Mechanism of the Exchange Reaction of Halodiazirines with Nucleophiles Revisited. Synthesis of Neutral, Mono-or Dicationic 4-16-Membered Phosphorus Heterocycles - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 1996

Mechanism of the Exchange Reaction of Halodiazirines with Nucleophiles Revisited. Synthesis of Neutral, Mono-or Dicationic 4-16-Membered Phosphorus Heterocycles

Gilles Alcaraz
Valérie Piquet
  • Fonction : Auteur
Antoine Baceiredo
Françoise Dahan
  • Fonction : Auteur
Wolfgang W Schoeller
  • Fonction : Auteur
Guy Bertrand

Résumé

Trimethyl-, diphenylmethyl-, triphenyl-, diphenylthienyl-, and bis(dimethylamino)(isopropylthio)phosphine react with bromophenyldiazirine (1) giving cationic N,N′-bis(phosphine) adducts 2a-c, 7, and 8 in 83-95% yields. Depending on the experimental conditions used, addition of 1,2-bis(diphenylphosphino)ethane to 1 leads to dicationic 14-and monocationic seven-membered heterocycles 3 (90% yield) and 4 (60% yield) or cationic N,N′-bis(diphosphine) adduct 5 (86% yield); similarly, when diphenyl(isopropylthio)phosphine is used, competitive reactions occur, leading to cationic five-membered heterocycle 9 (34% yield) and/or N,N′-Bis(diphosphine) adduct 10 (65% yield). 1,3-bis-(diphenylphosphino)propane also reacts with 1, affording dicationic 16-membered heterocycle 6 (75% yield). Addition of bis(diisopropylamino)(trimethylstannyl)phosphine to 1 gives rise to a mixture of N-[(trimethylstannyl)imino]bis-(diisopropylamino)bromophosphorane (11) (32%), 2,2-bis(diisopropylamino)-4-phenyl-1,3,2λ 5-diazaphosphete (12) (26% yield), 1,3,5,2λ 5-triazaphosphinine 13 (3% yield), benzonitrile (35%), and bromotrimethylstannane (60%). The mechanisms involved in these reactions are studied. Scheme 2 Scheme 3

Domaines

Chimie organique
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Dates et versions

hal-03435664 , version 1 (19-11-2021)

Identifiants

  • HAL Id : hal-03435664 , version 1

Citer

Gilles Alcaraz, Valérie Piquet, Antoine Baceiredo, Françoise Dahan, Wolfgang W Schoeller, et al.. Mechanism of the Exchange Reaction of Halodiazirines with Nucleophiles Revisited. Synthesis of Neutral, Mono-or Dicationic 4-16-Membered Phosphorus Heterocycles. Journal of the American Chemical Society, 1996. ⟨hal-03435664⟩
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