37267-80-4

Upstream product

• 126-91-0 linalool 
• 79-21-0 peracetic acid 
• 2311-91-3 monoperoxyphthalic acid 
• 16262-93-4 5,6-epoxy-6-methyl-2-heptanone 
• 1826-67-1 vinyl magnesium bromide 
• 78-70-6 3,7-dimethylocta-1,6-dien-3-ol 
• 111-66-0 oct-1-ene 
• 29171-20-8 3,7-dimethyloct-6-en-1-yn-3-ol 
• 126-90-9 (S)-(+)-linalool 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 122313-77-3 (6S,2E)-6,7-dihydroxy-3,7-dimethyl-2-octen-1-yl phenylcarbamate 
• 19493-09-5 Methylenetriphenylphosphorane 
• 364045-87-4 (2S,5S)-2-hydrocarbonyl-5-(1-hydroxyl-1-methylethyl)-2-methyltetrahydrofuran 
• 110-93-0 6-Methyl-hept-5-en-2-on 

Relevant academic research and scientific papers

Anodic coupling reactions: probing the stereochemistry of tetrahydrofuran formation. A short, convenient synthesis of linalool oxide.

[reaction: see text]. Intramolecular coupling reactions between enol ether radical cations and oxygen nucleophiles are primarily governed by stereoelectronics. By taking advantage of this observation, a tetrahydrofuran building block for use in constructing (+)-linalool oxide and rotundisine has been synthesized in four steps from a commercially available starting material. The synthesis of (+)-linalool oxide has been completed.

UTL titanosilicate: An extra-large pore epoxidation catalyst with tunable textural properties

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.

VOLATILE OIL CONSTITUENTS OF SAGEBRUSH

The volatile oil of Artemisia arbuscula arbuscula contained a new irregular monoterpene, 2,5-dimethyl-4-vinyl-1,5-hexadiene-3-ol (isolyratol), which was isolated and identified by spectral means.The optically pure furanoid (2S,5S)-trans-5-methyl-5-vinyltetrahydrofur-2-yl methyl ketone (arbusculone), was also characterized by transformation to known (2S,5S)-trans-linalyl oxide.The former component has never been isolated from natural sources prior to this study.The neutral pentane extract also contained several previously characterized non-head-to-tail monoterpenes including artemiseole, artemisia ketone, artemisyl acetate, methyl santolinate, and santolina triene, as well as the regular monoterpenes 1,8-cineole, camphor, p-cymene, camphene and the C6 fragment, terelactone. - Key Word Index: Artemisia arbuscula arbuscula; Asteraceae (Compositae); volatile oil; monoterpenes; irregular monoterpenes.

One-pot synthesis at room temperature of epoxides and linalool derivative pyrans in monolacunary Na7PW11O39-catalyzed oxidation reactions by hydrogen peroxide

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

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

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.

A protecting-group-free synthesis of arbusculone, andirolactone, pinnatolide, ipomolactone, cyclocapitelline and isocyclocapitelline

A general approach for a collective synthesis of natural products containing substituted THF ring is described. In this paper, Arbusculone, a small molecule natural product accomplished using a short route, is used as the key intermediate to achieve the total synthesis of Andirolactone, Pinnatolide, Ipomolactone, Cyclocapitelline, Isocyclocapitelline and their two isomers in less than ten steps. The present effort highlights protecting-group-free total syntheses and the shortest route to access these natural products from commercially available cheap starting materials.

Antimalarial Properties of Simplified Kalihinol Analogues

Several kalihinol natural products, members of the broader isocyanoterpene family of antimalarial agents, are potent inhibitors of Plasmodium falciparum, the agent of the most severe form of human malaria. Our previous total synthesis of kalihinol B provided a blueprint to generate many analogues within this family, some as complex as the natural product and some much simplified and easier to access. Each analogue was tested for blood-stage antimalarial activity using both drug-sensitive and -resistant P. falciparum strains. Many considerably simpler analogues of the kalihinols retained potent activity, as did a compound with a different decalin scaffold made in only three steps from sclareolide. Finally, one representative compound showed reasonable stability toward microsomal metabolism, suggesting that the isonitrile functional group that is critical for activity is not an inherent liability in these compounds.

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

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

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.