通过光氧化还原介导的C-H官能化与Minisci反应相结合实现醚的直接α-芳基化。
Direct α-arylation of ethers through the combination of photoredox-mediated C-H functionalization and the Minisci reaction.
作者信息
Jin Jian, MacMillan David W C
机构信息
Merck Center for Catalysis at Princeton University, Washington Road, Princeton, NJ 08544 (USA) http://www.princeton.edu/chemistry/macmillan/
出版信息
Angew Chem Int Ed Engl. 2015 Jan 26;54(5):1565-9. doi: 10.1002/anie.201410432. Epub 2014 Dec 2.
Abstract
The direct α-arylation of cyclic and acyclic ethers with heteroarenes has been accomplished through the design of a photoredox-mediated CH functionalization pathway. Transiently generated α-oxyalkyl radicals, produced from a variety of widely available ethers through hydrogen atom transfer (HAT), were coupled with a range of electron-deficient heteroarenes in a Minisci-type mechanism. This mild, visible-light-driven protocol allows direct access to medicinal pharmacophores of broad utility using feedstock substrates and a commercial photocatalyst.
摘要
通过设计光氧化还原介导的CH官能化途径，实现了环状和非环状醚与杂芳烃的直接α-芳基化反应。通过氢原子转移（HAT）从各种广泛可得的醚类中瞬态生成的α-氧代烷基自由基，以Minisci型机理与一系列缺电子杂芳烃偶联。这种温和的可见光驱动方法允许使用原料底物和市售光催化剂直接获得具有广泛用途的药用基团。
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J Org Chem. 2014 Nov 7;79(21):10682-8. doi: 10.1021/jo5020432. Epub 2014 Oct 24.
2
Late-stage functionalization of biologically active heterocycles through photoredox catalysis.通过光氧化还原催化对生物活性杂环进行晚期功能化。
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3
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4
Solar synthesis: prospects in visible light photocatalysis.太阳能合成：可见光光催化中的前景。
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5
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Chemistry. 2014 Mar 3;20(10):2960-5. doi: 10.1002/chem.201304120. Epub 2014 Feb 5.
6
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7
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Angew Chem Int Ed Engl. 2013 Apr 26;52(18):4734-43. doi: 10.1002/anie.201210276. Epub 2013 Apr 10.
8
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9
Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis.过渡金属配合物可见光光氧化还原催化：在有机合成中的应用
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10
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