Preparation of Aroma Compounds by Microbial Transformation of Isophorone with<i>Aspergillus niger</i>

Mikami, Yoichi; Fukunaga, Yumiko; Arita, Masatoshi; Obi, Yukiteru; Kisaki, Takuro

doi:10.1080/00021369.1981.10864606

Cited by 5 publications

(4 citation statements)

References 2 publications

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“…Analysis of the MS fragmentation patterns of the three products suggested they were isophorone oxide ( 8a ), 4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one ( 8b , 4-hydroxyisophorone), and 3-hydroxymethyl-5,5-dimethyl-2-cyclohexen-1-one ( 8c , 7-hydroxyisophorone) (Figure S4e in the Supporting Information and Scheme ). , The results from a selection of other smaller monoterpenoid organic molecules are discussed in the next section.…”

Section: Resultsmentioning

confidence: 99%

Improving the Monooxygenase Activity and the Regio- and Stereoselectivity of Terpenoid Hydroxylation Using Ester Directing Groups

et al. 2016

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The monooxygenase enzyme CYP101B1, from Novosphingobium aromaticivorans DSM12444, binds norisoprenoids more tightly than monoterpenoids and oxidized these substrates with high regioselectivity. Ionols bound less tightly to CYP101B1 than ionones, but the levels of product formation remained high and the selectivity of oxidation was similar to that observed for the parent norisoprenoid. The structurally related sesquiterpene lactone (+)-sclareolide (9) was stereoselectively hydroxylated by CYP101B1 to (S)-(+)-3-hydroxysclareolide (9a). The turnover of monoterpenoid derivatives showed low levels of product formation and selectivity despite promising binding data. CYP101B1 catalyzed the selective oxidation of (1R)-(−)-nopol (14) and cis-jasmone (15), generating >90% (1R)-(−)-5-hydroxynopol (14a) and 4-hydroxy-cis-jasmone (15a), respectively. To develop strategies for the efficient and selective oxidation of monoterpenoid-based substrates using CYP101B1, we investigated the binding and catalytic properties of terpenoid acetates. The ester functional group of these substrates mimicked the carbonyl moiety of norisoprenoids and anchored the monoterpenoid acetates in the active site of CYP101B1 with high affinity for the monoterpenoid acetates. The oxidation of these substrates by CYP101B1 occurred with product formation rates in excess of 1000 min–1 and total turnover numbers of greater than 5000 being observed in all but one instance. Critically, the oxidations were regioselective, with several being stereoselective. (−)-Myrtenyl acetate (20) was oxidized regioselectively (>95%) to yield cis-4-hydroxy-myrtenyl acetate (20a), which was further oxidized to 4-oxomyrtenyl acetate (20b) using a whole-cell system, providing a biocatalytic route to generate intermediates used in the production of cannabinoid derivatives. The ester carbonyl moiety could also be used as a directing group also to enhance the activity and control the selectivity of P450-catalyzed reactions; for example, the turnover of l-(−)-bornyl acetate (18) and isobornyl acetate (19) by CYP101B1 generated 9-hydroxybornyl acetate (18a) and 5-exo-hydroxyisobornyl acetate (19a), respectively, as the sole products.

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Section: Resultsmentioning

confidence: 99%

Improving the Monooxygenase Activity and the Regio- and Stereoselectivity of Terpenoid Hydroxylation Using Ester Directing Groups

et al. 2016

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“…Silica gel chromatography purification (cyclohexane with increasing amounts of EtOAc) afforded 6 and 7 of sufficient purity. Compound 7 was identified by comparison of its 1 H NMR spectrum with literature data . 1 H NMR (400 MHz, CDCl 3 ): δ =6.15 (s, 1 H), 4.23 (s, 2 H), 2.27 (s, 2 H), 2.14 (s, 2 H), 1.05 ppm (s, 6 H).…”

Section: Methodsmentioning

confidence: 99%

One‐Pot Biocatalytic Double Oxidation of α‐Isophorone for the Synthesis of Ketoisophorone

et al. 2017

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The chemical synthesis of ketoisophorone, a valuable building block of vitamins and pharmaceuticals, suffers from several drawbacks in terms of reaction conditions and selectivity. Herein, the first biocatalytic one‐pot double oxidation of the readily available α‐isophorone to ketoisophorone is described. Variants of the self‐sufficient P450cam‐RhFRed with improved activity have been identified to perform the first step of the designed cascade (regio‐ and enantioselective allylic oxidation of α‐isophorone to 4‐hydroxy‐α‐isophorone). For the second step, the screening of a broad panel of alcohol dehydrogenases (ADHs) led to the identification of Cm‐ADH10 from Candida magnoliae. The crystal structure of Cm‐ADH10 was solved and docking experiments confirmed the preferred position and geometry of the substrate for catalysis. The synthesis of ketoisophorone was demonstrated both as a one‐pot two‐step process and as a cascade process employing designer cells co‐expressing the two biocatalysts, with a productivity of up to 1.4 g L−1 d−1.

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“…The authors have been studying the production of tobacco flavoring and focused on the microbial conversion for this purpose,' since, microbial conversion normally creates this product with a naturally occurring structure. Mikami et al have reported on the bioconversion of p-ionone by Aspergillus niger JTS 19 1 .2- 5 They attempted the screening of microorganisms capable of ionone conversion, and found that A . niger JTS191 was capable of converting p-ionone to a mixture of its derivatives.…”

Section: Introductionmentioning

confidence: 99%

Microbial conversion of β‐ionone by immobilized Aspergillus niger in the presence of an organic solvent

Sode

Karube

Araki

et al. 1989

Biotech & Bioengineering

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Aspergillus niger JTS191 was capable of the conversion of beta-ionone to a mixture of its derivatives that is utilized to an essential oil of tobacco. The authors attempted this microbial conversion in the presence of an organic solvent to improve its reaction rate. The addition of isooctane accelerated the microbial conversion of beta-ionone. It took three days to complete the reaction whereas without isooctane it took more than six days. The addition of isooctane also improved the resistance of A. niger to the antifungal property of beta-ionone. A. niger pellets were immobilized in hydrophobic polymer, PU-3, and applied for the microbial conversion of beta-ionone. Further improvement of the resistance to the antifungal property of beta-ionone was achieved by immobilization. PU-3 immobilized A. niger was repeatedly used for microbial conversion of beta-ionone in the presence of isooctane for more than 480 hours.

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Preparation of Aroma Compounds by Microbial Transformation of Isophorone withAspergillus niger

Cited by 5 publications

References 2 publications

Improving the Monooxygenase Activity and the Regio- and Stereoselectivity of Terpenoid Hydroxylation Using Ester Directing Groups

Improving the Monooxygenase Activity and the Regio- and Stereoselectivity of Terpenoid Hydroxylation Using Ester Directing Groups

One‐Pot Biocatalytic Double Oxidation of α‐Isophorone for the Synthesis of Ketoisophorone

Microbial conversion of β‐ionone by immobilized Aspergillus niger in the presence of an organic solvent

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