Development of Dehydrative S-Allylation toward Synthetic Biology

s -烯丙化半胱氨酸和多肽具有多种生物活性。为了高效地生成一系列化学文库，天然形式的含硫醇氨基酸和肽的直接s -烯丙基化是首选。我们的催化体系由[CpRu(CH3CN)3]PF6和2-喹啉羧酸或对烯丙基Ru络合物组成，首次实现了这一理想过程。s -烯丙化过程即使在含乙酸缓冲体系的水介质中也具有高反应活性和s -化学选择性，表明本方法可能应用于含半胱氨酸的蛋白质。可以利用多种C(2)取代烯丙醇，为构建新型脂肽库铺平了道路

S-Allylated cysteine and peptides show various biological activities. In order to efficient generate a series of chemical libraries, direct S-allylation of thiol-containing amino acid and peptides in the native form is favored. This ideal process has been firstly realized by use of our catalytic system consisting of either [CpRu(CH3CN)3]PF6 and 2-quinolinecarboxylic acid or the pai-allyl Ru complex. The S-allylation process even in aqueous media including an acetate buffer system with high reactivity and S-chemoselectivity, suggesting a possibility of application of the present method for cysteine-containing proteins. Various C(2)-substituted allyl alcohols can be utilized, paving a way to a new type of lipopeptide library