Copper-Catalyzed Tertiary Alkylative Cyanation for the Synthesis of Cyanated Peptide Building Blocks

Naoki Miwa; Chihiro Tanaka; Syo Ishida; Goki Hirata; Jizhou Song; Takeru Torigoe; Yoichiro Kuninobu; Takashi Nishikata

doi:10.1021/jacs.9b11349

Copper-Catalyzed Tertiary Alkylative Cyanation for the Synthesis of Cyanated Peptide Building Blocks

J Am Chem Soc. 2020 Jan 29;142(4):1692-1697. doi: 10.1021/jacs.9b11349. Epub 2020 Jan 15.

Authors

Naoki Miwa¹, Chihiro Tanaka¹, Syo Ishida¹, Goki Hirata¹, Jizhou Song², Takeru Torigoe^{2

3}, Yoichiro Kuninobu^{2

3}, Takashi Nishikata¹

Affiliations

¹ Graduate School of Science and Engineering , Yamaguchi University , 2-16-1 Tokiwadai , Ube , Yamaguchi 755-8611 , Japan.
² Interdisciplinary Graduate School of Engineering Sciences , Kyushu University , 6-1 Kasugakoen , Kasuga , Fukuoka 816-8580 , Japan.
³ Institute for Materials Chemistry and Engineering , Kyushu University , 6-1 Kasugakoen , Kasuga , Fukuoka 816-8580 , Japan.

PMID: 31939289
DOI: 10.1021/jacs.9b11349

Abstract

In this paper, we report efficient cyanation of various peptides containing the α-bromocarbonyl moiety using a Cu-catalyzed radical-based methodology employing zinc cyanide as the cyanide source. Mechanistic studies revealed that in situ formed CuCN was a key intermediate during the catalytic cycle. Our method could be useful for the synthesis of modified peptides containing quaternary carbons.

Publication types

Research Support, Non-U.S. Gov't