• Media type: E-Article
  • Title: Iron(II)‐Catalyzed Hydrophosphination of Isocyanates
  • Contributor: Sharpe, Helen R.; Geer, Ana M.; Lewis, William; Blake, Alexander J.; Kays, Deborah L.
  • Published: Wiley, 2017
  • Published in: Angewandte Chemie International Edition, 56 (2017) 17, Seite 4845-4848
  • Language: English
  • DOI: 10.1002/anie.201701051
  • ISSN: 1433-7851; 1521-3773
  • Origination:
  • Footnote:
  • Description: AbstractThe first transition metal catalyzed hydrophosphination of isocyanates is presented. The use of low‐coordinate iron(II) precatalysts leads to an unprecedented catalytic double insertion of isocyanates into the P−H bond of diphenylphosphine to yield phosphinodicarboxamides [Ph2PC(=O)N(R)C(=O)N(H)R], a new family of derivatized organophosphorus compounds. This remarkable result can be attributed to the low‐coordinate nature of the iron(II) centers whose inherent electron deficiency enables a Lewis‐acid mechanism in which a combination of the steric pocket of the metal center and substrate size determines the reaction products and regioselectivity.