Direct esterification of phosphinic acids under microwave conditions: Extension to the synthesis of thiophosphinates and new mechanistic insights

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Abstract

The direct esterification of phosphinic acids has been extended to the preparation of thiophosphinates using thiols, but the conversions are only ca. 50%. The outcome is in agreement with the unexpectedly high enthalpy of activation and endothermicity suggested by quantum chemical calculations. At the same time, formation of the thiophosphinates confirms the AAC2 (phosphinylation) mechanism and excludes the SN reaction paths. Formation of an olefinic intermediate under the reaction conditions is also excluded experimentally.

Original languageEnglish
Pages (from-to)466-469
Number of pages4
JournalTetrahedron Letters
Volume54
Issue number6
DOIs
Publication statusPublished - Feb 6 2013

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Phosphinic Acids
Esterification
Microwaves
Sulfhydryl Compounds
Enthalpy
Chemical activation

Keywords

  • Esterification
  • Mechanism
  • Microwave
  • Phosphinic acids
  • Theoretical calculations
  • Thiophosphinates

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

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title = "Direct esterification of phosphinic acids under microwave conditions: Extension to the synthesis of thiophosphinates and new mechanistic insights",
abstract = "The direct esterification of phosphinic acids has been extended to the preparation of thiophosphinates using thiols, but the conversions are only ca. 50{\%}. The outcome is in agreement with the unexpectedly high enthalpy of activation and endothermicity suggested by quantum chemical calculations. At the same time, formation of the thiophosphinates confirms the AAC2 (phosphinylation) mechanism and excludes the SN reaction paths. Formation of an olefinic intermediate under the reaction conditions is also excluded experimentally.",
keywords = "Esterification, Mechanism, Microwave, Phosphinic acids, Theoretical calculations, Thiophosphinates",
author = "G. Keglevich and Kiss, {N{\'o}ra Zsuzsa} and L. Drahos and T. K{\"o}rtv{\'e}lyesi",
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T1 - Direct esterification of phosphinic acids under microwave conditions

T2 - Extension to the synthesis of thiophosphinates and new mechanistic insights

AU - Keglevich, G.

AU - Kiss, Nóra Zsuzsa

AU - Drahos, L.

AU - Körtvélyesi, T.

PY - 2013/2/6

Y1 - 2013/2/6

N2 - The direct esterification of phosphinic acids has been extended to the preparation of thiophosphinates using thiols, but the conversions are only ca. 50%. The outcome is in agreement with the unexpectedly high enthalpy of activation and endothermicity suggested by quantum chemical calculations. At the same time, formation of the thiophosphinates confirms the AAC2 (phosphinylation) mechanism and excludes the SN reaction paths. Formation of an olefinic intermediate under the reaction conditions is also excluded experimentally.

AB - The direct esterification of phosphinic acids has been extended to the preparation of thiophosphinates using thiols, but the conversions are only ca. 50%. The outcome is in agreement with the unexpectedly high enthalpy of activation and endothermicity suggested by quantum chemical calculations. At the same time, formation of the thiophosphinates confirms the AAC2 (phosphinylation) mechanism and excludes the SN reaction paths. Formation of an olefinic intermediate under the reaction conditions is also excluded experimentally.

KW - Esterification

KW - Mechanism

KW - Microwave

KW - Phosphinic acids

KW - Theoretical calculations

KW - Thiophosphinates

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EP - 469

JO - Tetrahedron Letters

JF - Tetrahedron Letters

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