23007-29-6

Upstream product

• 126-91-0 linalool 
• 1260148-31-9 C₁₂H₂₂O₅ 
• 61302-43-0 Essigsaeure-<(6S,2E)-6,7-dihydroxy-3,7-dimethyl-2-octen-1-yl>ester 
• 188579-26-2 Carbonic acid (E)-6,7-dihydroxy-3,7-dimethyl-oct-2-enyl ester ethyl ester 
• 78-70-6 3,7-dimethylocta-1,6-dien-3-ol 
• 40036-54-2 (E)-5-(3,3-dimethyloxiran-2-yl)-3-methylpent-2-en-1-ol 
• 106-24-1 Geraniol 
• 123-35-3 7-methyl-3-methene-1,6-octadiene 
• 85217-73-8 (Z)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate 
• 106-25-2 Nerol 
• 128344-89-8 syn-N-<1-(5-ethenyltetrahydro-5-methylfuran-2-yl)-1-methylethoxy>-2,2,6,6-tetramethylpiperidine 
• 128344-89-8 anti-N-<1-(5-ethenyltetrahydro-5-methylfuran-2-yl)-1-methylethoxy>-2,2,6,6-tetramethylpiperidine 
• 75-16-1 methylmagnesium bromide 
• 685507-90-8 2,6-dimethyl-oct-7-ene-2,3,6-triol 

Relevant academic research and scientific papers

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.

PREPRATION D'OXYDES DE LINALOL PAR BIOCONVERSION

Microbial cyclisation of linalol (+), (-) and (+-) by a nigericin-producing Streptomyces albus gives linalol oxydes.Cis linalol oxyde gives opposite signs for the rotatory power when measured neat or in solution.

Synthesis of All Four Stereoisomers of Enantiomerically Pure cis- and trans-Linalyl Oxides

The four enantiomerically pure cis- and trans-linalyl oxides can be prepared in one step and good yield from (6S)- or (6R)-6,7-dihydroxygeranyl phenylcarbamate.

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.

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.

Cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes as catalysts for oxidative alkenol cyclization by tert-butyl hydroperoxide

cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes are Lewis acids able to catalyze oxidative cyclization of alkenols by tert-butyl hydroperoxide (TBHP). Terminal dimethyl-substituted (prenyl-type) 4-pentenols bearing an alkyl or a phenyl group in position 1 afford under such conditions 2,5-cis-derivatives of 2-(tetrahydrofuran-2-yl)-2-propanol as major and tetrahydropyran-3-ols as minor products (four examples). Oxidizing 1-phenyl-6-methylhept-5-en-1-ol yields a 75/25-mixture of the derived 2-(tetrahydropyran-2-yl)-2-propanol and an oxepan-3-ol, whereas 2-propenols give epoxides in up to 94% yield. Epoxidizing geraniol by TBHP in the presence of a vanadium catalyst prepared from (2S,6R)-2-diphenylmethanol-6- hydroxymethylpiperidine occurs enantioselectively. Highfield shifts of vanadium-51 resonances upon adding alkyl hydroperoxides to solutions of cis-2,6-bis-(methanolate)-piperidine vanadium(V) complexes point to vanadium(V) tert-butyl peroxy complex formation as key step for activating peroxides.

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.

Vanadium(V)-catalyzed oxidation of (3R)-linalool - The selective formation of furanoid linalool oxides and their conversion into isocyclocapitelline derivatives

Oxidation of (3R)-linalool (2) with tert-butyl hydroperoxide (TBHP) occurs at the 6,7-position to selectively afford linalool oxide cis-1, if catalyzed by vanadium(V) Schiff base complexes 4. Substituted tetrahydrofuran cis-1 and its isomer trans-1 served