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

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Citation

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.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0014-A4E9-E
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, (kcat/KM)/kuncat, 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.