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ID 118080
Author
Ohkawachi, Kento Tokushima University
Anzaki, Kaito Tokushima University
Kobayashi, Daishiro Tokushima University
Kyan, Ryuji Fukuyama University
Yasuda, Takuma Kyoto University
Harada, Norio Kyoto University
Inagaki, Nobuya Kyoto University
Keywords
peptide modification
Tyr sulfenylation
Trp sulfenylation
S-protected cysteine sulfoxide
SEAr reaction
Content Type
Journal Article
Description
A tyrosine (Tyr)- or tryptophan (Trp)-selective metal-free C−H sulfenylation reaction using an acid-activated Sacetamidomethyl cysteine (Cys) sulfoxide, Cys(Acm)(O), has been achieved. The dually protonated intermediate produced from the Cys(Acm)(O) under acidic conditions allows the sulfenylation of Tyr. Significantly, the reaction in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) mainly affords a Cys-Tyr-linked peptide even in the presence of Trp residues. In contrast, a Cys-Trplinked peptide was selectively obtained from the reaction in the presence of guanidine hydrochloride (Gn·HCl) under acidic conditions. Established Tyr- and Trp-selective sulfenylation methods were used in the Cys-Tyr stapling and Trp-lipidation of glucagon-like peptides 1 in a one-pot/stepwise manner. Investigation of the mechanism showed that orbital- and charge-controlled reactions are responsible for the Trp and Tyr selectivity, respectively.
Journal Title
Chemistry- A European Journal
ISSN
15213765
NCID
AA11076269
Publisher
Wiley-VCH
Volume
29
Issue
26
Start Page
e202300799
Published Date
2023-03-15
Rights
This is the peer reviewed version of the following article: Ohkawachi, Kento, Anzaki, Kaito, Kobayashi, Daishiro, Kyan, Ryuji, Yasuda, Takuma, Denda, Masaya, Harada, Norio, Shigenaga, Akira, Inagaki, Nobuya, Otaka, Akira, Chem. Eur. J. 2023, 29, 26, e202300799., which has been published in final form at https://doi.org/10.1002/chem.202300799. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
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language
eng
TextVersion
Author
departments
Pharmaceutical Sciences