A Catalytic Enantioselective Route to Hydroxy-Substituted Quaternary Carbon 
Centers: Resolution of Tertiary Aldols with a Catalytic Antibody

List, Benjamin; Shabat, Doron; Zhong, Guofu; Turner, James M.; Li, Anthony; Bui, Tommy; Anderson, James; Lerner, Richard A.; Barbas III, Carlos F.

doi:10.1021/ja991507g

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A Catalytic Enantioselective Route to Hydroxy-Substituted Quaternary Carbon Centers: Resolution of Tertiary Aldols with a Catalytic Antibody

List, B., Shabat, D., Zhong, G., Turner, J. M., Li, A., Bui, T., et al. (1999). A Catalytic Enantioselective Route to Hydroxy-Substituted Quaternary Carbon Centers: Resolution of Tertiary Aldols with a Catalytic Antibody. Journal of the American Chemical Society, 121(32), 7283-7291. doi:10.1021/ja991507g.

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Item Permalink: https://hdl.handle.net/11858/00-001M-0000-0014-A4E9-E Version Permalink: https://hdl.handle.net/21.11116/0000-0007-60E1-E

Genre: Journal Article

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Creators:
List, Benjamin¹, Author
Shabat, Doron¹, Author
Zhong, Guofu¹, Author
Turner, James M.¹, Author
Li, Anthony¹, Author
Bui, Tommy¹, Author
Anderson, James¹, Author
Lerner, Richard A.¹, Author
Barbas III, Carlos F.¹, Author

Affiliations:
1The Skaggs Institute for Chemical Biology and the Department of Molecular Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA., ou_persistent22

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Abstract: Aldolase antibody 38C2-catalyzed resolutions of tertiary aldols were studied. Tertiary aldols proved to be very good substrates for antibody catalyzed retro-aldol reactions. The catalytic proficiency, (k_cat/K_M)/k_uncat, of the antibody for these reactions was on the order of 10¹⁰ M^-1. A fluorogenic tertiary aldol allowed for the quantitative study of enantiomeric excess as a function of reaction conversion, revealing an E value of ca. 160 in this case. Study of a variety of substrates demonstrated that antibody-catalyzed retro-aldolization provides rapid entry to highly enantiomerically enriched tertiary aldols, typically >95% ee, containing structurally varied, heteroatom-substituted quaternary carbon centers. The utility of this approach to natural product syntheses has been demonstrated with the syntheses of (+)-frontalin, the side chain of Saframycin H, and formal syntheses of (+)- and (−)-mevalonolactone.

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Language(s): eng - English

Dates: Submitted: 1999-05-06Published Online: 1999-07-28Date issued: 1999-08-01

Publication Status: Issued

Pages: 9

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Rev. Type: Peer

Identifiers: DOI: 10.1021/ja991507g

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Title: Journal of the American Chemical Society

Other : JACS

Abbreviation : J. Am. Chem. Soc.

Source Genre: Journal

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Publ. Info: Washington, DC : American Chemical Society

Pages: - Volume / Issue: 121 (32) Sequence Number: - Start / End Page: 7283 - 7291 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870