Assignment of the Nitrogen-15 Nuclear Magnetic Resonances of Biotin and Unequivocal Synthesis of (+)-[1-^(15)N]Biotin
Abstract
(+)-Biotin (1) is an essential cofactor for several enzymes involving carboxylation and carbonyl-exchange reactiom It participates in the fixation, activation, and transfer of carbon dioxide by forming an N-carboxybiotin in which N1 was established as the point of attachment. The chemical reactivity of the the two ureido nitrogens of 1 is strikingly different. Thus, N1-and N3-acylated products in an 100:7 ratio resulted from the reaction of methyl chloroformate with biotin methyl ester. The low proportion of the N3 product was attributed to steric hindrance to the approach of the reagent to N3 because of the presence of the carboxylbutyl side chain. A similar argument was employed to account for the difference in exchange rates for the ureido protons with ethanol.
Additional Information
© 1981 American Chemical Society. Received December 24, 1980. This work was supported at the University of Illinois by Research Grants CHE-76-23543 and CHE-79-22001 from the National Science Foundation and at the California Institute of Technology by the National Science Foundation and the US. Public Health Service, Research Grant GM-11072 from the Division of General Medical Sciences. We thank Dr. Janis Vasilevskis, Dr. Milan B. Uskoković, and Stanley D. Hutchings of the Chemical Research Department, Hoffmann-LaRoche, Inc., Nutley, NJ, for their generous help in materials and methodology.Additional details
- Eprint ID
- 60795
- DOI
- 10.1021/ja00406a054
- Resolver ID
- CaltechAUTHORS:20151006-073240480
- CHE-76-23543
- NSF
- CHE-79-22001
- NSF
- GM-11072
- U.S. Public Health Service (USPHS)
- Created
-
2015-10-06Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Gates and Crellin Laboratories of Chemistry
- Other Numbering System Identifier
- 6345