Angewandte Chemie International Edition · 2020 · 16 citations · 50 references
Natural SciencesChemistryComputational ChemistryOrganometallic ChemistryStructure-activity RelationshipsChemical BondingPhotocatalysisPhotochemical SynthesisPhotochemistryReaction MechanismsFrustrated Lewis PairsPhotocatalytic SynthesisPhotochemical Bond CleavagePhotochemical FunctionalizationPhotochemical RearrangementReaction Mechanism ElucidationRearrangement Reactions
Abstract An unprecedented photo‐promoted skeletal rearrangement reaction of phosphine–borane frustrated Lewis pairs, o‐(borylaryl)phosphines, involving cleavage of an unstrained sp 2 C–sp 3 C σ‐bond is reported. The reaction realizes an efficient synthesis of cyclic phosphonium borate compounds. The reaction mechanism via a boranorcaradiene intermediate is proposed based on theoretical calculations. This work sheds light on the new photoreactivity of phosphine–borane FLPs.
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