Cysteine as a sustainable sulfur reagent for the protecting-group-free synthesis of sulfur-containing amino acids: biomimetic synthesis of L-ergothioneine in water
Cysteine as a sustainable sulfur reagent for the protecting-group-free synthesis of sulfur-containing amino acids: biomimetic synthesis of L-ergothioneine in water
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DOI：
10.1039/c2gc35367a
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发表时间：
2012-01-01
期刊：
影响因子：
9.8
通讯作者：
Yadan, Jean-Claude
中科院分区：
文献类型：
--
作者：
Erdelmeier, Irene;Daunay, Sylvain;Yadan, Jean-Claude
生物质半胱氨酸被用作合成稀有含硫氨基酸的可持续硫源，如可能是一种新维生素的L-麦角硫氨酸(4)和各种L-或D-2-硫代组氨酸化合物。在水中这一简单的一锅两步程序的关键是溴诱导的区域选择性引入半胱氨酸，然后在硫醇存在下进行新的热裂解反应，这是危险红磷的更安全的替代品。除了避免危险的硫磺试剂外，新的无保护基方法与所描述的步骤相比，大大减少了步骤总数。通过对四种原位生成溴或高溴的替代方法的评价，解决了主要缺点，即将液态溴作为水中的活化剂和氧化剂，并首次描述了令人鼓舞的结果。
Biomass-derived cysteine was used as a sustainable sulfur source for the synthesis of rare sulfur-containing amino acids, such as L-ergothioneine (4), which might be a new vitamin, and various L- or D-2-thiohistidine compounds. Key in this simple, one-pot two-step procedure in water is a bromine-induced regioselective introduction of cysteine followed by a novel thermal cleavage reaction in the presence of thiols, a safer alternative to hazardous red phosphorus. Besides avoiding hazardous sulfur reagents, the new protecting-group-free approach reduces drastically the total number of steps, compared to described procedures. The main drawback, i.e. handling of liquid bromine as an activating and oxidizing reagent in water, was addressed by evaluating four alternative methods using in situ generation of bromine or HOBr, and first encouraging results are described.