Synthesis and lipase catalyzed hydrolysis of thiolesters of 2‐, 3‐ and 4‐methyl octanoic acids

Sonnet, Philip E.; Baillargeon, Mary Welch

doi:10.1007/bf02535152

Cited by 14 publications

(3 citation statements)

References 18 publications

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“…Medium chain acyl-CoA dehydrogenase was isolated from pig kidney as described previously (Gorelick et al, 1985) and was quantitated using an extinction coefficient of 15.4 mM_1 cm-1 at 446 nm (Thorpe et al, 1979). /?-(+)and S-(-)-3-methyloctanoic acids were generous gifts from Dr. Philip Sonnet (USDA Agricultural Research Service, Philadelphia, PA), with each isomer having >97% configurational purity (Sonnet & Gazzillo, 1990;Sonnet & Baillargeon, 1989). Ferricenium hexafluorophosphate was a gift from Ms. Ruth A. Schaller .…”

Section: Methodsmentioning

confidence: 99%

3-Methylene-octanoyl-CoA and 3-methyl-trans-2-octenoyl-CoA: Two new mechanism-based inhibitors of medium chain acyl-CoA dehydrogenase from pig kidney

Cummings¹,

Thorpe²

1994

Biochemistry

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The medium chain acyl-CoA dehydrogenase catalyzes the FAD-dependent oxidation of a variety of acyl-CoA substrates to the corresponding trans-2-enoyl-CoA thioesters. This work identifies 3-methyleneoctanoyl-CoA and 3-methyl-trans-2-octenoyl-CoA as representatives of a new class of mechanism-based inhibitor of the dehydrogenase. One equivalent of either compound generates an inactive reduced flavin species with low absorption at 450 nm and a shoulder at 320 nm suggestive of an N-5 adduct. Reduction is rapid with the 3-methylene analogue (10/s at 1 degree C), but comparatively slow for 3-methyl-trans-2-octenoyl-CoA (1.1 x 10(-4)/s, under the same conditions). The reduced species is very stable, but the adduct can be slowly displaced with a large excess of octanoyl-CoA. The reduced adduct resists oxidation by the facile one-electron oxidant of the dehydrogenase, ferricenium hexafluorophosphate. Evidence that both isomeric inhibitors generate the same reduced flavin species includes an essentially identical visible spectrum, the same kinetics of displacement using octanoyl-CoA, and the same mixture of products on HPLC after denaturation of the treated enzyme with trichloroacetic acid, methanol, or by boiling. Experiments with the corresponding shorter analogues of these inhibitors, 3-methylenebutanoyl-CoA and 3-methyl-2-butenoyl-CoA confirm and extend these findings. These reduced adducts are less stable, allowing the dehydrogenase to catalyze the interconversion of the unconjugated 3-methylenebutanoyl-CoA to the more stable conjugated 3-methyl-2-butenoyl-CoA thioester (Keq ca. 150). These data suggest that alpha-proton abstraction from the 3-methylene derivatives or gamma-proton removal from the 3-methyl-2-enoyl analogues generates a common carbanionic intermediate which attacks oxidized flavin. As would be expected, the unconjugated 3-methylene derivatives are more effective inhibitors of the dehydrogenase than the thermodynamically more stable 3-methylenoyl analogues.

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Section: Methodsmentioning

confidence: 99%

3-Methylene-octanoyl-CoA and 3-methyl-trans-2-octenoyl-CoA: Two new mechanism-based inhibitors of medium chain acyl-CoA dehydrogenase from pig kidney

Cummings¹,

Thorpe²

1994

Biochemistry

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“…12 Various methods for the racemic synthesis of ethyl 4-methyloctanoate (1) and its acid derivative 2 have been documented in the literature. 4,[13][14][15][16][17] Most of the asymmetric syntheses for (R)-and (S)-ethyl 4methyloctanoate (1) and its acid 2 described employed either use of chromatographic diastereomeric separation of phenylethylamides 18 or phenylglycinol amides, 19 chiral citronellol as starting material or enzymatic resolution. [20][21][22] More recently, Guerrero and co-worker reported the asymmetric synthesis of (R)and (S)-4-methyloctanoic acid (2) via chirality induction through Myers alkylation reaction as key step.…”

Section: Introductionmentioning

confidence: 99%

Concise asymmetric syntheses of (S)-ethyl 4-methyloctanoate and its acid: aggregation pheromones of rhinoceros beetles of the genus Oryctes

Pandey¹,

Prakash²

2018

Arkivoc

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A concise stereoselective approach to the asymmetric syntheses of (S)-ethyl 4-methyloctanoate and its acid, main aggregation pheromones of the genus Oryctes and an important fragrance compounds, is described. The synthesis utilizes the organocatalyzed MacMillan's cross aldol reaction as key step. The synthetic approach outlined permits synthesis of a variety of enantiopure branched methyl unsaturated and saturated fatty acids.

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“…The above presented methods involve not readily available substrates (13,14), starting materials already lacking the methyl group (15,16), or the use of organometallic syntheses (1,6,7,12) unsuitable for large-scale preparations.…”

Section: Introductionmentioning

confidence: 99%

Efficient Synthesis of (±)-4-Methyloctanoic Acid, Aggregation Pheromone of Rhinoceros Beetles of the Genus Oryctes (Coleoptera: Dynastidae, Scarabaeidae)

Ragoussis

Giannikopoulos

Skoka

et al. 2007

J. Agric. Food Chem.

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(+/-)-4-Methyloctanoic acid and its ethyl ester are aggregation pheromones of many rhinoceros beetles of the genus Oryctes and are investigated for the control of these pests by olfactory trapping. A simple, economical, and high-yield (>50%) synthesis of (+/-)-4-methyloctanoic acid and its ethyl ester is presented starting from n-hexanal. The key step in this sequence is an orthoester Claisen rearrangement for the elongation of the carbon chain by two.

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Synthesis and lipase catalyzed hydrolysis of thiolesters of 2‐, 3‐ and 4‐methyl octanoic acids

Cited by 14 publications

References 18 publications

3-Methylene-octanoyl-CoA and 3-methyl-trans-2-octenoyl-CoA: Two new mechanism-based inhibitors of medium chain acyl-CoA dehydrogenase from pig kidney

3-Methylene-octanoyl-CoA and 3-methyl-trans-2-octenoyl-CoA: Two new mechanism-based inhibitors of medium chain acyl-CoA dehydrogenase from pig kidney

Concise asymmetric syntheses of (S)-ethyl 4-methyloctanoate and its acid: aggregation pheromones of rhinoceros beetles of the genus Oryctes

Efficient Synthesis of (±)-4-Methyloctanoic Acid, Aggregation Pheromone of Rhinoceros Beetles of the Genus Oryctes (Coleoptera: Dynastidae, Scarabaeidae)

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