Bofill Josep Maria, Severi Marco, Quapp Wolfgang, Ribas-Ariño Jordi, de P R Moreira Ibério, Albareda Guillermo
Departament de Química Inorgànica i Orgànica, Secció de Química Orgànica, Universitat de Barcelona, C/Martí i Franquès 1, 08028, Barcelona, Spain.
Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/Martí i Franquès 1, 08028, Barcelona, Spain.
Chemistry. 2024 May 14;30(27):e202400173. doi: 10.1002/chem.202400173. Epub 2024 Apr 9.
The Wittig reaction is one of the most important processes in organic chemistry for the asymmetric synthesis of olefinic compounds. In view of the increasingly acknowledged potentiality of the electric fields in promoting reactions, here we will consider the effect of the oriented external electric field (OEEF) on the second step of Wittig reaction (i. e. the ring opening oxaphosphetane) in a model system for non-stabilized ylides. In particular, we have determined the optimal direction and strength of the electric field that should be applied to annihilate the reaction barrier of the ring opening through the polarizable molecular electric dipole (PMED) model that we have recently developed. We conclude that the application of the optimal external electric field for the oxaphosphetane ring opening favours a Bestmann-like mechanism.
维蒂希反应是有机化学中用于烯烃化合物不对称合成的最重要过程之一。鉴于电场在促进反应方面的潜力日益得到认可，在此我们将考虑在非稳定叶立德的模型体系中，定向外部电场（OEEF）对维蒂希反应第二步（即氧杂磷杂环丁烷开环）的影响。特别是，我们通过最近开发的可极化分子电偶极（PMED）模型确定了应施加的电场的最佳方向和强度，以消除开环反应的势垒。我们得出结论，对氧杂磷杂环丁烷开环施加最佳外部电场有利于类似贝斯曼的反应机理。
