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Iron(II)‐Catalyzed Hydrophosphination of Isocyanates
Author(s) -
Sharpe Helen R.,
Geer Ana M.,
Lewis William,
Blake Alexander J.,
Kays Deborah L.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201701051
Subject(s) - chemistry , regioselectivity , catalysis , steric effects , diphenylphosphine , transition metal , yield (engineering) , lewis acids and bases , metal , polymer chemistry , medicinal chemistry , stereochemistry , organic chemistry , phosphine , materials science , metallurgy
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 [Ph 2 PC(=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.