†State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
J Am Chem Soc. 2015 Jun 24;137(24):7564-7. doi: 10.1021/jacs.5b03488. Epub 2015 Jun 11.
A new strategy is reported for intramolecular sp(3) C-H amination under mild reaction conditions using iodoarene as catalyst and m-CPBA as oxidant. This C-H functionalization involving iodine(III) reagents generated in situ occurs readily at sterically hindered tertiary C-H bonds. DFT (M06-2X) calculations show that the preferred pathway involves an iodonium cation intermediate and proceeds via an energetically concerted transition state, through hydride transfer followed by the spontaneous C-N bond formation. This leads to the experimentally observed amination at a chiral center without loss of stereochemical information.
报道了一种新的策略，即在温和的反应条件下，使用碘芳烃作为催化剂和间氯过氧苯甲酸（m-CPBA）作为氧化剂，实现分子内 sp(3) C-H 胺化。这种涉及原位生成的碘(III)试剂的 C-H 官能化反应很容易发生在空间位阻较大的叔 C-H 键上。密度泛函理论（M06-2X）计算表明，优先途径涉及碘翁阳离子中间体，并通过协同的过渡态进行，通过氢化物转移，然后自发形成 C-N 键。这导致在手性中心发生实验观察到的胺化，而不会失去立体化学信息。
