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首页> 外文期刊>Chemistry: A European journal >Divergent Reactivity of In Situ Generated Metal Azides: Reaction with N,N-Bis(oxy)enamines as a Case Study
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Divergent Reactivity of In Situ Generated Metal Azides: Reaction with N,N-Bis(oxy)enamines as a Case Study

机译：原位产生的金属叠氮化物的发散反应性：与N，N-BIS（氧）烯胺的反应作为案例研究

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摘要

Metal azides generated in situ by ion exchange exhibit divergent reactivity in reaction with cyclic N-alkoxy,Nsiloxy- enamines. Depending on the nature of metal and the [M]/N_3~- ratio, addition of the azide ion to the C,C-double bond proceeds with regioselective cleavage of either exo- or endo-cyclic N-O bond leading to cyclic or open-chain a-azidooxime derivatives, respectively. Mechanistic studies in combination with solvent state FTIR spectroscopy and DFT calculations revealed that covalently bound metal azides (Co, Cu, Zn) transfer N_3~- anion to the C,C-double bond through a Lewis acid-assisted S_N' substitution of trialkylsilyloxy- group. More ionic metal azides (N1, Mg, Al, Sc, Ni, Yb) tend to react by initial nucleophilic attack of N_3~- anion on the silicon atom generating conjugated nitrosoalkenes. a- Azidooxime derivatives prepared by using the designed protocols were stereoselectively reduced to valuable 1,2-diaminoalcohols bearing up to four contiguous stereogenic centers. By reducing the a-azidooxime fragment in a stepwise manner site-selective protection and reductive amination of each of the emerging primary amino groups was achieved.
机译：通过离子交换原位原位产生的金属叠氮化物在与环状N-烷氧基，甲硅烷胺反应中表现出发散的反应性。取决于金属的性质和[M] / N_3〜 - 比，将叠氮化物离子加入C，C双键与外部或内循环的区域选择性切割没有导致循环或开放的粘合连锁A-亚氮肟衍生物。机械研究与溶剂状态FTIR光谱和DFT计算结合揭示了通过路易斯酸辅助S_N'替代的三烷基甲硅烷基溶解的C-C-双键的共价结合金属叠氮化物（CO，Cu，Zn）转移N_3〜 - 双键 - 团体。更多离子金属叠氮化物（N1，Mg，Al，Sc，Ni，Yb）倾向于通过在硅原子上产生共轭亚硝基烯烃的N_3〜 - 阴离子的初始亲核侵蚀反应。通过使用所设计的方案制备的A-氮杂肟衍生物是立体化的，对高达四个连续的立体醇的有价值的1,2-二氨基醇。通过以逐步的方式减少α-氮杂肟片段，达到每种新出现的初级氨基的选择性保护和还原胺化。

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  • 来源
    《Chemistry: A European journal》 |2017年第19期|共9页
  • 作者

    Petr A. Zhmurov; Yulia A. Khoroshutina; Roman A. Novikov; Ivan S. Golovanov; Alexey Yu. Sukhorukov; Sema L. Ioffe;

  • 作者单位

    Laboratory of Functional Organic Compounds N. D. Zelinsky Institute of Organic Chemistry 119991 Leninsky Prospect 47 Moscow (Russia);

    Laboratory of Functional Organic Compounds N. D. Zelinsky Institute of Organic Chemistry 119991 Leninsky Prospect 47 Moscow (Russia);

    Laboratory of Functional Organic Compounds N. D. Zelinsky Institute of Organic Chemistry 119991 Leninsky Prospect 47 Moscow (Russia);

    Laboratory of Functional Organic Compounds N. D. Zelinsky Institute of Organic Chemistry 119991 Leninsky Prospect 47 Moscow (Russia);

    Laboratory of Functional Organic Compounds N. D. Zelinsky Institute of Organic Chemistry 119991 Leninsky Prospect 47 Moscow (Russia);

    Laboratory of Functional Organic Compounds N. D. Zelinsky Institute of Organic Chemistry 119991 Leninsky Prospect 47 Moscow (Russia);

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 应用化学;
  • 关键词

    1; 2-diamines; Lewis acids; metal azides; nitrogen-oxygen bond; organic azides;

    机译：1;2-二胺;路易斯酸;金属叠氮化物;氮氧键;有机叠氮化物;

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