Iron(II)-Catalyzed Hydrophosphination of Isocyanates

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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