- +-Nootkatone derivative
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The invention discloses a preparation method for +-nootkatone derivative. The present invention uses the +-nootkatone derivative extracted from cedar leaves as the main material, a chemical compound II is obtained after the restoration through sodium borohydride, the chemical compound II reacts to obtain a chemical compound III and a chemical compound IV through the decomposition of enzymatic dynamics, or decomposes through dynamic kinetics to obtain a chemical compound III with more than 90% yield, a chemical compound V is obtained after hydrolyzing the chemical compound III. The present invention turns the latent chiral ketone group in +-nootkatone into a chirality hydroxy center, and splits further; the present invention has the characteristics of being simple in operation, being high in product yield and with good optics purity.
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Paragraph 0006; 0012
(2017/08/27)
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- Studies towards the synthetic applicability of biocatalytic allylic oxidations with the lyophilisate of Pleurotus sapidus
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The edible fungus Pleurotus sapidus (PSA) is a particularly interesting biocatalytic system for allylic oxidation and has a remarkably broad substrate range from terpenoids to fatty acids. The oxidations are most likely catalyzed by a lipoxygenase and involve the formation of peroxides via radical intermediates in the first rate-limiting step. We provide herein a rationalization of the observed regioselectivity of these conversions by means of computational determination of bond dissociation enthalpies of a set of tailor-made spirocyclic terpenoids. It was found that only strongly activated allylic positions (BDH298 of 80 kcal/mol) with neighboring heteroatoms or with activating alkyl groups are oxidized to the corresponding unsaturated lactones or enones, respectively. With the synthesis and purification of allylic hydroperoxide intermediates, we have been able to characterize the putative direct precursors of enones in PSA oxidations. Our results suggest a two-step oxidation mechanism involving hydroperoxide intermediates which are rapidly converted to the observed enones by an enzymatic reaction.
- Weidmann, Verena,Kliewer, Serge,Sick, Marko,Bycinskij, Sergej,Kleczka, Margarethe,Rehbein, Julia,Griesbeck, Axel G.,Zorn, Holger,Maison, Wolfgang
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- Selective enzymatic synthesis of the grapefruit flavor (+)-nootkatone
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(+)-Nootkatone is a high-value sesquiterpenoid known for its grapefruit-odor impression. Its isolation from natural plant sources suffers from low yields, and chemical syntheses involve carcinogenic or hazardous compounds. Herein, a biocatalytic route for the synthesis of (+)-nootkatone that combines two enzymes in one pot is presented. In the first step, a cytochrome P450 monooxygenase catalyzes the selective allylic hydroxylation of the sesquiterpene (+)-valencene to the intermediate alcohol nootkatol. In the second step, nootkatol is further oxidized to (+)-nootkatone by an alcohol dehydrogenase (ADH). The challenging task of finding a suitable cofactor regeneration system was solved by careful selection of an appropriate cosubstrate for the ADH, which works in a dual-functional mode. After reaction optimization, involving cosolvent and cosubstrate screening, (+)-nootkatone concentrations of up to 360mg L-1 and a space-time yield of 18mg L-1 h-1 were achieved. Fruitful synthesis: A P450 monooxygenase and an alcohol dehydrogenase are combined in a one-pot cascade to afford the high-value grapefruit flavor (+)-nootkatone by selective oxidation of (+)-valencene.
- Schulz, Sebastian,Girhard, Marco,Gassmeyer, Sarah K.,J?ger, Vera D.,Schwarze, Daniel,Vogel, Andreas,Urlacher, Vlada B.
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p. 601 - 604
(2015/02/19)
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- Pest control compositions and methods for their use
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Compositions and methods for controlling an arthropod pest population that include an eremophilane sesquiterpene pest control agent (such as, nootkatone or 13-hydroxy-valencene) and a dialkyl-substituted phenol pest control agent (such as, carvacrol) are disclosed. The compounds present in the compositions may be isolated from natural sources, semi-synthesized from naturally occurring compounds, or completely synthesized. The pest control compositions may be applied directly to a pest or the locus of a pest, and function as topical or ingestible pest toxins.
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- Method for separation of reaction products from catalysts
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A method separates a reaction product from an imide compound catalyst represented by Formula (1) or an altered derivative thereof in a reaction mixture obtained as a result of a reaction in the presence of the imide compound catalyst by performing an extraction process using two organic solvents separable from each other to thereby separate the reaction product into one organic solvent layer and the imide compound catalyst or an altered derivative thereof into the other organic solvent layer, respectively: wherein R1 and R2 are each, for example, a hydrogen atom or an alkyl group, where R1 and R2 may be combined to form a double bond, an aromatic ring, or a non-aromatic ring; and X is an oxygen atom or a hydroxyl group. The method of the invention can efficiently and simply separate a reaction product from a catalyst and/or an altered derivative of the catalyst in a reaction mixture obtained as a result of a reaction of a substrate such as a hydrocarbon using N-hydroxyphthalimide or another imide compound as the catalyst.
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- METHOD FOR SEPARATION OF REACTION PRODUCTS FROM CATALYSTS
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A method separates a reaction product from an imide compound catalyst represented by Formula (1) or an altered derivative thereof in a reaction mixture obtained as a result of a reaction in the presence of the imide compound catalyst by performing an extraction process using two organic solvents separable from each other to thereby separate the reaction product into one organic solvent layer and the imide compound catalyst or an altered derivative thereof into the other organic solvent layer, respectively: wherein R1 and R2 are each, for example, a hydrogen atom or an alkyl group, where R1 and R2 may be combined to form a double bond, an aromatic ring, or a non-aromatic ring; and X is an oxygen atom or a hydroxyl group. The method of the invention can efficiently and simply separate a reaction product from a catalyst and/or an altered derivative of the catalyst in a reaction mixture obtained as a result of a reaction of a substrate such as a hydrocarbon using N-hydroxyphthalimide or another imide compound as the catalyst.
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- Process for producing organic compounds by catalysis of imide compounds
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A process produces an organic compound by catalysis of an imide compound of Formula (1): wherein R1 and R2 are each an alkyl group, aryl group, cycloalkyl group, etc., where R1 and R2 may be combined to form a double bond, or an aromatic or non-aromatic ring; and X is an oxygen atom or a hydroxyl group. In this process, the imide compound catalyst is added in installments to the reaction system to perform a reaction. Such reactions include, for example, oxidation reactions, carboxylation reactions, nitration reactions, sulfonation reactions, and carbon-carbon bond formation reactions. This process can produce a target compound with a higher conversion or selectivity in the production of the organic compound by catalysis of the imide compound catalyst such as N-hydroxyphthalimide.
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- Regioselectivities in the Catalyzed Conjugate Addition of Organoaluminium and Organotitanium Reagents to Sterically Hindered Enones: Investigation of the Methylation of 10β-Methyl-Δ1,9-2-octalones
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Regioselectivities in Michael-type reactions of organoaluminium and organotitanium reagents with sterically hindered carbonyl compounds 1 and 5 concerning 1,2- versus 1,4-addition were determined.Throughout this investigation Me3Al/cat.Ni(acac)2 was found to be the most useful reagent for strongly hindered systems. - Key Words: Conjugate alkylation/ Organoaluminium/ Organotitanium/ Copper catalysis/ Nickel catalysis
- Kabbara, Jazid,Flemming, Steffen,Nickisch, Klaus,Neh, Harribert,Westermann, Juergen
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p. 401 - 406
(2007/10/02)
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