Tan Zhuotao, Zhang Xiaowang, Xu Mengjiao, Fu Yaping, Zhuang Wei, Li Ming, Wu Xiaojin, Ying Hanjie, Ouyang Pingkai, Zhu Chenjie
College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing, China.
National Engineering Research Center for Biotechnology, Nanjing, China.
Sci Adv. 2022 Sep 9;8(36):eadd1912. doi: 10.1126/sciadv.add1912. Epub 2022 Sep 7.
Inspired by Nature's ingenuity, considerable progress has been made in recent years to develop chemoenzymatic processes by the integration of environmentally friendly feature of biocatalysis with versatile reactivity of chemocatalysis. However, the current types of chemoenzymatic processes are relatively few and mostly rely on metal catalysts. Here, we report a previously unexplored cooperative chemoenzymatic system for the synthesis of N-heterocycles. Starting from alcohols and amines, benzimidazole, pyrazine, quinazoline, indole, and quinoline can be obtained in excellent yields in water with O as the terminal oxidant. Synthetic bridged flavin analog is served as a bifunctional organocatalyst for the regeneration of cofactor nicotinamide adenine dinucleotide in the bioprocess and oxidative cyclodehydrogenation in the chemoprocess. Compared to the classical acceptorless dehydrogenative coupling strategy, being metal and base free, requiring only water as solvent, and not needing atmosphere protection were observed for the present method, exhibiting a favorable green and sustainable alternative.
受大自然智慧的启发，近年来通过将生物催化的环境友好特性与化学催化的多功能反应性相结合，在开发化学酶促过程方面取得了相当大的进展。然而，目前化学酶促过程的类型相对较少，并且大多依赖于金属催化剂。在此，我们报道了一种用于合成氮杂环的前所未有的协同化学酶促体系。以醇类和胺类为起始原料，以氧气作为终端氧化剂，在水中可以以优异的产率获得苯并咪唑、吡嗪、喹唑啉、吲哚和喹啉。合成的桥连黄素类似物作为双功能有机催化剂，用于生物过程中辅因子烟酰胺腺嘌呤二核苷酸的再生以及化学过程中的氧化环脱氢反应。与经典的无受体脱氢偶联策略相比，本方法无金属和碱，仅需水作为溶剂，且无需空气保护，展现出一种良好的绿色可持续替代方案。
