Anionic Amino-Cope Rearrangement Cascade Synthesis of 2,4-Substituted Benzoate Esters from Acyclic Building Blocks
Anionic Amino-Cope Rearrangement Cascade Synthesis of 2,4-Substituted Benzoate Esters from Acyclic Building Blocks
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由无环结构单元阴离子氨基-Cope重排级联合成 2,4-取代苯甲酸酯
DOI：
10.1021/acs.orglett.2c03134
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发表时间：
2022
期刊：
影响因子：
5.2
通讯作者：
Njardarson, Jon T.
中科院分区：
文献类型：
--
作者：
Qureshi, M. Haziq;Njardarson, Jon T.
我们报道了一种新的阴离子级联反应，用于从外消旋的β-氟取代的共轭叔丁基亚胺和3-取代的2-丁烯酸甲酯中组装2，4-取代苯甲酸酯。二烯酸酯的形成触发了Mannich加成，然后是类似氨基的重排，这导致锂化烯胺立即消除了氟化物。新形成的1，4-二烯中间体含有一个高酸性的质子，该质子被自发地去质子化，导致简单的分子内环化，随后亚磺酰胺基团消除和芳构化。
We report a new anionic cascade for assembling 2,4-substituted benzoate esters in one pot from racemic β-fluoro-substituted conjugatedtert-butylsulfinyl imines and 3-substituted methyl 2-butenoates. Dienolate formation triggers a Mannich addition followed by an amino-Cope like rearrangement, which results in immediate elimination of fluoride by a lithiated enamine. The newly formed 1,4-diene intermediate contains a highly acidic proton which is spontaneously deprotonated, leading to a facile intramolecular cyclization followed by sulfinamide group elimination and aromatization.