Organocopper cross-coupling reaction for C-C bond formation on highly sterically hindered structures
Organocopper cross-coupling reaction for C-C bond formation on highly sterically hindered structures
复制标题
DOI：
10.1039/c9sc00891h
复制
发表时间：
2019-06-28
期刊：
影响因子：
8.4
通讯作者：
Uchiyama, Masanobu
中科院分区：
文献类型：
--
作者：
Oi, Miku;Takita, Ryo;Uchiyama, Masanobu
我们描述了一个强大的，广泛适用的交叉偶联协议，使碳碳键形成高度立体阻碍碳中心(sp（2)和sp(3)）通过使用有机铜试剂在钯催化下。实验研究和理论计算表明，铜具有独特的反应活性的关键是由于Cu(i)-Pd（ii）相互作用导致的致密金属转化过渡态的活化能相对较低，这与反应物的变形能值较小有关。该反应适用于各种笨重的底物，包括对以前的交叉偶联化学惰性的化合物，并且具有高官能团耐受性。
We describe a powerful, broadly applicable cross-coupling protocol that enables carbon-carbon bond formation at highly sterically hindered carbon centers (both sp(2) and sp(3)) by employing organocopper reagents under palladium catalysis. Experimental studies and theoretical calculations indicated that the key to the unique reactivity of copper is the relatively low activation energy of the compact transmetalation transition state, due to Cu(i)-Pd(ii) interaction, which is associated with small values of deformation energy of the reactants. This reaction is applicable to a variety of bulky substrates, including compounds inert to previous cross-coupling chemistry and has high functional group tolerance.