Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1, Hongo, Tokyo 113-0033, Japan.
Chem Rec. 2011 Sep;11(5):236-41. doi: 10.1002/tcr.201100024. Epub 2011 Sep 6.
Outer-sphere redox catalysis is key to efficient C-H activation, which has attracted increased interest in organic chemistry. In this account, we describe a Cu(I) -catalyzed oxidative coupling between nitrones and various ethers or amines as an example. Predictable site-selective C-C bond formation was achieved through activation of the C-H bonds in each coupling partner and the migration of a C-N double bond. Mechanistic studies strongly suggested that the reaction proceeded via an oxonium/iminium cation species as the key intermediate. The mechanistic information allows for future extension of outer-sphere redox catalysis.
外层氧化还原催化对于有效的 C-H 活化至关重要，这在有机化学中引起了越来越多的关注。在本说明中，我们以 Cu(I) 催化的硝酮与各种醚或胺之间的氧化偶联为例进行了描述。通过每种偶联物中 C-H 键的活化以及 C-N 双键的迁移，实现了可预测的位点选择性 C-C 键形成。机理研究强烈表明，反应是通过作为关键中间体的氧鎓/亚铵阳离子物种进行的。该机理信息允许进一步扩展外层氧化还原催化。
