Exploiting single-electron transfer in Lewis pairs for catalytic bond-forming reactions.

Exploiting single-electron transfer in Lewis pairs for catalytic bond-forming reactions.
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DOI:
10.1039/d0sc01159b
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发表时间:
2020-03-20
期刊:
影响因子:
8.4
通讯作者:
Ooi T
Ooi T
中科院分区:
化学1区
文献类型:
--
作者:
Aramaki Y;Imaizumi N;Hotta M;Kumagai J;Ooi T

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报道了三(五氟苯基)硼烷(B(C6 F5)3)与N,N-二烷基苯胺之间的单电子转移(SET)反应,根据苯胺衍生物的结构,在黑暗条件或可见光照射下,通过形成电子给体-受体(EDA)络合物作为关键中间体,该络合物涉及π轨道相互作用.刘易斯对中的这种固有SET引发相应的α-氨基烷基自由基的产生及其对缺电子烯烃的加成,揭示了B(C6 F5)3作为有效的单电子氧化还原催化剂的能力。从普通刘易斯对产生自由基离子对及其在催化碳-碳键形成中的应用。
A single-electron transfer (SET) between tris(pentafluorophenyl)borane (B(C6F5)3) and N,N-dialkylanilines is reported, which is operative via the formation of an electron donor–acceptor (EDA) complex involving π-orbital interactions as a key intermediate under dark conditions or visible-light irradiation depending on the structure of the aniline derivatives. This inherent SET in the Lewis pairs initiates the generation of the corresponding α-aminoalkyl radicals and their additions to electron-deficient olefins, revealing the ability of B(C6F5)3 to act as an effective one-electron redox catalyst. Radical–ion pair generation from common Lewis pairs and its application to catalytic carbon–carbon bond formation.
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