钒依赖型氯过氧化物酶催化脱肟反应研究

Study on Vanadium-Dependent Chlorperoxidase-Catalyzed Deoximation Reactions

目的研究一种新型的绿色脱肟方法即卤过氧化物酶催化脱肟反应,同时尝试与醇脱氢酶(ADH)级联扩大脱肟反应应用范围。方法在室温条件下,以钒依赖型氯过氧化物酶(Ci VCPO)为催化剂,向柠檬酸缓冲液中加入肟类化合物、H_(2)O_(2)、NaCl。随后,调控反应液pH同时加入Tg ADH与辅因子。结果确定最优体系为50mmol/L H_(2)O_(2)、100mmol/L柠檬酸缓冲液(pH=4)及0.5μmol/L Ci VCPO。此条件下测试了7种肟类底物,顺利得到了相应的醛酮产物,产率23%~98%。进一步地,与Tg ADH级联反应得到了相应的醇类化合物。结论Ci VCPO对脱肟反应具有良好的催化活性,并能通过“一锅法”与Tg ADH级联反应获得相应的醇。

Objective To explore a new green deoximation reaction catalyzed by haloperoxidase,and expand the application scope of deoximation reaction cascaded with alcohol dehydrogenase(ADH).Methods Atroom temperature,oximes,H_(2)O_(2) and NaCl were added into sodium citrate-hydrochloric acid buffer solution by using vanadium dependent chlorperoxidase(Ci VCPO)as the catalyst.Then,the pH was regulated,while Tg ADH as well as NADH was added.Results The optimal reaction conditions were 50mmol/L of H_(2)O_(2),100mmol/L of sodium citrate-hydrochloric acid buffer solution(pH=4)and 0.5μmol/L of Ci VCPO,respectively.Under the conditions,seven oximes were employed and the corresponding aldehydes and ketones were obtained smoothly with the yield of 23%~98%.Furthermore,some of the deoximation reactions as mentioned were cascaded with Tg ADH,which finally gave the resultant alcohols.Conclusion Ci VCPO exhibited a good activity for deoximation,which then cascaded successfully with Tg ADH to gain the corresponding alcohol via a one pot strategy.