Nickel/Photoredox Dual Catalytic Cross-Coupling of Alkyl and Amidyl Radicals to Construct C(sp3)–N Bonds,ACS Catalysis

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Nickel/Photoredox Dual Catalytic Cross-Coupling of Alkyl and Amidyl Radicals to Construct C(sp3)–N Bonds
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-04-09 , DOI: 10.1021/acscatal.1c00731
Shaofang Zhou ₁ , Kang Lv _{1,

2} , Rui Fu ₁ , Changlei Zhu ₁ , Xiaoguang Bao ₁

Affiliation

The construction of C(sp³)–N bonds via direct radical–radical cross-coupling under benign conditions is a desirable but challenging approach. Herein, the cross-coupling of alkyl and amidyl radicals to build aliphatic C–N bonds in a concise, mild, and oxidant-free manner is implemented by nickel/photoredox dual catalysis. In this protocol, the single electron transfer strategy is successfully employed to generate N- and C-centered radicals from sulfonyl azides/azidoformates and alkyltrifluoroborates, respectively. The photocatalyst-induced triplet–triplet energy-transfer mechanism, however, might not be applicable to this reaction. The oxidative quenching pathway of the excited photocatalyst (Ru^II/*Ru^II/Ru^III/Ru^II) combined with a possible Ni^I/Ni^II/Ni^III/Ni^I catalytic cycle is proposed to account for the nickel/photoredox dual-catalyzed C(sp³)–N bond formation based on synergistic experimental and computational studies.

中文翻译：

镍/光氧化还原双催化交叉偶联烷基和酰胺基自由基以构建C（sp ³）–N键

在良性条件下通过直接自由基-自由基交叉偶联来构建C（sp ³）-N键是一种理想但具有挑战性的方法。在此，通过镍/光氧化还原双重催化，以简明，温和且无氧化剂的方式将烷基和and基自由基交叉偶联以建立脂族C–N键。在该协议中，成功地采用了单电子转移策略，分别从磺酰基叠氮化物/叠氮基甲酸酯和烷基三氟硼酸酯生成N-和C-中心的自由基。然而，光催化剂诱导的三重态-三重态能量转移机制可能不适用于该反应。激发的光催化剂（Ru ^II / * Ru ^II / Ru ^III / Ru ^II的氧化猝灭途径））结合可能的Ni ^I / Ni ^II / Ni ^III / Ni ^I催化循环，基于协同实验和计算研究，提出了镍/光氧化还原双催化C（sp ³）–N键形成的方法。

更新日期：2021-05-07

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