Angewandte Chemie - International Edition, volume 61, issue 37
An Iron‐Catalyzed Route to Dewar 1,3,5‐Triphosphabenzene and Subsequent Reactivity
A N Barrett
1
,
Martin Diefenbach
2
,
Mary F. Mahon
1
,
Vera Krewald
2
,
R L Webster
1
Publication type: Journal Article
Publication date: 2022-08-09
scimago Q1
SJR: 5.300
CiteScore: 26.6
Impact factor: 16.1
ISSN: 14337851, 15213773
General Chemistry
Catalysis
Abstract
The application of an alkyne cyclotrimerization regime with an [Fe(salen)]2 -μ-oxo (1) catalyst to triphenylmethylphosphaalkyne (2) yields gram-scale quantities of 2,4,6-tris(triphenylmethyl)-Dewar-1,3,5-triphosphabenzene (3). Bulky lithium salt LiHMDS facilitates a rearrangement of 3 to the 1,3,5-triphosphabenzene valence isomer (3'), which subsequently undergoes an intriguing phosphorus migration reaction to form the ring-contracted species (3''). Density functional theory calculations provide a plausible mechanism for this rearrangement. Given the stability of 3, a diverse array of unprecedented transformations was investigated. We report novel crystallographically characterized products of successful nucleophilic/electrophilic addition and protonation/oxidation reactions.
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