Oxidation of a P-C Bond under Mild Conditions

Oxidation of a P-C Bond under Mild Conditions

The reactivity of phosphenium dication [(Ph3P)2C-P-NiPr2]2+, 12+, towards pyridine N-oxide (O-py) has been investigated. The resulting oxophosphonium dication [(Ph3P)2C(NiPr2)P(O)(O-py)]2+, 22+, was surprisingly stabilized by a less nucleophilic O-py ligand instead of pyridine (py). This compound wa...

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Bibliographic Details
Main Authors: Ilić, Gordana, Gaguly, Rakesh, Petković, Milena, Vidović, Dragoslav
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2016
Subjects:
Baeyer-Villiger oxidation
phosphenium dication
Online Access:https://hdl.handle.net/10356/81917
http://hdl.handle.net/10220/39725
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Institution: Nanyang Technological University
Language: English
Description
Summary:The reactivity of phosphenium dication [(Ph3P)2C-P-NiPr2]2+, 12+, towards pyridine N-oxide (O-py) has been investigated. The resulting oxophosphonium dication [(Ph3P)2C(NiPr2)P(O)(O-py)]2+, 22+, 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[BOND]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.

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