Copper‐Catalyzed Ring‐Expansion/Thiolactonization via Azidation of Internal Olefinic C–H Bond under Mild Conditions,Advanced Synthesis & Catalysis

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Copper‐Catalyzed Ring‐Expansion/Thiolactonization via Azidation of Internal Olefinic C–H Bond under Mild Conditions
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2016-09-15 , DOI: 10.1002/adsc.201600675
Tenglong Guo ₁ , Quanbin Jiang ₁ , Zhengkun Yu _{1,

2}

Affiliation

A copper(I)‐catalyzed, (diacetoxyiodo)benzene [PhI(OAc)₂]‐mediated ring‐expansion/thiolactonization of α‐oxo ketene dithioacetals was efficiently realized via azidation of the internal olefinic C−H bond with sodium azide under mild conditions. Sequential amination, ring‐expansion rearrangement, and thiolactonization occurred to form aminated thiolactones in the presence of acetic anhydride as the additive, while only C−H amination to afford the unprotected enamines occurred when using ammonium sulfide as a reducing additive. The in situ generated vinyl azides were confirmed as the reactive intermediates, which were captured by phenylacetylene to produce triazoles. This protocol provides a concise route to thiolactone derivatives and unprotected enamines.

中文翻译：

在温和条件下通过内部烯烃C–H键的叠氮化进行铜催化的扩环/硫内酯化

通过在温和的条件下用叠氮化钠将内部C-H键与叠氮化钠叠氮化可以有效地实现铜（I）催化的（diacetoxyiodo）苯[PhI（OAc）₂ ]介导的α-氧代乙烯酮二硫缩醛的扩环/硫内酯化反应条件。在使用乙酸酐作为添加剂的情况下，发生了顺序胺化，扩环重排和硫代内酯化反应，形成胺化的硫内酯，而当使用硫化铵作为还原性添加剂时，只有进行C-H胺化处理才能得到未保护的烯胺。该原位生成的乙烯基叠氮化物被证实为活性中间体，这是由苯乙炔捕获，以产生三唑。该方案为硫代内酯衍生物和未保护的烯胺提供了一条简明的途径。

更新日期：2016-09-15

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