Iridium(I)-Catalyzed Intramolecular Hydrocarbonation of Alkenes: Efficient Access to Cyclic Systems Bearing Quaternary Stereocenters

Iridium(I)-Catalyzed Intramolecular Hydrocarbonation of Alkenes: Efficient Access to Cyclic Systems Bearing Quaternary Stereocenters
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DOI:
10.1002/anie.201705105
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发表时间:
2017-08-01
影响因子:
16.6
通讯作者:
Lopez, Fernando
Lopez, Fernando
中科院分区:
化学1区
文献类型:
--
作者:
Fernandez, David F.;Gulias, Moises;Lopez, Fernando

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描述了一种催化的、通用的和原子经济的C-H官能化方法,该方法提供了各种各样的以甲基取代的季立体中心为特征的环状体系。该方法依赖于使用阳离子Ir-1-双膦催化剂,其促进烯属C(sp(2))-H键的甲酰胺辅助活化,随后外环化为栓系的1,1-二取代的烯烃。该方法的延伸到芳香族和杂芳香族的C-H键,以及对映体选择性的变体上的发展,也进行了描述。
A catalytic, versatile and atom-economical C-H functionalization process that provides a wide variety of cyclic systems featuring methyl-substituted quaternary stereocenters is described. The method relies on the use of a cationic Ir-I-bisphosphine catalyst, which promotes a carboxamide-assisted activation of an olefinic C(sp(2))-H bond followed by exo-cyclization to a tethered 1,1-disubstituted alkene. The extension of the method to aromatic and heteroaromatic C-H bonds, as well as developments on an enantioselective variant, are also described.