Details

Autor(en) / Beteiligte

• Sharpe, Helen R.
• Geer, Ana M.
• Lewis, William
• Blake, Alexander J.
• Kays, Deborah L.

Titel

Iron(II)‐Catalyzed Hydrophosphination of Isocyanates

Ist Teil von

• Angewandte Chemie (International ed.), 2017-04, Vol.56 (17), p.4845-4848

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2017

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The 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. Seeing double: Low‐coordinate iron(II) complexes have been used in the hydrophosphination of isocyanates to produce, by mono‐ and/or diinsertion, phosphinocarboxamides, a new family of derivatized organophosphorus compounds. Small changes in reaction conditions drastically alter the product selectivity.