Catalyst-Free Deaminative Functionalizations of Primary Amines by Photoinduced Single-Electron Transfer

Catalyst-Free Deaminative Functionalizations of Primary Amines by Photoinduced Single-Electron Transfer
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通过光诱导单电子转移对伯胺进行无催化剂脱氨基功能化

DOI:
10.1002/ange.201814452
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发表时间:
2019
期刊:
影响因子:
--
通讯作者:
Wu J
Wu J
中科院分区:
--
文献类型:
--
作者:
Wu J

文献摘要

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描述了吡啶钥活化的伯胺作为光活性官能团用于在无催化剂条件下脱氨基生成烷基自由基的用途。通过利用Katritzky吡啶鎓盐与Hantzsch酯或Et 3 N之间的电子供体-受体络合物的可见光吸收率,可以在不存在光催化剂的情况下引发光诱导的单电子转移。该通用反应性平台已应用于脱氨基烷基化(Giese)、烯丙基化、乙烯基化、炔基化、硫醚化和加氢脱氨基反应。温和的条件适用于各种伯和仲烷基吡啶鎓,并表现出广泛的官能团耐受性。
The use of pyridinium‐activated primary amines as photoactive functional groups for deaminative generation of alkyl radicals under catalyst‐free conditions is described. By taking advantage of the visible light absorptivity of electron donor–acceptor complexes between Katritzky pyridinium salts and either Hantzsch ester or Et3N, photoinduced single‐electron transfer could be initiated in the absence of a photocatalyst. This general reactivity platform has been applied to deaminative alkylation (Giese), allylation, vinylation, alkynylation, thioetherification, and hydrodeamination reactions. The mild conditions are amenable to a diverse range of primary and secondary alkyl pyridiniums and demonstrate broad functional group tolerance.