Asymmetric Radical Process for General Synthesis of Chiral Heteroaryl Cyclopropanes.
Asymmetric Radical Process for General Synthesis of Chiral Heteroaryl Cyclopropanes.
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DOI：
10.1021/jacs.1c04655
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发表时间：
2021-07-28
影响因子：
15
通讯作者：
Zhang XP
中科院分区：
文献类型：
--
作者：
Wang X;Ke J;Zhu Y;Deb A;Xu Y;Zhang XP
采用Co（II）基金属催化（MRC）方法，建立了烯烃与原位生成的α-杂芳基重氮甲烷进行不对称自由基环丙烷化反应的高效催化方法。通过对新合成的d2对称手性酰胺卟啉作为支撑配体的类腔环境进行精细调整，优化后的Co（II）基金属体系可广泛应用于α-吡啶和其他α-杂芳基重氮甲烷的不对称环丙烷化反应，包括几种具有挑战性的底物。这种新的催化方法为高收率的手性杂芳基环丙烷提供了一种普遍的途径，具有优异的非对映选择性和对映选择性。计算和实验相结合的研究进一步支持了Co（II）基烯烃环丙化反应中以α-和γ-金属烷基自由基为关键中间体的逐步自由基机制。
A highly efficient catalytic method has been developed for asymmetric radical cyclopropanation of alkenes with in situ-generated α-heteroaryldiazomethanes via Co(II)-based metalloradical catalysis (MRC). Through fine-tuning the cavity-like environments of newly-synthesized D2-symmetric chiral amidoporphyrins as the supporting ligand, the optimized Co(II)-based metalloradical system is broadly applicable to α-pyridyl and other α-heteroaryldiazomethanes for asymmetric cyclopropanation of wide-ranging alkenes, including several types of challenging substrates. This new catalytic methodology provides a general access to valuable chiral heteroaryl cyclopropanes in high yields with excellent both diastereoselectivities and enantioselectivities. Combined computational and experimental studies further support the underlying stepwise radical mechanism of the Co(II)-based olefin cyclopropanation involving α- and γ-metalloalkyl radicals as the key intermediates.
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