Alemán José, Humbrías-Martín Jorge, Del Río-Rodríguez Roberto, Aguilar-Galindo Fernando, Díaz-Tendero Sergio, Fernández-Salas Jose A
Departamento de Química Orgánica (módulo 1), Universidad Autónoma de Madrid, Cantoblanco, Madrid, Spain.
Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Madrid, Spain.
Nat Commun. 2024 Jun 3;15(1):4727. doi: 10.1038/s41467-024-48832-x.
Herein, an enantioselective desymmetrization of cyclic keto sulfonium salts through enantioselective deprotonation/ring opening process by anion-binding catalysis is presented. We report a squaramide/HCO complex as catalytic active species which is able to stereo-differentiate two enantiomeric protons, triggering the ring opening event taking advantage of the great tendency of sulfonium salts to act as leaving groups. Thus, this desymmetrization methodology give rise to β-methylsulfenylated sulfa-Michael addition type products with excellent yields and very good enantioselectivities. The bifunctional organocatalyst has been demonstrated to be capable of activating simultaneously the base and the keto sulfonium salt by DFT calculations and experimental proofs.
在此，我们报道了一种通过阴离子结合催化的对映选择性去质子化/开环过程实现环状酮锍盐的对映选择性去对称化反应。我们报告了一种方酰胺/HCO络合物作为催化活性物种，它能够立体区分两个对映体质子，利用锍盐作为离去基团的强烈倾向引发开环反应。因此，这种去对称化方法能以优异的产率和非常好的对映选择性得到β-甲基亚磺酰基硫醚-Michael加成型产物。通过密度泛函理论计算和实验证明，这种双功能有机催化剂能够同时活化碱和酮锍盐。
