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Gold(I)‐Catalyzed Conia‐ene Cyclization of Internal ϵ‐Acetylenic β‐Ketoesters under High Pressure.
ChemCatChem ( IF 4.5 ) Pub Date : 2017-12-08 , DOI: 10.1002/cctc.201701388
Wojciech Chaładaj 1 , Agata Kołodziejczyk 1, 2 , Sylwester Domański 1
Affiliation  

The influence of pressure on the gold(I)‐catalyzed Conia‐ene cyclization of ϵ‐acetylenic‐β‐ketoesters bearing an internal alkyne moiety was investigated for the first time. The reaction catalyzed by commercially available PPh3AuNTf2 complex, which is sluggish at ambient pressure owing to steric reasons, proceeds smoothly under high‐pressure conditions (6 kbar). Mechanistic aspects of the reaction proceeding via 5exo‐dig and 6endo‐dig cyclization pathways were also studied employing DFT methods. Differences in the reactivity of substrates containing terminal and internal alkynes is discussed.

中文翻译:

高压下金(I)催化的内部ϵ-乙炔β-酮酸酯的对苯二烯环化反应。

压力对金(I)的影响催化的的Conia烯环化ε -acetylenic-β酮酯轴承内部炔部分进行了研究,第一次。由商业上可获得的PPh 3 AuNTf 2络合物催化的反应由于在空间压力下由于空间原因而缓慢,在高压条件下(6 kbar)顺利进行。通过反应的进行的机械方面5 -外切挖6 -内切挖环化途径进行了研究采用DFT方法。讨论了包含末端炔烃和内部炔烃的底物反应性的差异。
更新日期:2017-12-08
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