DNA催化水相体系中的二硫缩醛反应(英文)

DNA Catalyzed Dithioacetalization in Water

在各种生命起源假说中,比较公认的是原生生命起源于RNA.在RNA世界中,RNA不仅是遗传物质,并且是具有酶活性的催化剂.DNA在自然界中普遍以双螺旋结构存在,一直被认为只是生命体遗传信息的载体,但是DNA和RNA相似的化学组成引发了研究者探究DNA是否具有催化功能.尽管到目前为止在自然界还没有发现具有催化活性的DNA,研究者利用有机反应模型已经开展研究DNA的相关催化功能,例如利用DNA为模板进行有机合成和利用DNA的手性结构进行手性合成.但是,直接利用DNA作为催化剂进行有机反应的研究还不多见.本文报道了源于鲱鱼精的双链DNA可以催化水相体系中一系列醛的二硫缩醛反应.通过实验推断DNA中的磷酸基团为主要的催化活性中心,并且DNA的双螺旋结构对反应也起到一定的促进作用.

The most popular hypothesis of precellular life is the ＂RNA World＂, which is utilizing RNA as both genetic as well as catalytic material. The chemical similarity between RNA and DNA leads researchers to investigate whether DNA has the catalytic function, although DNA is commonly viewed as a genetic carrier with a ubiquitous double-stranded architecture in living world. Nevertheless, the catalytic DNA has not been discovered in nature to date. In recent years, the catalytic func- tion of DNA in nonbiological applications has aroused much interest to chemists in chemical synthesis such as DNA-templated organic synthesis and DNA-based asymmetric catalysis. However, the investigation of DNA as a direct cata- lyst for organic synthesis is largely elusive. Here we report that double-stranded DNA from herring sperm can catalyze the dithioacetalization in water for a wide range of aldehydes under mild reaction conditions. It is proposed that the phosphate groups of DNA together with the duplex architecture are responsible for the catalytic reaction.