Insutitute of Biomedical Sciences and Graduate School of Pharmaceutical Sciences, Tokushima University, Tokushima 770-8505, Japan.
Org Biomol Chem. 2020 Nov 14;18(42):8638-8645. doi: 10.1039/d0ob01475c. Epub 2020 Aug 28.
Ring-opening by CuSO of a 1,3-thiazolidine carbonyl structure (Thz) as an N-terminal cysteine (Cys) residue revealed that an intramolecular S-acetamidomethyl cysteine (Cys(Acm)) can also be deprotected with concomitant formation of a disulphide bond connecting the two Cys residues. A mechanistic study on the disulphide formation led to a general protocol for deprotection of the S-Acm group by CuSO and a 1,2-aminothiol under aerobic conditions. Application of this new deprotection reaction allowed for the synthesis of Apamin, a peptide with two-disulphides in a one-pot/stepwise disulphide-bridging procedure.
通过 CuSO 打开 1,3-噻唑烷羰基结构 (Thz) 作为 N-端半胱氨酸 (Cys) 残基，揭示了一个分子内 S-乙酰氨甲基半胱氨酸 (Cys(Acm)) 也可以被保护，同时形成连接两个 Cys 残基的二硫键。对二硫键形成的机制研究导致了一种通用的保护基 S-Acm 组的方案，通过 CuSO 和 1,2-氨硫醇在有氧条件下进行。这种新的保护反应的应用允许合成 Apamin，一种具有两个二硫键的肽，在一锅/分步二硫键桥接程序中。
