41720-60-9

Upstream product

• 78-70-6 3,7-dimethylocta-1,6-dien-3-ol 
• 126-90-9 (S)-(+)-linalool 
• 15249-35-1 6,7-epoxylinalool 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 364045-87-4 (2S,5S)-2-hydrocarbonyl-5-(1-hydroxyl-1-methylethyl)-2-methyltetrahydrofuran 
• 174599-43-0 (-)-5,6-dihydroxy-6-methylheptan-2-one 
• 1260148-31-9 C₁₂H₂₂O₅ 
• 61302-43-0 Essigsaeure-<(6S,2E)-6,7-dihydroxy-3,7-dimethyl-2-octen-1-yl>ester 
• 128344-89-8 anti-N-<1-(5-ethenyltetrahydro-5-methylfuran-2-yl)-1-methylethoxy>-2,2,6,6-tetramethylpiperidine 
• 106-24-1 Geraniol 
• 40036-54-2 (E)-5-(3,3-dimethyloxiran-2-yl)-3-methylpent-2-en-1-ol 
• 128344-89-8 syn-N-<1-(5-ethenyltetrahydro-5-methylfuran-2-yl)-1-methylethoxy>-2,2,6,6-tetramethylpiperidine 
• 123-35-3 7-methyl-3-methene-1,6-octadiene 
• 85217-73-8 (Z)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate 

Relevant 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

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.).

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.

Trans-2-tritylcyclohexanol as a chiral auxiliary in permanganate-mediated oxidative cyclization of 2-methylenehept-5-enoates: Application to the synthesis of trans-(+)-linalool oxide

The permanganate-mediated oxidative cyclization of a series of 2-methylenehept-5-eneoates bearing different chiral auxiliaries was investigated, leading to the discovery of trans-2-tritylcyclohexanol (TTC) as a highly effective chiral controller for the f

Biotransformations of terpenes by fungi from amazonian Citrus plants

The biotransformations of (RS)-linalool (1), (S)-citronellal (2), and sabinene (3) with fungi isolated from the epicarp of fruits of Citrus genus of the Amazonian forest (i.e., C. limon, C. aurantifolia, C. aurantium, and C. paradisiaca) are reported. The

Two-step, stereoselective synthesis of linalyl oxides by asymmetric allylic O-alkylation

Each of the four tetrahydrofuran linalyl oxides was prepared by a Sharpless asymmetric dihydroxylation of geranyl acetate with AD-mix-α or AD-mix-β, followed by a stereoselective palladium-mediated cyclization using the chiral ligand C3-TunePhos.

Fungal biotransformation of (±)-linalool

The biotransformation of (±)-linalool was investigated by screening 19 fungi. Product accumulation was enhanced by substrate feeding and, for the first time, lilac aldehydes and lilac alcohols were identified as fungal biotransformation byproduct using SPME-GC-MS headspace analysis. Aspergillus niger DSM 821, Botrytis cinerea 5901/02, and B. cinerea 02/FBII/2.1 produced different isomers of lilac aldehyde and lilac alcohol from linalool via 8-hydroxylinalool as postulated intermediate. Linalool oxides and 8-hydroxylinalool were the major products of fungal (±)-linalool biotransformations. Furanoid trans-(2R,5R)- and cis-(2S,5R)-linalool oxide as well as pyranoid trans-(2R,5S)- and cis-(2S, 5S)-linalool oxide were identified as the main stereoisomers with (3S,6S)-6,7-epoxylinalool and (3R,6S)-6,7-epoxylinalool as postulated key intermediates of fungal (±)-linalool oxyfunctionalization, respectively. With a conversion yield close to 100% and a productivity of 120 mg/L·day linalool oxides, Corynespora cassiicola DSM 62485 was identified as a novel highly stereoselective linalool transforming biocatalyst showing the highest productivity reported so far.

From rational octahedron design to reticulation serendipity. A thermally stable rare earth polymeric disulfonate family with CdI2-like structure, bifunctional catalysis and optical properties

A new family of lanthanide disulfonates Ln(OH)(NDS)- (H2O), (Ln = La, Pr and Nd; NDS = 1,5-naphthalenedisulfonate) was designed and hydrothermally synthesized; this is the first example of a disulfonate ligand coordinated to six different Ln atoms; these materials, with high thermal stability, act as active and selective bifunctional catalysts in oxidation and epoxide ring opening; strong luminescence from the optically active Nd center was observed.

Rearrangements of epoxides of linalool and nerolidyl acetate in acid media

The behavior of epoxides of linalool and cis-nerolidyl acetate was comparatively investigated in acids of various strength with the goal of establishing the effect of the structure of the initial compound and the medium character on the main direction of cationoid rearrangement. Linalool epoxides undergo cyclization of solid acid catalysts affording oxygen-containing heterocyclic compounds whereas the nerolidyl acetate epoxides yield the ketones originating from the opening of the epoxy ring followed by 1,2-hydride shift. 10,11-Epoxy derivative of cis-nerolidyl acetate affords 7-oxanorbornane as a minor product.

Oxidative cyclization based on reversing the polarity of enol ethers and ketene dithioacetals. Construction of a tetrahydrofuran ring and application to the synthesis of (+)-nemorensic acid

The utility of oxidative cyclization reactions for the construction of tetrahydrofuran rings has been examined. In these experiments, alcohol nucleophiles were found to be effective traps for radical cation intermediates generated from both enol ether and ketene dithioacetal groups, The reactivity of the alcohol trapping group appeared to lie between that of an enol ether and an allylsilane trapping group. The stereochemical outcome of cyclization reactions originating from the oxidation of an enol ether was found to be controlled by stereoelectronic factors. The utility of these cyclization reactions was illustrated with the synthesis of a key tetrahydrofuran building block for the synthesis of linalool oxide and rotundisine. Cyclization reactions triggered by the oxidation of a ketene dithioacetal led to far greater levels of stereoselectivity. The stereochemical outcome of these reactions was shown to arise from steric factors involving the larger ketene acetal group. The synthetic utility of cyclizations utilizing ketene dithioacetal derived radical cations was demonstrated by completing an asymmetric synthesis of (+)-nemorensic acid. Finally, the reactions were shown to be compatible with the use of an amide nucleophile and the direct formation of a lactone product.