Stereoselective Radical C-H Alkylation with Acceptor/Acceptor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis.
Stereoselective Radical C-H Alkylation with Acceptor/Acceptor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis.
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DOI：
10.1039/c4sc02610a
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发表时间：
2015-02
期刊：
影响因子：
8.4
通讯作者：
Zhang XP
中科院分区：
文献类型：
--
作者：
Cui X;Xu X;Jin LM;Wojtas L;Zhang XP
Co(II)基金属催化剂首次成功地用于受体/受体取代的重氮试剂的不对称分子内C-H烷基化反应。Co(II)基金属催化剂首次成功地用于受体/受体取代的重氮试剂的不对称分子内C-H烷基化反应。通过设计和合成一种新的D2对称的手性氨基卟啉作为支撑配体，基于Co(II)的金属体系能够在室温下进行1，5-C-H烷基化反应，得到具有广泛电子性质的α-甲氧羰基-α-重氮砜，提供了高产率的5元环丁砜衍生物，具有良好的非对映选择性和对映体选择性。除了对烯丙基和烯丙基C-H键的完全化学选择性外，基于Co(II)的金属催化剂对不对称C-H烷基化反应具有显著的官能团耐受性。
Co(ii)-based metalloradical catalysis has, for the first time, been successfully applied for asymmetric intramolecular C–H alkylation of acceptor/acceptor-substituted diazo reagents. Co(ii)-based metalloradical catalysis has, for the first time, been successfully applied for asymmetric intramolecular C–H alkylation of acceptor/acceptor-substituted diazo reagents. Through the design and synthesis of a new D 2-symmetric chiral amidoporphyrin as the supporting ligand, the Co(ii)-based metalloradical system, which operates at room temperature, is capable of 1,5-C–H alkylation of α-methoxycarbonyl-α-diazosulfones with a broad range of electronic properties, providing the 5-membered sulfolane derivatives in high yields with excellent diastereoselectivities and enantioselectivities. In addition to complete chemoselectivity toward allylic and allenic C–H bonds, the Co(ii)-based metalloradical catalysis for asymmetric C–H alkylation features a remarkable degree of functional group tolerance.