An Umpolung Approach for the Chemoselective Arylation of Selenocysteine in Unprotected Peptides.
An Umpolung Approach for the Chemoselective Arylation of Selenocysteine in Unprotected Peptides.
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DOI：
10.1021/jacs.5b05447
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发表时间：
2015-08-12
影响因子：
15
通讯作者：
Buchwald SL
中科院分区：
文献类型：
--
作者：
Cohen DT;Zhang C;Pentelute BL;Buchwald SL
在这里，我们报告了一种未受保护的多肽中硒半胱氨酸的生物偶联策略。这种温和且操作简单的方法利用了氧化的硒半胱氨酸(Se-S键)的亲电性，与亲核的芳基硼酸反应，在数小时内得到芳基化的硒半胱氨酸。该反应可与多种具有不同生物可提官能团的硼酸反应，并且是硒半胱氨酸所特有的。实验证据表明，在氧化条件下，芳基化衍生物比相应的烷基化硒半胱氨酸更稳定。
Herein we report an umpolung strategy for the bioconjugation of selenocysteine in unprotected peptides. This mild and operationally simple approach takes advantage of the electrophilic character of an oxidized selenocysteine (Se–S bond) to react with a nucleophilic arylboronic acid to provide the arylated selenocysteine within hours. This reaction is amenable to a wide range of boronic acids with different biorelevant functional groups and is unique to selenocysteine. Experimental evidence indicates that under oxidative conditions the arylated derivatives are more stable than the corresponding alkylated selenocysteine.