Reaction of elemental phosphorus with α-methylstyrenes

One-pot synthesis of secondary and tertiary phosphines, prospective bulky ligands for Pd(II) catalysts

Alexander V. Artem'ev, Svetlana F. Malysheva, Nina K. Gusarova, Nataliya A. Belogorlova, Boris G. Sukhov, Anastasiya O. Sutyrina, Elena A. Matveeva, Sergey F. Vasilevsky, Anastasiya I. Govdi, Yuriy V. Gatilov, Alexander I. Albanov, Boris A. Trofimov

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

α-Methylstyrene and 4-chloro-α-methylstyrene react readily with elemental (red) phosphorus under microwave-irradiation in the superbase KOH/DMSO suspension to afford, depending on the reactant ratio and reaction time, either corresponding bis(2-arylpropyl)phosphines or tris(2-arylpropyl)phosphines in 46-54% and 69-77% yields, respectively. Upon the heating only (110-130 °C, 3 h), this reaction provides mainly tris(2-arylpropyl)phosphine oxides (up to 78% yield) along with (2-arylpropyl)phosphinic acids (up to 43%). The synthesized phosphines are prospective bulky ligands for metal catalysts that has been demonstrated by the preparation of a new Pd(II) complex, trans-[Pd(PR 3 ) 2 Cl 2 ], which proves to be active in the Sonogashira couplings.

Original languageEnglish
Pages (from-to)443-450
Number of pages8
JournalTetrahedron
Volume72
Issue number4
DOIs
Publication statusPublished - 28 Jan 2016
Externally publishedYes

Fingerprint

Phosphines
Phosphorus
phosphine
Ligands
Catalysts
Phosphinic Acids
Microwave irradiation
Microwaves
Dimethyl Sulfoxide
Heating
Oxides
Suspensions
Metals
vinyltoluene

Keywords

  • Elemental phosphorus
  • Phosphines
  • Sonogashira coupling
  • Superbases
  • α-Methylstyrene

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Artem'ev, A. V., Malysheva, S. F., Gusarova, N. K., Belogorlova, N. A., Sukhov, B. G., Sutyrina, A. O., ... Trofimov, B. A. (2016). Reaction of elemental phosphorus with α-methylstyrenes: One-pot synthesis of secondary and tertiary phosphines, prospective bulky ligands for Pd(II) catalysts. Tetrahedron, 72(4), 443-450. https://doi.org/10.1016/j.tet.2015.11.009

Reaction of elemental phosphorus with α-methylstyrenes : One-pot synthesis of secondary and tertiary phosphines, prospective bulky ligands for Pd(II) catalysts. / Artem'ev, Alexander V.; Malysheva, Svetlana F.; Gusarova, Nina K.; Belogorlova, Nataliya A.; Sukhov, Boris G.; Sutyrina, Anastasiya O.; Matveeva, Elena A.; Vasilevsky, Sergey F.; Govdi, Anastasiya I.; Gatilov, Yuriy V.; Albanov, Alexander I.; Trofimov, Boris A.

In: Tetrahedron, Vol. 72, No. 4, 28.01.2016, p. 443-450.

Research output: Contribution to journalArticle

Artem'ev, AV, Malysheva, SF, Gusarova, NK, Belogorlova, NA, Sukhov, BG, Sutyrina, AO, Matveeva, EA, Vasilevsky, SF, Govdi, AI, Gatilov, YV, Albanov, AI & Trofimov, BA 2016, 'Reaction of elemental phosphorus with α-methylstyrenes: One-pot synthesis of secondary and tertiary phosphines, prospective bulky ligands for Pd(II) catalysts', Tetrahedron, vol. 72, no. 4, pp. 443-450. https://doi.org/10.1016/j.tet.2015.11.009
Artem'ev, Alexander V. ; Malysheva, Svetlana F. ; Gusarova, Nina K. ; Belogorlova, Nataliya A. ; Sukhov, Boris G. ; Sutyrina, Anastasiya O. ; Matveeva, Elena A. ; Vasilevsky, Sergey F. ; Govdi, Anastasiya I. ; Gatilov, Yuriy V. ; Albanov, Alexander I. ; Trofimov, Boris A. / Reaction of elemental phosphorus with α-methylstyrenes : One-pot synthesis of secondary and tertiary phosphines, prospective bulky ligands for Pd(II) catalysts. In: Tetrahedron. 2016 ; Vol. 72, No. 4. pp. 443-450.
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abstract = "α-Methylstyrene and 4-chloro-α-methylstyrene react readily with elemental (red) phosphorus under microwave-irradiation in the superbase KOH/DMSO suspension to afford, depending on the reactant ratio and reaction time, either corresponding bis(2-arylpropyl)phosphines or tris(2-arylpropyl)phosphines in 46-54{\%} and 69-77{\%} yields, respectively. Upon the heating only (110-130 °C, 3 h), this reaction provides mainly tris(2-arylpropyl)phosphine oxides (up to 78{\%} yield) along with (2-arylpropyl)phosphinic acids (up to 43{\%}). The synthesized phosphines are prospective bulky ligands for metal catalysts that has been demonstrated by the preparation of a new Pd(II) complex, trans-[Pd(PR 3 ) 2 Cl 2 ], which proves to be active in the Sonogashira couplings.",
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AU - Matveeva, Elena A.

AU - Vasilevsky, Sergey F.

AU - Govdi, Anastasiya I.

AU - Gatilov, Yuriy V.

AU - Albanov, Alexander I.

AU - Trofimov, Boris A.

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AB - α-Methylstyrene and 4-chloro-α-methylstyrene react readily with elemental (red) phosphorus under microwave-irradiation in the superbase KOH/DMSO suspension to afford, depending on the reactant ratio and reaction time, either corresponding bis(2-arylpropyl)phosphines or tris(2-arylpropyl)phosphines in 46-54% and 69-77% yields, respectively. Upon the heating only (110-130 °C, 3 h), this reaction provides mainly tris(2-arylpropyl)phosphine oxides (up to 78% yield) along with (2-arylpropyl)phosphinic acids (up to 43%). The synthesized phosphines are prospective bulky ligands for metal catalysts that has been demonstrated by the preparation of a new Pd(II) complex, trans-[Pd(PR 3 ) 2 Cl 2 ], which proves to be active in the Sonogashira couplings.

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