17102-64-6Relevant academic research and scientific papers
Eleuthesides and their analogs: VII. Synthesis of menthane derivatives by the Diels-Alder reaction of levoglucosenone with (2E,4E)-hexa-2,4-dien-1-yl acetate
Pilipenko,Sharipov,Valeev
, p. 1504 - 1510 (2014)
The Diels-Alder reaction of levoglucosenone with (2E,4E)-hexa-2,4-dien-1-yl acetate was used to synthesize chiral functionalized derivatives of isopropyl(methyl)cyclohexene fused to a carbohydrate fragment.
Catalytic Asymmetric Allylic Substitution with Copper(I) Homoenolates Generated from Cyclopropanols
Shi, Chang-Yun,Yin, Liang,Zhang, Qi,Zhou, Si-Wei
supporting information, p. 26351 - 26356 (2021/11/09)
By using copper(I) homoenolates as nucleophiles, which are generated through the ring-opening of 1-substituted cyclopropane-1-ols, a catalytic asymmetric allylic substitution with allyl phosphates is achieved in high to excellent yields with high enantioselectivity. Both 1-substituted cyclopropane-1-ols and allylic phosphates enjoy broad substrate scopes. Remarkably, various functional groups, such as ether, ester, tosylate, imide, alcohol, nitro, and carbamate are well tolerated. Moreover, the present method is nicely extended to the asymmetric construction of quaternary carbon centers. Some control experiments argue against a radical-based reaction mechanism and a catalytic cycle based on a two-electron process is proposed. Finally, the synthetic utilities of the product are showcased by means of the transformations of the terminal olefin group and the ketone group.
Step-Economic Synthesis of Biomimetic β-Ketopolyene Thioesters and Demonstration of Their Usefulness in Enzymatic Biosynthesis Studies
Hahn, Frank,Ro?, Theresa,Schr?der, Marius,Wunderlich, Johannes
supporting information, (2020/07/04)
Studies on the biosynthetic processing of polyene thioester intermediates are complicated by limited access to appropriate substrate surrogates. We present a step-economic synthetic access to biomimetic β-ketopolyene thioesters that is based on an Ir-catalyzed reductive Horner-Wadsworth-Emmons olefination. New β-ketotriene and pentaenethioates of pantetheine and N-acetylcysteamine were exemplarily synthesized via short and concise routes. The usefulness of these compounds was demonstrated in an in vitro assay with the ketoreductase domain MycKRB from mycolactone biosynthesis.
Synthesis method of laspeyresia pomonella sex pheromone
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Paragraph 0030-0032; 0039-0041, (2019/09/17)
The invention relates to a synthesis method of laspeyresi pomonella sex pheromone. The method comprises the steps as follows: (1) methanol is added to methyl sorbate as a raw material, and an intermediate A sorbic alcohol is obtained through 5% palladium-carbon catalytic hydrogenation reduction; (2) the intermediate A sorbitol obtained in (1) and acetic anhydride are subjected to a reaction in ethyl acetate, triethylamine and water to obtain an intermediate B sorbic acetate; (3) 6-chlorohexanol is subjected to a reaction with trimethylchlorosilane in toluene in the presence of ethyl acetate and triethylamine, after the reaction, water is added, stirring and layering are performed, and an intermediate C6-chlorohexanol trimethylsilyl ester is obtained; (4) the intermediate B sorbic acetate and the intermediate C6-chlorohexanol trimethylsilyl ester are subjected to a reaction with sodium sand in a toluene solution, then, water and sulfuric acid are dropwise added, layering and rectification are performed, and a target product E8,E10-dodecadiene-1-ol is obtained. The synthesis method has the advantages as follows: the laspeyresi pomonella sex pheromone is synthesized from available rawmaterials, the reaction route is short, and the selectivity and product yield can be increased.
One Stone for Three Birds-Rhodium-Catalyzed Highly Diastereoselective Intramolecular [4+2] Cycloaddition of Optically Active Allene-1,3-dienes
Han, Yulin,Qin, Anni,Ma, Shengming
, p. 486 - 496 (2019/04/04)
RhCl(PPh3)3-catalyzed [4+2] intramolecular cycloaddition of optically active axially chiral allene-dienes afforded cis-fused [3.4.0]-bicyclic products with three chiral centers in good yields with an excellent chemo- and diastereoselectivity. A pair of enantiomers of such products was generated highly selectively from both enantiomers of starting allene-dienes, indicating that the axial chirality dictated the absolute configurations of the three in situ generated chiral centers with a very high efficiency of chirality transfer.
Biocatalysed reduction of carboxylic acids to primary alcohols in aqueous medium: A novel synthetic capability of the zygomycete fungus Syncephalastrum racemosum
Brenna, Elisabetta,Cannavale, Flavia,Crotti, Michele,Parmeggiani, Fabio,Romagnolo, Alice,Spina, Federica,Varese, Giovanna Cristina
, p. 83 - 88 (2015/04/14)
Abstract The zygomycete fungus Syncephalastrum racemosum shows the remarkable capability of reducing carboxylic acids to primary alcohols in water medium, at ambient temperature and pressure. The reaction does not require molecular hydrogen, and in most cases affords quantitative transformations. The results herein reported highlight the basic molecular scaffold that can be accepted by the fungus, the effects due to substituents, and also the possibility that carboxylic acids can be generated in the reaction medium by enzymatic hydrolysis of the corresponding methyl esters. This biocatalysed reduction implements the scarcely supplied enzymatic toolbox for the conversion of carboxylic groups into primary alcohols, which can be exploited for the optimisation of sustainable synthetic procedures.
SYNTHESIS OF OLEFINIC ALCOHOLS VIA ENZYMATIC TERMINAL HYDROXYLATION
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Paragraph 0314; 0315, (2016/01/30)
In certain aspects, the present invention provides methods for producing terminally hydroxylated alkenes and alkynes by contacting an unsaturated or saturated hydrocarbon substrate with a hydroxylase enzyme. Exemplary terminal hydroxylases useful for carrying out the methods of the invention exhibit strong selectivity towards one terminal carbon of a hydrocarbon substrate and include, but are not limited to, non-heme diiron alkane monooxygenases, cytochromes P450 (e.g., cytochromes P450 of the CYP52 and CYP153 family), as well as long chain alkane hydroxylases. In some embodiments, the terminally hydroxylated alkene or alkyne is further converted to a terminal alkenal. In certain embodiments, terminally hydroxylated alkenes and alkynes are useful as insect pheromones which modify insect behavior. In other embodiments, terminally hydroxylated alkenes and alkynes are useful intermediates for producing pheromones via acetylation or oxidation of the alcohol moiety.
Z-Stereoselective semi-reduction of alkynes: Modification of the Boland protocol
Mohamed, Yasser M.A.,Hansen, Trond Vidar
, p. 3872 - 3877 (2013/06/27)
Highly Z-selective semi-reduction of alkynes has been achieved by adding TMSCl to a mixture of Zn(Cu/Ag), water, and methanol. The conjugated Z-alkenes have been prepared in high yields at ambient temperature. The formation of isomeric E-alkenes and over-reduction to alkanes were suppressed in our modified Boland reduction protocol. The methodology was extended to the preparation of Z-substituted stilbenes.
Reduction of carboxylic acids using esters of benzotriazole as high-reactivity intermediates
Morales-Serna, Jose Antonio,Garcia-Rios, Erendira,Bernal, Jorge,Paleo, Ehecatl,Gavino, Ruben,Cardenas, Jorge
scheme or table, p. 1375 - 1382 (2011/06/19)
Herein, we describe a simple and practical protocol for the reduction of carboxylic acids via the in situ formation of hydroxybenzotriazole esters followed by reaction with sodium borohydride to give the corresponding alcohols. The reaction proceeds with excellent yields in the presence of water. Georg Thieme Verlag Stuttgart - New York.
Supramolecular catalyst for aldehyde hydrogenation and tandem hydroformylation-hydrogenation
Diab, Lisa,Smejkal, Tomas,Geier, Jens,Breit, Bernhard
supporting information; experimental part, p. 8022 - 8026 (2010/02/28)
The chemoselective reduction of aldehydes and the tandem hydroformylation-hydrogenation of terminal alkenes are possible with a supramolecular catalyst that operates by a novel mechanism involving substrate activation by hydrogen bonding and subsequent metalligand bifunctional hydrogenation (see scheme).
