Regio- and Enantioselective Intramolecular Amide Carbene Insertion into Primary C-H Bonds Using Ru(II)-Pheox Catalyst
Regio- and Enantioselective Intramolecular Amide Carbene Insertion into Primary C-H Bonds Using Ru(II)-Pheox Catalyst
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DOI：
10.1021/acs.joc.8b03044
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发表时间：
2019-03-01
影响因子：
3.6
通讯作者：
Iwasa, Seiji
中科院分区：
文献类型：
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作者：
Nakagawa, Yoko;Chanthamath, Soda;Iwasa, Seiji
我们已经建立了一种通过分子内酰胺卡宾插入C-H键来实现叔丁基的高区域和对映选择性官能化的方法，以高达99%的产率得到了91%的ee的伽马内酰胺。该反应使用的是Ru(II)苯基恶唑啉(Ru(II)-Pheox)络合物。在1mol%Ru(II)-Pheox催化剂存在下，与次级C-H键、苄基次级C-H键、Tert-C-H键或sp(2)C-H键相比，催化分子内卡宾向初级C-H键的转移反应迅速且选择性地进行。这是第一个催化类卡宾插入未活化的叔丁基，并在类卡宾碳上进行对映体控制的例子。
We have established a method for the highly regio- and enantioselective functionalization of tert-butyl groups via intramolecular amide carbene insertion into C-H bonds, yielding gamma-lactams with 91% ee in up to 99% yield. This reaction uses a ruthenium(II) phenyl oxazoline (Ru(II)-Pheox) complex. The catalytic intramolecular carbene transfer reaction to the primary C-H bond proceeds rapidly and selectively compared to that with secondary C-H, benzylic secondary C-H, tert-C-H, or sp(2)C-H bonds in the presence of 1 mol % Ru(II)-Pheox catalyst. This is the first example of a catalytic carbenoid insertion into an unactivated tert-butyl group with enantiocontrol at the carbenoid carbon.