Oi Miku, Takita Ryo, Kanazawa Junichiro, Muranaka Atsuya, Wang Chao, Uchiyama Masanobu
Graduate School of Pharmaceutical Sciences , University of Tokyo , Hongo 7-3-1, Bunkyo-ku , Tokyo , Japan . Email:
Advanced Elements Chemistry Research Team , RIKEN Center for Sustainable Resource Science , Elements Chemistry Laboratory , RIKEN , Wako-shi , Saitama 351-0198 , Japan.
Chem Sci. 2019 May 10;10(24):6107-6112. doi: 10.1039/c9sc00891h. eCollection 2019 Jun 28.
We describe a powerful, broadly applicable cross-coupling protocol that enables carbon-carbon bond formation at highly sterically hindered carbon centers (both sp and sp) 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.
我们描述了一种强大且广泛适用的交叉偶联协议，该协议通过在钯催化下使用有机铜试剂，能够在高度空间位阻的碳中心（sp和sp）形成碳 - 碳键。实验研究和理论计算表明，铜独特反应性的关键在于由于Cu(i)-Pd(ii)相互作用，紧密的转金属化过渡态具有相对较低的活化能，这与反应物较小的变形能值相关。该反应适用于各种庞大的底物，包括对先前交叉偶联化学惰性的化合物，并且具有高官能团耐受性。
