二碘化钐参与及二茂钛催化的氮α-位碳自由基偶联反应及其在含氮杂环合成中的应用

郑啸; 黄培强*

doi:10.7536/PC171249

化学进展 ›› 2018, Vol. 30 ›› Issue (5) :528-546 DOI: 10.7536/PC171249

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二碘化钐参与及二茂钛催化的氮α-位碳自由基偶联反应及其在含氮杂环合成中的应用

郑啸, 黄培强*

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SmI₂ and Titanocene-Mediated Coupling Reactions of α-Aminoalkyl Radicals and Applications to the Synthesis of Aza-Heterocycles

Xiao Zheng, Pei-Qiang Huang*

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摘要

氮α-位碳-碳键的构造是含氮有机化合物合成中的基本方法。通过氮α-位的碳正离子（亚胺鎓）、碳负离子和碳自由基中间体是实现这一目标的主要途径。相对而言，通过氮α-位碳自由基中间体构造碳-碳键可在较温和的中性条件下进行，且可实现对亚胺鎓离子的极性反转，因而是对正、负离子极性反应的重要补充。作为温和的单电子还原剂，Kagan试剂（二碘化钐）可还原多种含氮有机物产生氮α-位自由基，进而发生自由基偶联反应，在形成氮α-位碳-碳键的方法学发展中扮演了重要的角色。本文综述了二碘化钐参与的氮α-位自由基偶联反应在有机合成中的研究进展，重点归纳评述了二碘化钐参与的亚胺、硝酮、氮杂半缩醛、酰亚胺和酰胺等底物与醛/酮及与缺电子烯烃的自由基偶联反应，为了探讨、克服二碘化钐在相关反应中的局限性，也介绍了二茂钛催化的氮α-位碳自由基偶联反应的最新进展。此外，还重点评述了这些合成方法在含氮活性化合物、生物碱和中间体的简捷合成中的应用。

Abstract

Carbon-carbon formation at N-α-carbon is an essential transformation in the synthesis of nitrogen-containing compounds. N-α-Carbocations (iminium ions), N-α-carbanions, and N-α-aminoalkyl radicals constitute three major classes of intermediates for this goal. The carbon-carbon forming reactions based on N-α-aminoalkyl radicals is advantageous over other two classes of intermediates for being able to run the reactions under mild neutral conditions. Moreover, because N-α-aminoalkyl radicals are umpolung of N-α-carbocations (iminium ions), the approaches based on these intermediates are complementary. In this regard, Kagan reagent (samarium diiodide, SmI₂), a mild single-electron reductant, has emerged as a versatile reagent for the generation and coupling of N-α-aminoalkyl radicals. In this review, recent progresses on the carbon-carbon forming reactions at N-α-carbon via Kagan reagent is summarized. A number of nitrogen-containing substrates including imines, nitrones, hemiaminals, imides and amides have been shown to be valuable precursors to generate α-aminoalkyl radicals. The in situ coupling reactions of the latter with aldehydes/ketones, or electron-deficient alkenes lead to the formation of N-α-C—C bonds. These methods allow flexible access to diverse N-α-C functionalized compounds. To overcome some limitations of Kagan reagent, methods based on the titanocene-catalyzed generation of N-α-aminoalkyl radicals have also been developed. Many of these methods have been applied to the concise syntheses of medicinal-relevant compounds, alkaloids or key intermediates.
Contents
1 Introduction
2 SmI₂-mediated radical coupling of imines
3 SmI₂-mediated radical coupling of nitrones
3.1 Methodology research
3.2 Synthetic application
4 SmI₂-mediated radical coupling of chiral N-tert-butanesulfinyl imines
4.1 Methodology research
4.2 Synthetic application
5 SmI₂-mediated radical coupling of hemiaminal
5.1 Methodology research
5.2 Synthetic application
6 SmI₂-mediated radical coupling of imides, amides and nitriles
6.1 Radical coupling of imides
6.2 Radical coupling of amides
6.3 Radical coupling of nitriles
7 An extension research:titanocene-catalyzed radical coupling reactions
8 Conclusion and outlook

Graphical abstract

关键词

氮α-位碳自由基 / 二碘化钐 / 偶联反应 / 二茂钛 / 含氮化合物 / 合成方法

Key words

α-aminoalkyl radical / samarium diiodide / coupling reaction / titanocene / N-containing compounds / synthetic methods

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郑啸, 黄培强*. 二碘化钐参与及二茂钛催化的氮α-位碳自由基偶联反应及其在含氮杂环合成中的应用[J]. 化学进展, 2018, 30(5): 528-546 DOI:10.7536/PC171249

Xiao Zheng, Pei-Qiang Huang*. SmI₂ and Titanocene-Mediated Coupling Reactions of α-Aminoalkyl Radicals and Applications to the Synthesis of Aza-Heterocycles[J]. Progress in Chemistry, 2018, 30(5): 528-546 DOI:10.7536/PC171249

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