Department of Chemistry , Lomonosov Moscow State University , Leninskie gory 1-3 , Moscow 119991 , Russia.
Institute of Bioorganic Chemistry , Uzbek Academy of Sciences , Mirzo Ulugbek str. 83 , Tashkent 100125 , Uzbekistan.
Org Lett. 2019 Feb 15;21(4):1087-1092. doi: 10.1021/acs.orglett.8b04135. Epub 2019 Feb 7.
Transformations of α-EWG-substituted (electron-withdrawing group, EWG) γ-azidobutyronitriles proceeding via unusual aza-Wittig reactions between the phosphazene and nitrile functions and affording pyrrole-derived iminophosphazenes were developed. α-EWGs were found to control chemoselectivity and, depending on their nature, act as CN group activators (e.g., ester, amide, or nitrile) or competitors (e.g., ketone) in aza-Wittig reactions. To demonstrate the synthetic utility of the obtained iminophosphazenes as N, N-binucleophiles, their transformations into pyrrole-fused systems, pyrrolo[1,2- a]imidazoles and pyrrolo[1,2- a][1,3]diazepines, were carried out.
发展了通过磷氮烯和腈官能团之间不寻常的氮杂 Wittig 反应进行的α-EWG-取代（吸电子基团，EWG）γ-叠氮丁腈的转化，并得到吡咯衍生的亚氨基磷氮杂环戊二烯。发现α-EWGs 可以控制化学选择性，并且根据其性质，在氮杂 Wittig 反应中充当 CN 基团的活化剂（例如酯、酰胺或腈）或竞争者（例如酮）。为了证明所获得的亚氨基磷氮杂环戊二烯作为 N，N-双亲核试剂的合成实用性，将其转化为吡咯稠合体系、吡咯并[1,2-a]咪唑和吡咯并[1,2-a][1,3]二氮杂环庚烷。
