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Rearrangements during Oxidations of the 9-Phosphabicyclo[6.1.0]nona-2,4,6-triene System: Formation of Phosphonin Oxides

Publication ,  Journal Article
Quin, LD; Rao, NS; Topping, RJ; McPhail, AT
Published in: Journal of the American Chemical Society
July 1, 1986

P-Phenyl and P-tert-butyl derivatives of the title compound react with hydrogen peroxide or tert-butyl hydroperoxide at -15 °C; the C-C bond of the three-membered ring is opened, and the first observable product is the cis,cis,cis,trans-phosphonin oxide. When this oxide warms to room temperature, intramolecular cycloaddition occurs to form the trans-3a,7a-dihydro-phosphindole oxide system. The products of both processes have the stereochemistry predicted from orbital symmetry rules; their structures were established by 31P, 1H, and 13C NMR studies, as well as by conversion to known derivatives. When oxygen was used as the oxidizing agent, a different product (anti-9-phenyl-9-phosphabicydo[4.2.1]nona-2,4,7-triene 9-oxide) was formed and was useful as a precursor, on ultraviolet irradiation, of syn-9-phenyl-9-phosphatricyclo[4.2.1.02,5]nona-3,7-diene oxide. This compound was also obtained by isomerization of the anti 9-phenyl derivative with water. These oxides were reduced to the phosphines, which were characterized by NMR techniques; the syn phenyl product, however, was unstable in concentrated media and unlike the anti isomer could not be isolated. The X-ray crystallographic analysis of syn-9-phenyl-9-phosphabi-cyclo[4.2.1]nona-2,4,7-triene confirmed the stereochemical assignment and provided a structural basis for other derivatives. © 1986, American Chemical Society. All rights reserved.

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

July 1, 1986

Volume

108

Issue

15

Start / End Page

4519 / 4526

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

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Quin, L. D., Rao, N. S., Topping, R. J., & McPhail, A. T. (1986). Rearrangements during Oxidations of the 9-Phosphabicyclo[6.1.0]nona-2,4,6-triene System: Formation of Phosphonin Oxides. Journal of the American Chemical Society, 108(15), 4519–4526. https://doi.org/10.1021/ja00275a044
Quin, L. D., N. S. Rao, R. J. Topping, and A. T. McPhail. “Rearrangements during Oxidations of the 9-Phosphabicyclo[6.1.0]nona-2,4,6-triene System: Formation of Phosphonin Oxides.” Journal of the American Chemical Society 108, no. 15 (July 1, 1986): 4519–26. https://doi.org/10.1021/ja00275a044.
Quin LD, Rao NS, Topping RJ, McPhail AT. Rearrangements during Oxidations of the 9-Phosphabicyclo[6.1.0]nona-2,4,6-triene System: Formation of Phosphonin Oxides. Journal of the American Chemical Society. 1986 Jul 1;108(15):4519–26.
Quin, L. D., et al. “Rearrangements during Oxidations of the 9-Phosphabicyclo[6.1.0]nona-2,4,6-triene System: Formation of Phosphonin Oxides.” Journal of the American Chemical Society, vol. 108, no. 15, July 1986, pp. 4519–26. Scopus, doi:10.1021/ja00275a044.
Quin LD, Rao NS, Topping RJ, McPhail AT. Rearrangements during Oxidations of the 9-Phosphabicyclo[6.1.0]nona-2,4,6-triene System: Formation of Phosphonin Oxides. Journal of the American Chemical Society. 1986 Jul 1;108(15):4519–4526.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

July 1, 1986

Volume

108

Issue

15

Start / End Page

4519 / 4526

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences