4031-48-5Relevant academic research and scientific papers
Fungal biotransformation of (±)-linalool
Mirata, Marco-Antonio,Wuest, Matthias,Mosandl, Armin,Schrader, Jens
, p. 3287 - 3296 (2008)
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.
One-pot synthesis at room temperature of epoxides and linalool derivative pyrans in monolacunary Na7PW11O39-catalyzed oxidation reactions by hydrogen peroxide
Da Silva, Márcio J.,Teixeira, Milena Galdino,Vilanculo, Castelo B.,Villarreal, Jesus Avendano
, p. 7691 - 7697 (2020/03/10)
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
van Lint, Matthijs J.,Gümüs, Aysegül,Ruijter, Eelco,Faber, Kurt,Orru, Romano V. A.,Hall, Mélanie
, p. 813 - 825 (2019/01/04)
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.).
Two-step, stereoselective synthesis of linalyl oxides by asymmetric allylic O-alkylation
Wan, Kanny K.,Litz, Jonathan P.,Vosburg, David A.
experimental part, p. 2425 - 2428 (2011/02/16)
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.
Gold catalysis in stereoselective natural product synthesis: (+)-linalool oxide, (-)-isocyclocapitelline, and (-)-isochrysotricine
Volz, Frank,Wadman, Sipke H.,Hoffmann-R?der, Anja,Krause, Norbert
experimental part, p. 1902 - 1910 (2009/06/20)
A stereoselective synthesis of the tetrahydrofuran-containing natural products (2S,5R)-(+)-linalool oxide (1), (-)-isocyclocapitelline (2), and (-)-isochrysotricine (3) is reported. Key steps are the copper-mediated SN2′-substitution of proparg
From rational octahedron design to reticulation serendipity. A thermally stable rare earth polymeric disulfonate family with CdI2-like structure, bifunctional catalysis and optical properties
Snejko, Natalia,Cascales, Concepcion,Gomez-Lor, Berta,Gutierrez-Puebla, Enrique,Iglesias, Marta,Ruiz-Valero, Caridad,Monge, M. Angeles
, p. 1366 - 1367 (2007/10/03)
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
Khomenko,Tatarova,Korchagina,Barkhash
, p. 498 - 506 (2007/10/03)
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.
Diastereoselective titanocene-catalyzed oxidative cyclization of bishomoallylic alcohols
Lattanzi,Della Sala,Russo,Scettri
, p. 1479 - 1481 (2007/10/03)
Bishomoallylic alcohols are converted in good yields and diastereoselectivity into tetrahydrofuranols and tetrahydropyranols by Cp2TiCl2/t-butyl hydroperoxide/activated 4? molecular sieves system.
Biotransformation of linalool to furanoid and pyranoid linalool oxides by Aspergillus niger
Demyttenaere, Jan C.R.,Willemen, Hendra M.
, p. 1029 - 1036 (2007/10/03)
Biotransformation of (±)-linalool with submerged shaking cultures of Aspergillus niger, particularly A. niger ATCC 9142, yielded a mixture of cis- and trans-furanoid linalool oxide (yield 15-24%) and cis- and trans-pyranoid linalool oxide (yield 5-9%). Biotransformation of (R)-(-)-linalool with the same strain yielded almost pure trans-furanoid and trans-pyranoid linalool oxide (ee > 95). These conversions were purely biocatalytic, since in acidified water (pH 3.5) almost 50% linalool was recovered unchanged, the rest was lost by evaporation. The biotransformation was also carried out with growing surface cultures.
Palladium(0)-catalysed synthesis of cis- and trans-linalyl oxides
Fournier-Nguefack, Christelle,Lhoste, Paul,Sinou, Denis
, p. 4353 - 4362 (2007/10/03)
Linalyl oxides are obtained from (Z)- or (E)-6,7-dihydroxy-3,7-dimethyl-oct-2-enyl carbonate in the presence of Pd2(dba)3 in association with various ligands.
