Tam J P, Lu Y A, Liu C F, Shao J
Department of Microbiology and Immunology, Vanderbilt University, Nashville, TN 37232-2363, USA.
Proc Natl Acad Sci U S A. 1995 Dec 19;92(26):12485-9. doi: 10.1073/pnas.92.26.12485.
We describe an approach to the synthesis of peptides from segments bearing no protecting groups through an orthogonal coupling method to capture the acyl segment as a thioester that then undergoes an intramolecular acyl transfer to the amine component with formation of a peptide bond. Two orthogonal coupling methods to give the covalent ester intermediate were achieved by either a thiol-thioester exchange mediated by a trialkylphosphine and an alkylthiol or a thioesterification by C alpha-thiocarboxylic acid reacting with a beta-bromo amino acid. With this approach, unprotected segments ranging from 4 to 37 residues were coupled to aqueous solution to give free peptides up to 54 residues long with high efficiency.
我们描述了一种通过正交偶联方法从无保护基团的片段合成肽的方法，该方法将酰基片段捕获为硫酯，然后硫酯进行分子内酰基转移至胺组分，形成肽键。通过三烷基膦和烷基硫醇介导的硫醇-硫酯交换或α-硫代羧酸与β-溴代氨基酸的硫酯化反应，实现了两种生成共价酯中间体的正交偶联方法。采用这种方法，将4至37个残基的未保护片段与水溶液偶联，高效得到了长达54个残基的游离肽。
