Catalytic Highly Regioselective C-H Oxygenation Using Water as the Oxygen Source: Preparation of 17O/18O-Isotope-Labeled Compounds

We found that the oxygen atom of water is activated to iodosylbenzene derivatives via reversible hydrolysis of PhI-(OOCR)(2) and can be used to the oxygen source for ruthenium(bpga)-catalyzed site-selective C-H oxygenation. Ru(bpga)/PhI-(OOCR)(2)/H2O system, sterically less bulky methinic and methylenic C-H bonds in various compounds can be converted to desired oxygen functional groups in a site-selective manner. Using this method, oxygen-isotope labeled compounds such as D-[3-O-17/O-18]-mannose can be prepared in a multigram scale.

我们发现，水的氧原子通过二（羧基过氧）碘苯（PhI-(OOCR)(2)）的可逆水解被活化成为亚碘酰苯衍生物，并且可作为钌（bpga）催化的位点选择性C - H氧化的氧源。在Ru(bpga)/PhI-(OOCR)(2)/H₂O体系中，各种化合物中空间位阻较小的次甲基和亚甲基C - H键能够以位点选择性的方式转化为所需的含氧官能团。利用这种方法，可以以数克规模制备氧同位素标记的化合物，例如D - [3 - O - ¹⁷O/¹⁸O] - 甘露糖。