Visible-Light-Mediated Decarboxylation/Oxidative Amidation of α-Keto Acids with Amines under Mild Reaction Conditions Using O2

Visible-Light-Mediated Decarboxylation/Oxidative Amidation of α-Keto Acids with Amines under Mild Reaction Conditions Using O2
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DOI:
10.1002/anie.201308614
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发表时间:
2014-01-07
影响因子:
16.6
通讯作者:
Lei, Aiwen
Lei, Aiwen
中科院分区:
化学1区
文献类型:
--
作者:
Liu, Jie;Liu, Qiang;Lei, Aiwen

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光化学开启了化学发展的新纪元,特别是近五年来,随着可见光光氧化还原催化与自由基反应的结合,光氧化还原催化已成为一个热门话题。报道了一种新颖、简单、高效的光催化剂[Ru(Phen)(3)]Cl2辅助下的自由基氧化脱羧化偶联反应。各种官能团在该反应中具有很好的耐受性,为开发先进的好氧氧化脱羧基方法提供了新的途径。初步的机理研究表明:1)[Ru(Phen)(3)](2+)*与苯胺之间的SET过程起重要作用;2)O-2的活化可能是速率决定步骤;3)脱羧基是一个不可逆的快速过程。
Photochemistry has ushered in a new era in the development of chemistry, and photoredox catalysis has become a hot topic, especially over the last five years, with the combination of visible-light photoredox catalysis and radical reactions. A novel, simple, and efficient radical oxidative decarboxylative coupling with the assistant of the photocatalyst [Ru(phen)(3)]Cl-2 is described. Various functional groups are well-tolerated in this reaction and thus provides a new approach to developing advanced methods for aerobic oxidative decarboxylation. The preliminary mechanistic studies revealed that: 1)an SET process between [Ru(phen)(3)](2+)* and aniline play an important role; 2)O-2 activation might be the rate-determining step; and 3)the decarboxylation step is an irreversible and fast process.