Serine-Selective Aerobic Cleavage of Peptides and a Protein Using a Water-Soluble Copper–Organoradical Conjugate†
Yohei Seki
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Search for more papers by this authorDr. Kana Tanabe
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Japan Science and Technology Agency (JST), ERATO, Kanai Life Science Catalysis Project, Bunkyo-ku, Tokyo 113-0033 (Japan)
Search for more papers by this authorDr. Daisuke Sasaki
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Japan Science and Technology Agency (JST), ERATO, Kanai Life Science Catalysis Project, Bunkyo-ku, Tokyo 113-0033 (Japan)
Search for more papers by this authorDr. Youhei Sohma
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Japan Science and Technology Agency (JST), ERATO, Kanai Life Science Catalysis Project, Bunkyo-ku, Tokyo 113-0033 (Japan)
Search for more papers by this authorCorresponding Author
Dr. Kounosuke Oisaki
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)Search for more papers by this authorCorresponding Author
Prof. Dr. Motomu Kanai
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Japan Science and Technology Agency (JST), ERATO, Kanai Life Science Catalysis Project, Bunkyo-ku, Tokyo 113-0033 (Japan)
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)Search for more papers by this authorYohei Seki
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Search for more papers by this authorDr. Kana Tanabe
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Japan Science and Technology Agency (JST), ERATO, Kanai Life Science Catalysis Project, Bunkyo-ku, Tokyo 113-0033 (Japan)
Search for more papers by this authorDr. Daisuke Sasaki
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Japan Science and Technology Agency (JST), ERATO, Kanai Life Science Catalysis Project, Bunkyo-ku, Tokyo 113-0033 (Japan)
Search for more papers by this authorDr. Youhei Sohma
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Japan Science and Technology Agency (JST), ERATO, Kanai Life Science Catalysis Project, Bunkyo-ku, Tokyo 113-0033 (Japan)
Search for more papers by this authorCorresponding Author
Dr. Kounosuke Oisaki
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)Search for more papers by this authorCorresponding Author
Prof. Dr. Motomu Kanai
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Japan Science and Technology Agency (JST), ERATO, Kanai Life Science Catalysis Project, Bunkyo-ku, Tokyo 113-0033 (Japan)
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)Search for more papers by this authorThis work was supported by a Grant in-Aid for Young Scientist B and Scientific Research C from JSPS (for K.O.), and ERATO from JST (for M.K.). We thank T. Sonobe, Dr. Y. Aoi, and Dr. S. Kawashima for fruitful discussions.
Abstract
The site-specific cleavage of peptide bonds is an important chemical modification of biologically relevant macromolecules. The reaction is not only used for routine structural determination of peptides, but is also a potential artificial modulator of protein function. Realizing the substrate scope beyond the conventional chemical or enzymatic cleavage of peptide bonds is, however, a formidable challenge. Here we report a serine-selective peptide-cleavage protocol that proceeds at room temperature and near neutral pH value, through mild aerobic oxidation promoted by a water-soluble copper–organoradical conjugate. The method is applicable to the site-selective cleavage of polypeptides that possess various functional groups. Peptides comprising D-amino acids or sensitive disulfide pairs are competent substrates. The system is extendable to the site-selective cleavage of a native protein, ubiquitin, which comprises more than 70 amino acid residues.
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