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Oxidation of a P−C Bond under Mild Conditions
Author(s) -
Ilić Gordana,
Gaguly Rakesh,
Petković Milena,
Vidović Dragoslav
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201503922
Subject(s) - dication , chemistry , pyridine , reactivity (psychology) , ligand (biochemistry) , medicinal chemistry , stereochemistry , nucleophile , ring (chemistry) , oxygen , photochemistry , molecule , catalysis , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
The reactivity of phosphenium dication [(Ph 3 P) 2 C‐P‐N i Pr 2 ] 2+ , 1 2+ , towards pyridine N‐oxide (O‐py) has been investigated. The resulting oxophosphonium dication [(Ph 3 P) 2 C(N i Pr 2 )P(O)(O‐py)] 2+ , 2 2+ , was surprisingly stabilized by a less nucleophilic O‐py ligand instead of pyridine (py). This compound was then identified as an analogue of the elusive Criegee intermediate as it underwent oxygen insertion into the P−C bond through a mechanism usually observed for Baeyer–Villiger oxidations. This oxygen insertion appears to be the first example of a Baeyer–Villiger oxidation involving O‐py.