无过渡金属超碱催化的醛亚胺与乙炔的C-H乙烯基化反应合成1-氮杂二烯
Transition-Metal-Free Superbase-Catalyzed C-H Vinylation of Aldimines with Acetylenes to 1-Azadienes.
作者信息
Schmidt Elena Yu, Bidusenko Ivan A, Protsuk Nadezhda I, Demyanov Yan V, Ushakov Igor A, Vashchenko Alexander V, Trofimov Boris A
机构信息
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation.
出版信息
J Org Chem. 2020 Mar 6;85(5):3417-3425. doi: 10.1021/acs.joc.9b03192. Epub 2020 Feb 14.
Aldimines react with aryl- and hetarylacetylenes in the presence of KOBu/dimethyl sulfoxide (DMSO) or NaOBu/DMSO systems under exceptionally mild conditions (14 °C, 1 h) to afford C-H-vinylated products, 1-azadienes of configuration relative to the C-C bond, in up to 72% yield. Vinylation involves the unprecedentedly fast multiposition proton transfer in the intermediate adducts of acetylene to the C═N bond. This new Csp-Csp bond-forming reaction opens a straightforward pot-, atom-, step-, and energy-economic access to synthetically valuable 1-azadienes.
在叔丁醇钾/二甲基亚砜（DMSO）或叔丁醇钠/DMSO体系存在下，醛亚胺与芳基乙炔和杂芳基乙炔在异常温和的条件下（14℃，1小时）反应，生成C-H-乙烯基化产物，即相对于C-C键具有特定构型的1-氮杂二烯，产率高达72%。乙烯基化涉及乙炔与C═N键的中间体加合物中前所未有的快速多位置质子转移。这种新的Csp-Csp键形成反应为合成有价值的1-氮杂二烯提供了一种直接的、一锅法、原子经济、步骤经济和能量经济的途径。
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