Synthesis and Characterization of Phosphinecarboxamide and Phosphinecarbothioamide, and Their Complexation with Palladium(II) Complex.

Reactions of isocyanates/isothiocyanates with primary and secondary phosphines without solvent at room temperature afforded phosphinecarboxamide/phosphinecarbothioamide, respectively, in excellent yields. Furthermore, palladium complex Pd(COD)Cl2 was allowed to react with Ph2PC(O)NHPh (1a) to afford [Pd{Ph2PC(O)NHPh-κP}2Cl2] (3). On the other hand, the reaction of Pd(COD)Cl2 with 1 eq. of Ph2PC(S)NHPh (2a) afforded [PdCl2{Ph2PC(S)NHPh-κP,S}] (4). In the case of a 1:2 molar ratio, [PdCl{Ph2PC(S)NHPh-κP,S}{Ph2PC(S)NHPh-κP}]Cl (5) was formed. The newly obtained compounds were fully characterized using multielement NMR measurements and elemental analyses. In addition, the molecular structures of Ph2PC(O)NH(CH2)2Cl (1j), Ph2PC(S)NHPh(4-Cl) (2c), and 3-5 were determined using single-crystal X-ray diffraction.

Oxovanadium(V)-Catalyzed Synthesis of Ureas from Disilylamines and Carbon Dioxide under Ambient Pressure.

Here, a commercially available easy-to-handle oxovanadium(V) compound is demonstrated to serve as an efficient catalyst for the synthesis of ureas from disilylamines and carbon dioxide under ambient pressure. The catalytic activation of carbon dioxide proceeds without any additives, demonstrating a broad substrate scope and easy scalability to validate this catalytic activation of carbon dioxide. This catalytic system can be applied to the synthesis of unsymmetric ureas and chiral urea with retention of chirality.

Correction: Oxovanadium(v)-catalyzed amination of carbon dioxide under ambient pressure for the synthesis of ureas.

[This corrects the article DOI: 10.1039/D1RA04125H.].

Oxovanadium(v)-catalyzed amination of carbon dioxide under ambient pressure for the synthesis of ureas.

Carbon dioxide is regarded as a reliable C1 building block in organic synthesis because of the nontoxic, abundant, and economical characteristics of carbon dioxide. In this manuscript, a commercially available oxovanadium(v) compound was demonstrated to serve as an efficient catalyst for the catalytic amination of carbon dioxide under ambient pressure in the synthesis of ureas. The catalytic transformation of chiral amines into the corresponding chiral ureas without loss of chirality was also performed. Furthermore, a gram-scale catalytic urea synthesis under ambient pressure was successfully achieved to validate the scalability of this catalytic activation of carbon dioxide.

Convenient synthesis of phosphinecarboxamide and phosphinecarbothioamide by hydrophosphination of isocyanates and isothiocyanates.

Reactions of isocyanates with primary and secondary phosphines without solvent at room temperature afforded the corresponding phosphinecarboxamide (RN(H)COPR'2) in excellent yields. This reaction system is applicable for isothiocyanates. The compounds newly obtained were fully characterized using multielement NMR spectroscopy. In addition, the molecular structure of Cl(CH2)2N(H)COPPh2 was studied by single-crystal X-ray diffraction.