Cleavage of the Inert C(sp<sup>2</sup>)–Ar σ-Bond of Alkenes by a Spatial Constrained Interaction with Phosphinidene
Junjian Wang, Donghui Wei, Zheng Duan, François Mathey
Abstract
[1 + 2] cycloaddition is a classical reaction between the electrophilic phosphinidene and an alkene. However, a spatial constraint blocks this well-known reaction and enables an unprecedented chemoselective C(sp2)–Ar σ-bond insertion of the alkene. The theoretical calculations demonstrate that this C–C bond cleavage is energetically feasible and thermodynamically favored through an electrophilic rearrangement and concomitant 1,9-aryl migration without involving any strained intermediate.
Topics & Concepts
PhosphinideneChemistryAlkeneElectrophileBond cleavageElectrophilic additionArylCleavage (geology)CycloadditionPhotochemistryStereochemistryMedicinal chemistryComputational chemistryOrganic chemistryCatalysisAlkylFracture (geology)EngineeringGeotechnical engineeringOrganoboron and organosilicon chemistrySynthesis and characterization of novel inorganic/organometallic compoundsAsymmetric Hydrogenation and Catalysis