期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 56, 期 17, 页码 4845-4848出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201701051
关键词
homogeneous catalysis; hydrophosphination; iron; ligand design; reaction mechanisms
资金
- University of Nottingham
- EPSRC
- Leverhulme Trust
- EPSRC [EP/K038869/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K038869/1] Funding Source: researchfish
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.
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