-pinene catalysed by immobilised Picea abies cells
Vanek, Tomas,Halik, Jan,Vankova, Radmila,Valterova, Irena
, p. 321 - 325 (2007/10/03)
Both enantiomers and the raceinate of α-pinene were transformed by Picea abies cells immobilised on alginate. The main products were cis- and trans-verbenol, the later being further transformed to verbenone. The enantiomeric purity of each product more or less corresponded to that of the substrate. Transformation by free cells was faster than that by the immobilised cells. The ratio of products differed to some extent between the transformation by tree and immobilised cells.
Partial purification of Nigella sativa L. seed lipase and its application in transesterification reactions
Tuter, Melek,Secundo, Francesco,Riva, Sergio,Ayse Aksoy,Ustun, Guldem
, p. 43 - 48 (2007/10/03)
Nigella sativa L. seed lipase isolated from defatted seeds was partially purified and used as catalyst in transesterification reactions. Purification of an ammonium sulfate-precipitated sample (at 35% saturation, Nigella PL) by DEAE ion-exchange chromatography increased the specific activity from 13.9 to 156.7 U/mg protein. Nigella PL and Nigella CPL (the partially purified enzyme sample obtained by DEAE ion-exchange chromatography) catalyzed the transesterification of vinyl acetate with octanol, with racemic sulcatol (6-methyl-5-hepten-2-ol), and with racemic trans-sobrerol (trans-p-menth-6-ene-2,8-diol) in different organic solvents. Both activity and enantioselectivity of the enzyme samples used for these biotransformations were affected by the nature of the organic solvent.
