An antibody-catalyzed [2,3]-elimination reaction

Journal of the American Chemical Society

Volumn 118, Issue 46, 1996, Pages 11686-11687

  Yoon, Seung Soo ^a,b   Oei, Yoko ^a   Sweet, Elizabeth ^a   Schultz, Peter G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b Sungkyunkwan University   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

ANTIBODY; STYRENE DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029997136     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962257w     Document Type: Article

References (32)

1. (a) Andrews, G. D.; Smith, G. D.; Young, I. G. Biochemistry 1973, 12, 3492.
2. (b) Gorisch, H. Biochemistry 1978, 17, 3700.
3. (c) Guilford, W. J.; Copley, S. D.; Knowles, J. R. J. Am. Chem. Soc. 1987, 109, 5013.
4. (d) Laschat, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 289.
5. (e) Oikawa, H.; Katayama, K.; Suzuki, Y.; Ichihara, A. J. Chem. Soc., Chem. Commun. 1995, 1321.
6. (a) Hilvert, D.; Hill, K. W.; Nared, K. D.; Auditor, M. J. Am. Chem. Soc. 1989, 111, 9261.
7. (b) Braisted, A. C.; Schultz, P. G. J. Am. Chem. Soc. 1990, 112, 7430.
8. (c) Hilvert, D.; Carpenter, S. H.; Nared, K. D.; Auditor, M. Proc. Natl. Acad. Sci. U.S.A. 1988, 85, 4953.
9. (d) Jackson, D. Y.; Jacobs, J. W.; Sugasawara, R.; Reich, S. H.; Bartlett, P. A.; Schultz, P. G. J. Am. Chem. Soc. 1988, 110, 4841.
10. (e) Braisted, A. C.; Schultz, P. G. J. Am. Chem. Soc. 1994, 116, 2211.
11. (f) Gouverneur, V. E.; Houk, K. N.; Pascul-Teresa, B. D.; Beno, B.; Janda, K. D.; Lerner, R. A. Science 1993, 262, 204.
12. (g) Yli-Kauhaluoma, J. T.; Ashley, J. A.; Lo, C.-H.; Tucker, L.; Wolfe, M. M.; Janda, K. D. J. Am. Chem. Soc. 1995, 117, 7041.
13. (h) Suckling, C. J.; Tedford, M. C.; Bence, L. M.; Irvine, J. I.; Stimson, W. H. J. Chem. Soc., Perkin Trans. I 1993, 1925.
14. Cope, A. C.; Foster, T. T.; Towel, P. H. J. Am. Chem. Soc. 1949, 71, 3939.
15. Kwart, H. Acc. Chem. Res. 1982, 15, 401.
16. (a) Lewis, C.; Kramer, T.; Robinson, S.; Hilvert, D. Nature 1991, 253, 1019.
17. (b) Lewis, C.; Paneth, P.; O'Leahy, M. H.; Hilvert, D. J. Am. Chem. Soc. 1993, 115, 1410.
18. Hapten 3 was synthesized from the commercially available starting material, 2(5H)-furanone. A palladium-catalyzed coupling reaction of starting material with 4-iodoanisole followed by hydrogenation, Grignard reaction with methyl magnesium bromide, and acid-catalyzed cyclization in the presence of p-toluenesulfonic acid afforded 2-dimethyl-4-(4′-methoxyphenyl)tetrahydrofuran. Removal of the methyl protecting group of phenol with sodium hydride and ethanethiol, followed by Mitsunobu alkylation with ethyl 6-hydroxyhexanoate and subsequent hydrolysis of the ethyl ester, provided hapten 3. Substrate 1 was synthesized by an ethyl-(3-dimethylaminopropyl)dicarbodiimide coupling reaction of 4-methoxyphenylacetic acid with dimethylamine, followed by reduction with borane-THF complex and oxidation with m-chloroperbenzoic acid.
19. Jacobs, J. W. Ph.D. Thesis, University of California, Berkeley, CA 94720.
20. (a) Kronvall, G.; Grey, H.; Williams, R. J. Immunol. 1972, 105, 1116.
21. (b) Harlow, E.; Lane, D. Antibodies. A Laboratory Manual; Cold Spring Harbor Laboratory: New York, 1988.
22. HPLC assays were carried out with a Microsorb C18 reverse-phase column with a gradient starting a 10% acetonitrile in water and increasing to 100% acetonitrile over 25 min. Product formation was monitored at 270 nm and quantitated against the internal standard, 4-(N-ethylamido)-benzoic acid methyl ester. The retention time of the product formed in the catalyzed and uncatalyzed reaction is identical with that of commercially available 4-methoxystyrene.
23. m + [1]) using the Levenverg-Marquart algorithm of the Kaleida Graph computer program (Abelbeck software). Antibody concentrations were 4.3 μM in binding sites.
24. 0 = initial velocity in the absence of inhibitor: Williams, J. W.; Morrison, J. F. Methods Enzymol. 1979, 63, 437.
25. 4, reductive dimethylation, and oxidation with m-chloroperbenzoic acid provided the deuterated substrate.
26. kcatD is uncorrectcd for secondary isotope effects.
27. D are 2.52 and 2.54 in dioxane and DMF, respectively.
28. 18
29. Dimroth, K.; Reichardt, C.; Siepmann, T.; Bohlmann, F. Ann. Chem. 1963, 661, 1.
30. (a) Chiao, W.-B.; Saunders, W. H., Jr. J. Am. Chem. Soc. 1978, 100, 2802.
31. (b) Cram, D. J.; Sahyun, M. R.; Knox, G. R. J. Am. Chem. Soc. 1962, 84, 1734.
32. Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry; 3rd ed.; Harper & Row: New York, 1987; p 209.