A Tunable Route for the Synthesis of Azomethine Imines and β-Aminocarbonyl Compounds from Alkenes
A Tunable Route for the Synthesis of Azomethine Imines and β-Aminocarbonyl Compounds from Alkenes
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DOI：
10.1021/ja305491t
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发表时间：
2012-10-03
影响因子：
15
通讯作者：
Beauchemin, Andre M.
中科院分区：
文献类型：
--
作者：
Clavette, Christian;Gan, Wei;Beauchemin, Andre M.
具有β-氨基甲酰基基序的环甲亚胺是从简单的烯烃和肼的起始原料中获得的。提出了一种涉及亚氨基-异氰酸酯中间体的热协同烯烃氨基甲基化反应途径，并得到了密度泛函理论计算的支持。该方法的一个显著特点是在形成的偶极中存在空间屏蔽，这允许通过层析或结晶轻松地提纯产物。此外，还报道了一种荧酮衍生试剂，该试剂可与几类烯烃反应，并允许将偶极温和地衍生化为β-氨基酰胺、β-氨基酯和β-氨基酸。
Cyclic azomethine imines possessing a beta-aminocarbonyl motif are accessed from simple alkene and hydrazone starting materials. A thermal, concerted alkene aminocarbonylation pathway involving an imino-isocyanate intermediate is proposed and supported by DFT calculations. A notable feature of the process is the steric shielding present in the dipoles formed, which allows for facile purification of the products by chromatography or crystallization. In addition, a fluorenone-derived reagent is reported, which provides reactivity with several alkene classes and allows for mild derivatization of the dipoles into beta-aminoamides, beta-aminoesters, and beta-amino acids.