Shabani Sadegh, Hutton Craig A
School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne, Victoria, 3010, Australia.
Chem Commun (Camb). 2021 Feb 25;57(16):2081-2084. doi: 10.1039/d0cc07747j. Epub 2021 Jan 29.
Macrolactonisation of peptides to generate cyclic depsipeptides is often challenging due to the low nucleophilicity of hydroxyl groups, epimerisation, cyclodimerisation, and potential acyl transfer reactions of the ester. Herein, we report a novel macrolactonisation strategy employing a Ag(i)-promoted conversion of peptide thioamides to isoimide intermediates, which undergo site-selective intramolecular acyl transfer to serine/threonine side chains to generate the macrolactone.
由于羟基的亲核性低、差向异构化、环二聚化以及酯的潜在酰基转移反应，肽的大环内酯化以生成环缩肽通常具有挑战性。在此，我们报道了一种新型的大环内酯化策略，该策略采用银（I）促进的肽硫代酰胺转化为异亚胺中间体，这些中间体经历位点选择性分子内酰基转移至丝氨酸/苏氨酸侧链以生成大环内酯。
