Candida rugosa lipase as an enantioselective catalyst in the esterification of methyl branched carboxylic acids: resolution of rac-3,7-dimethyl-6-octenoic acid (citronellic acid)

Nguyen, Ba‐Vu; Hedenström, Erik

doi:10.1016/s0957-4166(99)00178-0

Cited by 20 publications

(7 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We are currently studying this phenomenon further. Similar observations have recently been made in cases of CRL‐catalysed esterification of diastereomeric dimethyl‐substituted acids 16…”

Section: Resultssupporting

confidence: 83%

“…In this case, the “ E ” value was calculated to be 4.8 from the measured de p and c (54.5% and 40%, respectively) At this stage, for our requirements, the diastereomeric purity at C‐2 was unacceptably low. Candida rugosa lipase (CRL) had recently been used by two of us for successful catalysis of kinetic stereoselective separation by esterification of some dimethylcarboxylic acids, such as 2,6‐dimethyloctanoic acid 16. Therefore, we decided to apply this method to enhance the stereoisomeric purity of the obtained alcohol SR ‐8 .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Syntheses of the Sixteen Stereoisomers of 3,7,11-Trimethyl-2-tridecanol, Including the (2S,3S,7S,11R) and (2S,3S,7S,11S) Stereoisomers Identified as Pheromone Precursors in Females of the Pine SawflyMicrodiprion pallipes(Hymenoptera: Diprionidae)

et al. 2001

Self Cite

View full text Add to dashboard Cite

All sixteen stereoisomers of 3,7,11‐trimethyl‐2‐tridecanol were synthesised in high stereoisomerical purities (> 95%), for use in the identification of the stereoisomers present in females of the pine sawfly Microdiprion pallipes (Fallén) (Hymenoptera: Diprionidae) as the precursor of the actual sex pheromone (which is the propionate), and also for investigation of the biological activities of the esters. The key step in the syntheses was the coupling of each of the enantiomers of cis‐3,4‐dimethyl‐γ‐butyrolactone with each of the four pure stereoisomers of 1‐lithio‐2,6‐dimethyloctanes. The four corresponding alcohols were obtained by lipase‐catalysed (Amano PS) kinetic separation, based on selective acylation of either (2R/S,6S)‐ or (2R/S,6R)‐2,6‐dimethyl‐1‐octanol (obtained from the optically pure enantiomers of citronellal). Additionally, a mixture of the 16 possible stereoisomers of 3,7,11‐trimethyl‐2‐tridecanol was also prepared.

show abstract

Section: Resultssupporting

confidence: 83%

Section: Resultsmentioning

confidence: 99%

Syntheses of the Sixteen Stereoisomers of 3,7,11-Trimethyl-2-tridecanol, Including the (2S,3S,7S,11R) and (2S,3S,7S,11S) Stereoisomers Identified as Pheromone Precursors in Females of the Pine SawflyMicrodiprion pallipes(Hymenoptera: Diprionidae)

et al. 2001

Self Cite

View full text Add to dashboard Cite

show abstract

“…The enantioselective esterification of racemic 2-methylbutanoic acid with 1-hexadecanol yielded an extremely low enantioselectivity (E = 3.6) when catalyzed by CRL, as compared with 2-methylheptanoic acid (E = 23). The steric differences between the methyl and ethyl groups attached to the chiral carbon atom are too small to allow efficient stereochemical recognition (Nguyen and Hedenström 1999). Using the identical aforementioned alcohol and lipase, 2-methylheptanoic acid and 2-methylnonanoic acid, which own a longer alkyl chain length, demonstrated higher enantioselectivity: 126 and 85, respectively (Heinsman et al 2002).…”

Section: Resultsmentioning

confidence: 99%

Enantioselective esterification of (R,S)-2-methylalkanoic acid with Carica papaya lipase in organic solvents

Chang

2011

Biotechnol Lett

View full text Add to dashboard Cite

Isooctane was the best reaction medium for the enantioselective esterification of (R,S)-2-methylalkanoic acid with n-butanol using Carica papaya lipase as catalyst. Increasing linear alkyl-chain length of racemic 2-methylalkanoic acids from ethyl to hexyl increased the enantioselectivity (E) from 2.1 to 98.2 for the esterification of racemic 2-methylalkanoic acids with n-butanol at 35°C. Decreasing reaction temperature from 40 to 20°C increased the enantioselectivity (E) from 14 to 33 for the esterification of racemic 2-methylhexanoic acids with n-butanol. We obtained a maximum enantioselectivity, of E = 24.3, for the enantioselective esterification of racemic 2-methylhexanoic acids with n-butanol in isooctane at water activity 0.33, and at 35°C.

show abstract

“…In spite of the fact that several racemic carboxylic acids have been resolved by lipases, [13][14][15][16][17][18][19][20][21][22] a literature survey shows only few methodologies for the enantioselective esterification of 2-methylbutyric acid. This may be due to the fact that methyl and ethyl moieties have a small size difference making it difficult for the efficient recognition by the lipase.…”

Section: Introductionmentioning

confidence: 99%

Convenient enzymatic resolution of (R,S)‐2‐methylbutyric acid catalyzed by immobilized lipases

et al. 2017

View full text Add to dashboard Cite

The application of several immobilized lipases has been explored in the enantioselective esterification of (R,S)-2-methylbutyric acid, an insect pheromone precursor. With the use of Candida antarctica B, using hexane as solvent, (R)-pentyl 2-methylbutyrate was prepared in 2 h with c 40%, ee p 90%, and E = 35, while Thermomyces lanuginosus leads to c 18%, ee p 91%, and E = 26.The (S)-enantiomer was obtained by the use of Candida rugosa or Rhizopus oryzae (2-h reaction, c 34% and 35%, ee p 75 and 49%, and E = 10 and 4, respectively). Under optimal conditions, the effect of the solvent, the molar ratio, and the nucleophile were evaluated.

show abstract

Candida rugosa lipase as an enantioselective catalyst in the esterification of methyl branched carboxylic acids: resolution of rac-3,7-dimethyl-6-octenoic acid (citronellic acid)

Cited by 20 publications

References 21 publications

Syntheses of the Sixteen Stereoisomers of 3,7,11-Trimethyl-2-tridecanol, Including the (2S,3S,7S,11R) and (2S,3S,7S,11S) Stereoisomers Identified as Pheromone Precursors in Females of the Pine SawflyMicrodiprion pallipes(Hymenoptera: Diprionidae)

Syntheses of the Sixteen Stereoisomers of 3,7,11-Trimethyl-2-tridecanol, Including the (2S,3S,7S,11R) and (2S,3S,7S,11S) Stereoisomers Identified as Pheromone Precursors in Females of the Pine SawflyMicrodiprion pallipes(Hymenoptera: Diprionidae)

Enantioselective esterification of (R,S)-2-methylalkanoic acid with Carica papaya lipase in organic solvents

Convenient enzymatic resolution of (R,S)‐2‐methylbutyric acid catalyzed by immobilized lipases

Contact Info

Product

Resources

About