School of Chemical Sciences, University of Auckland, 23 Symonds St, Auckland, 1010, New Zealand.
Angew Chem Int Ed Engl. 2017 Jun 19;56(26):7420-7424. doi: 10.1002/anie.201702727. Epub 2017 May 23.
The unexpected synthesis of industrially important N-vinyl amides directly from aldehydes and α,β-unsaturated N-vinyl amides from esters is reported. This reaction probably proceeds through an initial [3+2] azide-enolate cycloaddition involving a vinyl azide generated in situ. A survey of the reaction scope and preliminary mechanistic findings supported by quantum computational analysis are reported, with implications for the future development of atom-efficient amide synthesis. Intriguingly, this study suggests that (cautious) reevaluation of azidoethene as a synthetic reagent may be warranted.
本文报道了一种直接从醛和α,β-不饱和 N-乙烯基酰胺酯合成工业上重要的 N-乙烯基酰胺的意外方法。该反应可能通过涉及原位生成的乙烯基叠氮化物的初始[3+2]叠氮化物-烯醇化物环加成进行。本文还报道了对反应范围的调查和初步的量子计算分析支持的反应机理研究结果，这对未来发展高效原子经济性酰胺合成具有重要意义。有趣的是，该研究表明，有必要（谨慎）重新评估叠氮乙烯作为一种合成试剂的价值。
