Xie Haisheng, Ye Zongren, Ke Zhuofeng, Lan Jianyong, Jiang Huanfeng, Zeng Wei
School of Chemistry and Chemical Engineering , South China University of Technology , No. 381 Wushan Road , Guangzhou , 510641 , P. R. China . Email:
School of Materials Science & Engineering , PCFM Lab , Sun Yat-sen University , Guangzhou , 510275 , P. R. China . Email:
Chem Sci. 2017 Nov 27;9(4):985-989. doi: 10.1039/c7sc03802j. eCollection 2018 Jan 28.
A Rh(iii)-catalyzed regioselective intermolecular carbenoid insertion into the -methylene Csp-H bond of acyclic aliphatic amides has been achieved, taking advantage of bidentate-chelation assistance. This methodology has been successfully applied to a broad range of linear and branched-chain -alkylamides, thus providing a practical method for the assembly of diverse beta-amino esters. Mechanism studies and density functional theory (DFT) calculations revealed that a singlet Fischer type carbene insertion an outer-sphere pathway was involved in this -methylene Csp-H bond carbenoid insertion.
利用双齿螯合辅助作用，实现了铑（III）催化的区域选择性分子间类卡宾插入无环脂肪族酰胺的亚甲基Csp-H键反应。该方法已成功应用于多种直链和支链β-烷基酰胺，从而为组装各种β-氨基酯提供了一种实用方法。机理研究和密度泛函理论（DFT）计算表明，该亚甲基Csp-H键类卡宾插入反应涉及单线态费舍尔型卡宾插入——一种外层球途径。
