Chemoenzymatic synthesis of some macrocyclic C13-lactones

Maguire, Nuala M.; Mahon, Mary F.; Molloy, Kieran C.; Read, G.; Roberts, Stanley M.; Šik, Vladimír

doi:10.1039/p19910002054

Cited by 17 publications

(13 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Methyl (11S,12S)-epoxy-13S-hydroxy-9Z-octadecenoate 2 {[α] D 25 +4.5°(c 1.0, CHCl 3 ), the erythro isomer, 84% de} was the major product. The erythro assignment of compound 2 was supported by the 1 H NMR shift of the hydroxyl proton of C13 at δ H 4.01 ppm [12], and the coupling constant J = 3.21 Hz confirmed that the adjacent proton of alcohol (C13) and epoxy proton at C12 were in the erythro configuration [14]. On the other hand, the titaniumcatalysed epoxidation of methyl 13S-HODE with TBHP in the presence of D-DIPT afforded methyl (11R,12R)-epoxy-13S-octadecenoate 3 {[α] D 25 +2.1°(c 1.0, CHCl 3 ), the threo isomer, 76% de} as a predominant product.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Asymmetric Sharpless epoxidation of 13S‐hydroxy‐ 9Z, 11E‐octadecadienoic acid (13S‐HODE)

Omar

Moynihan

Hamilton

2003

Euro J Lipid Sci & Tech

View full text Add to dashboard Cite

Asymmetric Sharpless epoxidation of 13S-hydroxy-9Z,11E-octadecadienoic acid (13S-HODE)The asymmetric Sharpless epoxidation of methyl 13S-hydroxy-9Z,11E-octadecadienoate (13S-HODE, 1) with tert-butyl hydroperoxide (TBHP) catalysed by titanium tetraisopropoxide {Ti( i OPr) 4 } in the presence of L(+)-diisopropyl tartrate (L-DIPT) gave methyl 13S-hydroxy-11S,12S-epoxy-9Z-octadecenoate 2 (erythro isomer) in 84% diastereomeric excess (de). The epoxidation of 1 with TBHP catalysed by Ti( i OPr) 4 in the presence of D(-)-DIPT yielded methyl 13S-hydroxy-11R,12R-epoxy-9Z-octadecenoate (threo isomer) 3 in 76% de.

show abstract

Section: Resultsmentioning

confidence: 99%

“…13S-HODE (1) was prepared from linoleic acid (Sigma, Dorset, UK) through a chemoenzymatic procedure [12] followed by methylation with diazomethane. 13S-HODE 1 (100 mg, 0.32 mmol) was transferred into a pear-shaped flask containing freshly distilled dichloromethane (10 ml) and molecular sieves (4 Å, 10 mg, Sigma).…”

Section: Methodsmentioning

confidence: 99%

Asymmetric Sharpless epoxidation of 13S‐hydroxy‐ 9Z, 11E‐octadecadienoic acid (13S‐HODE)

Omar

Moynihan

Hamilton

2003

Euro J Lipid Sci & Tech

View full text Add to dashboard Cite

show abstract

“…In the field of lactones, Maguire et al ( 1991 ) achieved the reaction of lactonization of the linoleic acid employing an immobilized soybean lipoxygenäse leading to a C13 macrocyclic lactone as a product. Willets e/ai.…”

Section: Other Oxidoreductasesmentioning

confidence: 99%

Enzymes and food flavor‐A review

Christen¹,

Munguía

1994

Food Biotechnology

View full text Add to dashboard Cite

The use of enzymes in flavor generation in food technology is reviewed. In the first part, important products derived from natural macromolecules present in foods such as fats, proteins, nucleic acids and flavor precursors are discussed in terms of the enzymes involved in the reactions and the relation of the products with flavor. Enzymes that are used to eliminate natural or process induced off-flavors are also discussed. In the second part, the use of enzymes for the direct synthesis of flavoring compounds is presented.

show abstract

“…Many studies have already reported on immobilization of enzymes related to the oxylipin pathway, such as the immobilization of LOX, using the adsorption method, on glutenin and gliadin as well as on glass and glass wool [6,7]. Several methods were developed to covalently immobilize LOX with cyanogen bromide (CNBr), glutardialdehyde (GDA) and oxirane acrylic beads; however, these methods failed to stabilize the enzymes [8,9]. Rice husk silica is known to be an efficient matrix for protein immobilization, owing to its nanoporous structure (pore size approximately 4-5 nm) and the availability of functional groups on the silica surface [10][11][12].…”

Section: Introductionmentioning

confidence: 99%

Covalent immobilization of oxylipin biosynthetic enzymes on nanoporous rice husk silica for production of cis(+)-12-oxophytodienoic acid

Han²,

Cho

et al. 2017

Artificial Cells, Nanomedicine, and Biotechnology

View full text Add to dashboard Cite

Soybean lipoxygenase, recombinant rice allene oxide synthase-1 and rice allene oxide cyclase were covalently immobilized on nanoporous rice husk silica using two types of linkers: glutardialdehyde and polyethylene glycol. The immobilization efficiency achieved using glutardialdehyde-linked rice husk silica was higher than that achieved using polyethylene glycol-linked rice husk silica (50-92% and 25-50%, respectively). Immobilization on both types of matrices significantly decreased the specific activities of the immobilized enzymes. Solid-phase reaction yields of the enzymes were determined relative to the yields observed for the solution-phase reactions. Yields of the solid-phase reactions catalyzed by immobilized soybean lipoxygenase, rice allene oxide synthase-1, and rice allene oxide cyclase ranged from 50% to 230% and were dependent on both the enzymes and linkers used. Production of cis(+)-12-oxophytodienoic acid from α-linolenic acid by consecutive reactions using all three enzymes in a co-immobilization system resulted in 83.6% and 65.1% yields on glutardialdehyde-linked and epichlorohydrin-polyethylene glycol-linked rice husk silica, respectively. Our results suggest that immobilization of biosynthetic enzymes of the octadecanoid pathway on rice husk silica may be an efficient method for the in vitro production of oxylipins. Additionally, enzyme immobilizations on rice husk silica matrices may be more broadly applicable for producing physiologically important compounds in other biosynthetic pathways.

show abstract

Chemoenzymatic synthesis of some macrocyclic C13-lactones

Abstract: Oxidation of linoleic acid using immobilised soybean lipoxygenase-I gave (1 3s) -1 3-hydroxyoctadeca-9,11 -dienoic acid 1 : lactonisation and Diels-Alder reactions involving this hydroxy acid have been explored.

Cited by 17 publications

References 9 publications

Asymmetric Sharpless epoxidation of 13S‐hydroxy‐ 9Z, 11E‐octadecadienoic acid (13S‐HODE)

Asymmetric Sharpless epoxidation of 13S‐hydroxy‐ 9Z, 11E‐octadecadienoic acid (13S‐HODE)

Enzymes and food flavor‐A review

Covalent immobilization of oxylipin biosynthetic enzymes on nanoporous rice husk silica for production of cis(+)-12-oxophytodienoic acid

Contact Info

Product

Resources

About