Regioselective formation of a 2,3-oxaphosphabicyclo[2.2.2] octene 3-oxide in baeyer-villiger type oxidation; a dual pathway for its fragmentation

Stefan Jankowski, János Kovács, Krzysztof Huben, Michał Błaszczyk, Marek Glówka, G. Keglevich

Research output: Contribution to journalArticle

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Abstract

The O-insertion reaction of a 7-phosphanorbornene (3) unsubstituted on the double-bond gave the corresponding 2,3-oxaphosphabicyclo-[2.2.2]octene oxide (4a) in a regioselective manner that was useful in the fragmentation-related phosphonylation of alcohols. Both the UV-light mediated and the thermoinduced phosponylation accomplished on the bridged P-heterocycle (4a) were found to be sensitive toward steric factors, suggesting that beside the well-known elimination-addition reaction path taking place via metaphosphonate (11), a competitive novel addition-elimination route involving an intermediate with a pentacoordinated P-atom (12) is also present. This was confirmed by the kinetic consideration of our experimental data.

Original languageEnglish
Pages (from-to)369-375
Number of pages7
JournalHeteroatom Chemistry
Volume17
Issue number5
DOIs
Publication statusPublished - 2006

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Addition reactions
Ultraviolet radiation
Oxides
Alcohols
Atoms
Oxidation
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)

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Regioselective formation of a 2,3-oxaphosphabicyclo[2.2.2] octene 3-oxide in baeyer-villiger type oxidation; a dual pathway for its fragmentation. / Jankowski, Stefan; Kovács, János; Huben, Krzysztof; Błaszczyk, Michał; Glówka, Marek; Keglevich, G.

In: Heteroatom Chemistry, Vol. 17, No. 5, 2006, p. 369-375.

Research output: Contribution to journalArticle

Jankowski, Stefan ; Kovács, János ; Huben, Krzysztof ; Błaszczyk, Michał ; Glówka, Marek ; Keglevich, G. / Regioselective formation of a 2,3-oxaphosphabicyclo[2.2.2] octene 3-oxide in baeyer-villiger type oxidation; a dual pathway for its fragmentation. In: Heteroatom Chemistry. 2006 ; Vol. 17, No. 5. pp. 369-375.
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