Tian Miaomiao, He Yan, Zhang Xinying, Fan Xuesen
School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Key Laboratory for Environmental Pollution Control, Henan Normal University, Xinxiang, Henan 453007, China.
J Org Chem. 2015 Aug 7;80(15):7447-55. doi: 10.1021/acs.joc.5b00997. Epub 2015 Jul 20.
A novel and efficient method for the construction of the pyrazolo[5,1-a]isoindole scaffold via a one-pot three-component cascade reaction of 1-(2-bromophenyl)buta-2,3-dien-1-one with hydrazine and isocyanide promoted by a Pd catalyst is described. This cascade process proceeds through initial condensation of the allenic ketone with hydrazine followed by Pd-catalyzed isocyanide insertion into the C-Br bond and intramolecular C-N bond formation. Interestingly, when acetohydrazide was used in place of hydrazine, a more sophisticated procedure involving condensation, isocyanide insertion into C-H and C-Br bonds, deacetylation, and formation of C-C, C-O, and C-N bonds occurred to afford pyrazolo[5,1-a]isoindole-3-carboxamides with good efficiency.
描述了一种新颖且高效的方法,通过钯催化剂促进的1-(2-溴苯基)丁-2,3-二烯-1-酮与肼和异腈的一锅三组分串联反应来构建吡唑并[5,1-a]异吲哚骨架。该串联过程首先通过烯丙基酮与肼的缩合,然后是钯催化的异腈插入C-Br键并形成分子内C-N键。有趣的是,当用乙酰肼代替肼时,会发生一个更复杂的过程,包括缩合、异腈插入C-H和C-Br键、脱乙酰化以及C-C、C-O和C-N键的形成,从而高效地得到吡唑并[5,1-a]异吲哚-3-甲酰胺。