Optimal Oriented External Electric Fields to Trigger a Barrierless Oxaphosphetane Ring Opening Step of the Wittig Reaction

• Published in: Chemistry : a European journal 2024-05, Vol.30 (27), p.e202400173-n/a
• Main Authors: Bofill, Josep Maria, Severi, Marco, Quapp, Wolfgang, Ribas‐Ariño, Jordi, P. R. Moreira, Ibério, Albareda, Guillermo
• Format: Article
• Language: English
• Subjects: Asymmetric synthesis; barrier breakdown; catastrophe theory in chemistry; Chemical synthesis; control theory in chemistry; Electric dipoles; Electric field strength; Electric fields; force displaced stationary points; optimal oriented external electric field; Organic chemistry; Ring opening; wittig reaction
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202400173

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. The perturbed potential energy surface of the oxaphosphetane ring opening due to the optimal electric field demonstrates that the process occurs by first breaking the P−C bond and then breaking the O−C bond.