Iron(II)-Catalyzed Hydrophosphination of Isocyanates.
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.
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Helen R
HR
Sharpe
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Ana M
0000-0003-1115-6759
AM
Geer
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
William
0000-0001-7103-6981
W
Lewis
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Alexander J
0000-0003-2257-8332
AJ
Blake
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Deborah L
0000-0002-4616-6001
DL
Kays
homogeneous catalysis; hydrophosphination; iron; ligand design; reaction mechanisms