Direct ortho cupration: A new route to regioselectively functionalized aromatics
Direct ortho cupration: A new route to regioselectively functionalized aromatics
复制标题
DOI：
10.1021/ja074669i
复制
发表时间：
2007-12-12
影响因子：
15
通讯作者：
Uchiyama, Masanobu
中科院分区：
文献类型：
--
作者：
Usui, Shinya;Hashimoto, Yuichi;Uchiyama, Masanobu
我们开发了一种直接区域选择性和化学选择性的方法，通过使用TMP的去质子化定向邻位铜化来生成官能化的芳香族铜酸盐化合物（四甲基哌啶子基）-铜酸盐（R（TMP）Cu（CN）Li-2; R =烷基、苯基或TMP），其通过将CuCN、RLi、和四甲基哌啶锂（LTMP）在各种官能化苯与TMP-铜酸盐被证明可有效地直接生成O -官能化的铜芳族和杂芳族衍生物，特别是具有亲电官能团如氰基、酰胺和卤素的那些。直接铜化亲电捕集法为1，2-或1，2，3-多取代芳香族化合物的制备提供了一种简便的方法。还发现官能化的芳香族铜酸盐中间体通过适当地改变氧化剂和铜酸盐而非常有效地进行氧化反应，并且具有高的区域选择性和化学选择性，以提供官能化的苯酚、配体（杂）偶联或均偶联产物。
We have developed a direct regio- and chemoselective method for generating functionalized aromatic cuprate compounds through deprotonative directed ortho cupration using TMP(tetramethylpiperidino)-cuprates (R(TMP)Cu(CN)Li-2; R = alkyl, phenyl, or TMP) that are prepared by mixing of CuCN, RLi, and lithium tetramethylpiperidide (LTMP) in THE Deprotonative cupration of various functionalized benzenes with TMP-cuprate proved effective for the direct generation of o -functionalized copper aromatic and heteroaromatic derivatives, particularly those with electrophilic functional groups, such as cyano, amide, and halogens. Direct cupration, followed by electrophilic trapping, provided a convenient preparative method for 1,2- or 1,2,3-multisubstituted aromatic compounds. The functionalized aromatic cuprate intermediates were also found to undergo oxidation reactions very efficiently and with high regio- and chemoselectivity to afford functionalized phenol, ligand(hetero)-coupling, or homocoupling products by appropriately changing the oxidants and cuprates.