The effect of a sterically demanding P-substituent on the reactivity of P-heterocycles

Selective transformations during the ring enlargement of a 1-(2,4,6-triisopropylphenyl)-2,5-dihydro-1H-phosphole 1-oxide

G. Keglevich, Gyorgy Miklôs Keserû, Henrietta Forintos, A. Szöllösy, K. Ludányi, L. Tőke

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Abstract

Dichlorocyclopropanation of the title dihydrophosphole oxide (5) by CHCl3-NaOH/H2O under phase transfer catalysis (PTC) gave adduct 6A in a selectivity of 80%. The use of sodium trichloroacetate as the precursor of dichlorocarbene resulted in, however, the exclusive formation of the other isomer (6B) exhibiting the same stereostructure, as the product formed in the liquid-liquid two-phase dichlorocyclopropanation of the phenyldihydrophosphole (1). The base- and thermo-induced cyclopropane ring opening of the adducts (6A and 6B) led, surprisingly, to distinct dihydrophosphinine isomers (7 and 8, respectively) in a fully selective manner. The unusual reactivity of the P-heterocycIes (5 and 6) is due to the sterically demanding P-aryl substituent. Semiempirical calculations on the .P-aryl dihydrophosphinines (7 and 8) revealed a geometry and electron distribution that explains the unique NMR features observed.

Original languageEnglish
Pages (from-to)1801-1805
Number of pages5
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number13
Publication statusPublished - 1999

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Isomers
Oxides
Trichloroacetic Acid
Catalyst selectivity
Liquids
Catalysis
Nuclear magnetic resonance
Geometry
Electrons
dichlorocarbene
cyclopropane

ASJC Scopus subject areas

  • Chemistry(all)
  • Organic Chemistry

Cite this

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title = "The effect of a sterically demanding P-substituent on the reactivity of P-heterocycles: Selective transformations during the ring enlargement of a 1-(2,4,6-triisopropylphenyl)-2,5-dihydro-1H-phosphole 1-oxide",
abstract = "Dichlorocyclopropanation of the title dihydrophosphole oxide (5) by CHCl3-NaOH/H2O under phase transfer catalysis (PTC) gave adduct 6A in a selectivity of 80{\%}. The use of sodium trichloroacetate as the precursor of dichlorocarbene resulted in, however, the exclusive formation of the other isomer (6B) exhibiting the same stereostructure, as the product formed in the liquid-liquid two-phase dichlorocyclopropanation of the phenyldihydrophosphole (1). The base- and thermo-induced cyclopropane ring opening of the adducts (6A and 6B) led, surprisingly, to distinct dihydrophosphinine isomers (7 and 8, respectively) in a fully selective manner. The unusual reactivity of the P-heterocycIes (5 and 6) is due to the sterically demanding P-aryl substituent. Semiempirical calculations on the .P-aryl dihydrophosphinines (7 and 8) revealed a geometry and electron distribution that explains the unique NMR features observed.",
author = "G. Keglevich and Keser{\^u}, {Gyorgy Mikl{\^o}s} and Henrietta Forintos and A. Sz{\"o}ll{\"o}sy and K. Lud{\'a}nyi and L. Tőke",
year = "1999",
language = "English",
pages = "1801--1805",
journal = "Journal of the Chemical Society, Perkin Transactions 1",
issn = "1472-7781",
publisher = "Chemical Society",
number = "13",

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TY - JOUR

T1 - The effect of a sterically demanding P-substituent on the reactivity of P-heterocycles

T2 - Selective transformations during the ring enlargement of a 1-(2,4,6-triisopropylphenyl)-2,5-dihydro-1H-phosphole 1-oxide

AU - Keglevich, G.

AU - Keserû, Gyorgy Miklôs

AU - Forintos, Henrietta

AU - Szöllösy, A.

AU - Ludányi, K.

AU - Tőke, L.

PY - 1999

Y1 - 1999

N2 - Dichlorocyclopropanation of the title dihydrophosphole oxide (5) by CHCl3-NaOH/H2O under phase transfer catalysis (PTC) gave adduct 6A in a selectivity of 80%. The use of sodium trichloroacetate as the precursor of dichlorocarbene resulted in, however, the exclusive formation of the other isomer (6B) exhibiting the same stereostructure, as the product formed in the liquid-liquid two-phase dichlorocyclopropanation of the phenyldihydrophosphole (1). The base- and thermo-induced cyclopropane ring opening of the adducts (6A and 6B) led, surprisingly, to distinct dihydrophosphinine isomers (7 and 8, respectively) in a fully selective manner. The unusual reactivity of the P-heterocycIes (5 and 6) is due to the sterically demanding P-aryl substituent. Semiempirical calculations on the .P-aryl dihydrophosphinines (7 and 8) revealed a geometry and electron distribution that explains the unique NMR features observed.

AB - Dichlorocyclopropanation of the title dihydrophosphole oxide (5) by CHCl3-NaOH/H2O under phase transfer catalysis (PTC) gave adduct 6A in a selectivity of 80%. The use of sodium trichloroacetate as the precursor of dichlorocarbene resulted in, however, the exclusive formation of the other isomer (6B) exhibiting the same stereostructure, as the product formed in the liquid-liquid two-phase dichlorocyclopropanation of the phenyldihydrophosphole (1). The base- and thermo-induced cyclopropane ring opening of the adducts (6A and 6B) led, surprisingly, to distinct dihydrophosphinine isomers (7 and 8, respectively) in a fully selective manner. The unusual reactivity of the P-heterocycIes (5 and 6) is due to the sterically demanding P-aryl substituent. Semiempirical calculations on the .P-aryl dihydrophosphinines (7 and 8) revealed a geometry and electron distribution that explains the unique NMR features observed.

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