School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Angew Chem Int Ed Engl. 2017 Apr 18;56(17):4845-4848. doi: 10.1002/anie.201701051. Epub 2017 Mar 24.
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 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.
首次提出了第一过渡金属催化的异氰酸酯氢膦化反应。使用低配位铁(II)前催化剂导致异氰酸酯对二苯膦的 P-H 键进行前所未有的催化双插入，生成磷酰基二羧酰胺[PhPC(=O)N(R)C(=O)N(H)R]，这是一类新型的衍生有机磷化合物。这一显著的结果可以归因于铁(II)中心的低配位性质，其固有电子缺失使路易斯酸机制成为可能，其中金属中心的位阻口袋和底物大小的组合决定了反应产物和区域选择性。
