Preparation of (R)-(+)-7-oxabicyclo[2.2.1]hept-5-ene-exo-2-carboxylic acid, a precursor to substrates for the ring opening metathesis polymerization

Tetrahedron Letters

Volumn 37, Issue 49, 1996, Pages 8853-8856

  Schueller, Christine M ^a   Manning, David D ^a   Kiessling, Laura L ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

NORBORNENE DERIVATIVE; TRIACYLGLYCEROL LIPASE;

ARTICLE; CANDIDA; CARBOHYDRATE SYNTHESIS; DRUG SYNTHESIS; ENANTIOMER; ENZYME ACTIVITY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYMERIZATION; REACTION ANALYSIS;

EID: 0030566838     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(96)02061-8     Document Type: Article

References (34)

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26. 12. Several lipases were found to be inactive or afford low enantioselectivity in the hydrolysis of (±)1. Lipases derived from Aspergillus niger, Mucor miehei, Pseudomonas sp. were obtained from Amano and found to be unsuitable, as were lipases supplied by Aldrich Chemical Co. from Porcine Pancreas and Candida Rugosa. 13. Resolution of (R)-(+)-7-oxabicyclo[2.2.1] hept-5-ene-exo-2-carboxylic acid methyl ester, 1R. Racemic 7-oxabicyclo[2.2.1]hept-5-ene-exo-2-carboxylic acid methyl ester (300 mg, 1.95 mmol) and Candida Rugosa lipase (300 mg) were dissolved in 0.1 M pH 7.0 phosphate buffer (45 mL), and the mixture was stirred at 32 °C for 7 hours. The reaction was cooled to room temperature and solid sodium bicarbonate was added until the pH of the solution was approximately 8. The unreacted ester was extracted from the reaction mixture with dichloromethane (4 × 50 mL). The reaction mixture was acidified with 1 M HCl and the carboxylic acid was extracted with ethyl acetate (6 × 50 mL). The dichloromethane extracts were dried with anhydrous magnesium sulfate and concentrated under reduced pressure to yield 1R (110 mg, 37% yield, 92% ee). The ethyl acetate extracts were dried with anhydrous magnesium sulfate and concentrated under reduced pressure to afford 2S (169 mg, 62% yield).
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28. 3): δ 6.40 (dd, J = 16.0, 1.5 Hz, 1H), 6.38 (dd, J = 16.0, 1.5 Hz, 1H), 5.23 (br s, 1H), 5.11 (br d, J = 4.0 Hz, 1H), 2.48 (dd, J = 8.5, 3.9 Hz, 1H), 2.17 (ddd, J = 11.6, 4.0, 3.9 Hz, 1H), 1.60 (dd, J = 11.6, 8.5 Hz, 1H).
29. D= +27.6° (EtOH).
30. 17. Ahmed, S. N.; Kazlauskas, R. J.; Morinville, A. H.; Grochulski, P.; Schrag, J. D.; Cygler, M. Biocatalysis 1994, 9, 209-225.
31. 3 307.0].
32. 19. The enantiomeric excess of the pentafluorophenyl ester 3 was determined to be greater than 99% by chiral HPLC using a Regis (R,R)-WHELK-O column, 20 cm × 4.6 mm I.D. (0.3% isopropanol in hexane eluent).
33. 20. The synthesis of 4 will be described elsewhere: D. D. Manning, L. L. Kiessling, in preparation.
34. -1.