Selective [3+1] Fragmentations of P4by “P” Transfer from a Lewis Acid Stabilized [RP4]Butterfly Anion

Jaap E. Borger, Andreas W. Ehlers, Martin Lutz, J. Chris Slootweg, Koop Lammertsma

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P4⋅ BPh3] (Mes*=2,4,6-tBu3C6H2) are reported. The reactions proceed by extrusion of a P1fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P3, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P1- and P3-containing organophosphorus compounds in two simple steps from white phosphorus.

Original languageEnglish
Pages (from-to)285-290
Number of pages6
JournalAngewandte Chemie - International Edition
Volume56
Issue number1
DOIs
Publication statusPublished - 2017

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Organophosphorus Compounds
Lewis Acids
Discrete Fourier transforms
Dimers
Phosphorus
Anions
Extrusion
Negative ions
Salts
Acids
1,3-cyclohexadiene

Keywords

  • anions
  • fragmentation
  • Lewis acids
  • organophosphorus compounds
  • phosphorus

Cite this

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title = "Selective [3+1] Fragmentations of P4by “P” Transfer from a Lewis Acid Stabilized [RP4]−Butterfly Anion",
abstract = "Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P4⋅ BPh3] (Mes*=2,4,6-tBu3C6H2) are reported. The reactions proceed by extrusion of a P1fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P3, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P1- and P3-containing organophosphorus compounds in two simple steps from white phosphorus.",
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author = "Borger, {Jaap E.} and Ehlers, {Andreas W.} and Martin Lutz and Slootweg, {J. Chris} and Koop Lammertsma",
year = "2017",
doi = "10.1002/anie.201607234",
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Selective [3+1] Fragmentations of P4by “P” Transfer from a Lewis Acid Stabilized [RP4]Butterfly Anion. / Borger, Jaap E.; Ehlers, Andreas W.; Lutz, Martin; Slootweg, J. Chris; Lammertsma, Koop.

In: Angewandte Chemie - International Edition, Vol. 56, No. 1, 2017, p. 285-290.

Research output: Contribution to JournalArticleAcademicpeer-review

TY - JOUR

T1 - Selective [3+1] Fragmentations of P4by “P” Transfer from a Lewis Acid Stabilized [RP4]−Butterfly Anion

AU - Borger, Jaap E.

AU - Ehlers, Andreas W.

AU - Lutz, Martin

AU - Slootweg, J. Chris

AU - Lammertsma, Koop

PY - 2017

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N2 - Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P4⋅ BPh3] (Mes*=2,4,6-tBu3C6H2) are reported. The reactions proceed by extrusion of a P1fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P3, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P1- and P3-containing organophosphorus compounds in two simple steps from white phosphorus.

AB - Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P4⋅ BPh3] (Mes*=2,4,6-tBu3C6H2) are reported. The reactions proceed by extrusion of a P1fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P3, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P1- and P3-containing organophosphorus compounds in two simple steps from white phosphorus.

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