Ruthenium-Catalyzed C-H Hydroxylation in Aqueous Acid Enables Selective Functionalization of Amine Derivatives
Ruthenium-Catalyzed C-H Hydroxylation in Aqueous Acid Enables Selective Functionalization of Amine Derivatives
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DOI：
10.1021/jacs.7b05469
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发表时间：
2017-07-19
影响因子：
15
通讯作者：
Sigman, Matthew S.
中科院分区：
文献类型：
--
作者：
Mack, James B. C.;Gipson, John D.;Sigman, Matthew S.
介绍了一种新的催化SP(3)C-H羟基化反应方案的确定、优化和评价。使用双(联吡啶)Ru催化剂在水溶液中进行反应，以使具有碱性胺官能团的底物能够被氧化。对于许多胺类化合物来说，叔基和苄基的C-H羟基化比N-氧化反应更受青睐。对于萜类衍生的底物，也观察到了向叔基和苄基C-H键反应的类似趋势。尽管反应介质的电离强度很高，但手性三中心的羟化反应是对映异构性的。初步的动力学实验表明，顺式和反式Ru异构体催化剂的反应活性有明显差异，表明该催化剂在反应条件下是稳定的。
The identification, optimization, and evaluation of a new catalytic protocol for sp(3) C-H hydroxylation is described. Reactions are performed in aqueous acid using a bis(bipyridine)Ru catalyst to enable oxidation of substrates possessing basic amine functional groups. Tertiary and benzylic C-H hydroxylation is strongly favored over N-oxidation for numerous amine derivatives. With terpene-derived substrates, similar trends in reactivity toward tertiary and benzylic C-H bonds are observed. Hydroxylation of chiral tertiary centers is enantiospecific in spite of the ionizing strength of the reaction medium. Preliminary kinetics experiments show a marked difference in reactivity between isomeric cis- and trans-Ru catalysts suggesting that the catalyst is configurationally stable under the reaction conditions.