TY - JOUR
T1 - An Iron-Catalyzed Route to Dewar 1,3,5-triphosphabenzene and Subsequent Reactivity
AU - Barrett, Adam N.
AU - Diefenbach, Martin
AU - Mahon, Mary F.
AU - Krewald, Vera
AU - Webster, Ruth L.
N1 - Engineering and Physical Sciences Research Council (Grant number(s): EP/P024254/1; Grant recipient(s): Ruth L. Webster, Adam N. Barrett);
Leverhulme Trust (Grant number(s): RPG-2020-3
PY - 2022/9/12
Y1 - 2022/9/12
N2 - 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.
AB - 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.
KW - Electrophilic Addition
KW - Iron
KW - Nucleophilic Addition
KW - Phosphorus Heterocycles
KW - Reaction Mechanisms
UR - http://www.scopus.com/inward/record.url?scp=85135760547&partnerID=8YFLogxK
U2 - 10.1002/ange.202208663
DO - 10.1002/ange.202208663
M3 - Article
SN - 1433-7851
VL - 61
JO - Angewandte Chemie-International Edition
JF - Angewandte Chemie-International Edition
IS - 37
M1 - e202208663
ER -