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Synthesis of five-membered unsaturated compounds from ketones via cyanophosphates under neutral conditions: [1,5]-CH insertion of alkylidene carbenes generated by tetrazole fragmentation
Tetrahedron ( IF 2.1 ) Pub Date : 2017-09-04 , DOI: 10.1016/j.tet.2017.08.054
Hiroki Yoneyama , Kenji Uemura , Yoshihide Usami , Shinya Harusawa

Cyanophosphates (CPs) can easily be prepared via the reactions of carbonyl compounds with diethyl phosphorocyanidate (DEPC) in the presence of LiCN (cat.) under non-aqueous conditions. Treatment of ketone-derived CPs with TMSN3/Bu2SnO (cat.) in toluene at reflux produces cyclopentenes or heterocyclic products in good yields under neutral conditions. In this two-step transformation, CPs may form tetrazolylphosphates, which subsequently undergo successive fragmentation to generate alkylidene carbenes, which undergo [1,5]-C–H insertions to yield five membered compounds.



中文翻译:

在中性条件下通过氰基磷酸酯从酮合成五元不饱和化合物:四唑裂解生成的亚烷基卡宾[1,5] -CH插入

在非水条件下,在LiCN(cat。)存在下,羰基化合物与磷腈二乙酯(DEPC)的反应可轻松制得氰基磷酸盐(CPs)。在中性条件下,用甲苯中的TMSN 3 / Bu 2 SnO(cat。)在甲苯中处理酮衍生的CP,可以高产率生产环戊烯或杂环产物。在此两步转化过程中,CP可能形成四唑基磷酸酯,随后对其进行连续裂解以生成亚烷基卡宾,这些卡宾经过[1,5] -CH插入可生成五元化合物。

更新日期:2017-09-04
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