7067-72-3Relevant academic research and scientific papers
The first ring-expanded NHC-copper(i) phosphides as catalysts in the highly selective hydrophosphination of isocyanates
Horsley Downie, Thomas M.,Hall, Jonathan W.,Collier Finn, Thomas P.,Liptrot, David J.,Lowe, John P.,Mahon, Mary F.,McMullin, Claire L.,Whittlesey, Michael K.
supporting information, p. 13359 - 13362 (2020/11/10)
A range of N-heterocyclic carbene-supported copper diphenylphosphides (NHC = IPr, 6-Dipp, SIMes and 6-Mes) were synthesised. These include the first reports of ring-expanded NHC-copper(i) phosphides. The compounds were characterised by NMR spectroscopy and X-ray crystallography. Reaction of (6-Dipp)CuPPh2 with isocyanates, isothiocyanates and carbon disulfide results in the insertion of the heterocumulene into the Cu-P bond. The NHC-copper phosphides were found to be the most selective catalysts yet reported for the hydrophosphination of isocyanates. They provide access to a broad range of phosphinocarboxamides in excellent conversion and good yield. This journal is
Convenient synthesis of phosphinecarboxamide and phosphinecarbothioamide by hydrophosphination of isocyanates and isothiocyanates
Itazaki, Masumi,Matsutani, Takanari,Nochida, Tomoya,Moriuchi, Toshiyuki,Nakazawa, Hiroshi
supporting information, p. 443 - 445 (2020/01/13)
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 co
Neutral and Cationic Zirconium Complexes Bearing Multidentate Aminophenolato Ligands for Hydrophosphination Reactions of Alkenes and Heterocumulenes
Zhang, Yu,Qu, Liye,Wang, Yaorong,Yuan, Dan,Yao, Yingming,Shen, Qi
, p. 139 - 149 (2018/01/11)
Zirconium complexes supported by multidentate aminophenolato ligands were synthesized and characterized. The catalytic activities of neutral zirconium complexes and their cationic derivatives in the hydrophosphination of alkenes as well as heterocumulenes have been investigated and compared. Neutral complex 1 bearing a multidentate amino mono(phenolato) ligand exhibited high activity in hydrophosphination of simple alkenes, and anti-Markovnikov products were obtained in 37-94% yields at room temperature. Cationic species generated in situ from complex 3 stabilized by a bis(phenolato) ligand were found to be more active for hydrophosphination of heterocumulenes, i.e., carbodiimides and isocyanates, and gave phosphaguanidines and phosphaureas in 67-93% yields. The Lewis acidity and coordination space of metal centers are modified through changes in the ligand structure, which is found to significantly influence catalytic activity. These complexes are among the most active group 4 metal-based catalysts for hydrophosphination reactions.
The phosphinoboration of carbodiimides, isocyanates, isothiocyanates and CO2
Geier, Stephen J.,Lafortune, James H. W.,Zhu, Diya,Kosnik, Stephanie C.,Macdonald, Charles L.B.,Stephan, Douglas W.,Westcott, Stephen A.
, p. 10876 - 10885 (2017/08/30)
The transition metal-free addition of phosphinoboronate ester Ph2PBpin (pin = 1,2-O2C2Me4) to heterocumulenes including carbodiimides, isocyanates, isothiocyanates and carbon dioxide has been investigated. The corresponding 1,2-addition products were readily prepared at room temperature without the need of a catalyst or added base. Addition of methanol to the compounds derived from addition of Ph2PBpin to carbodiimides, isocyanates, and isothiocyanates resulted in traditional hydrophosphination products. The methodology developed in this study provides a simple and elegant route for the generation of a wide range of functionalized phosphines. The phosphinoboronate ester Ph2PBpin also selectively and reversibly adds to CO2 at room temperature in a 1,2-manner.
Iron(II)-Catalyzed Hydrophosphination of Isocyanates
Sharpe, Helen R.,Geer, Ana M.,Lewis, William,Blake, Alexander J.,Kays, Deborah L.
, p. 4845 - 4848 (2017/04/11)
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.
Addition of E-H (E = N, P, C, O, S) Bonds to Heterocumulenes Catalyzed by Benzimidazolin-2-iminato Actinide Complexes
Liu, Heng,Fridman, Natalia,Tamm, Matthias,Eisen, Moris S.
supporting information, p. 3896 - 3903 (2017/10/30)
The synthesis and characterization of benzimidazolin-2-iminato actinide(IV) complexes [(BimR1/R2N)An(N{SiMe3}2)3] (An = U, Th) (1-6) is reported. All complexes were obtained in high yields, and their solid state structures were established through single-crystal X-ray diffraction analysis. Using 1-6 as precatalysts, the addition of mono- and bifunctional E-H (E = N, P, C, O, S) substrates to various heterocumulenes, including carbodiimides, isocyanates, and isothiocyanates, was investigated, affording the respective addition products in high yields under very mild reaction conditions. Various amines were applicable to this reaction, indicating a large scope capability of amine nucleophiles for the insertion process.
Catalytic insertion of E-H bonds (E = C, N, P, S) into heterocumulenes by amido-actinide complexes
Batrice, Rami J.,Eisen, Moris S.
, p. 939 - 944 (2016/02/05)
We report herein the actinide-mediated insertion of E-H bonds (E = C, N, P, S) into various heterocumulenes including carbodiimides, isocyanates, and isothiocyanates. The precatalysts are prepared by a simple, one-pot procedure using readily available sta
Actinide-Mediated Catalytic Addition of E-H Bonds (E=N, P, S) to Carbodiimides, Isocyanates, and Isothiocyanates
Karmel, Isabell S.R.,Tamm, Matthias,Eisen, Moris S.
supporting information, p. 12422 - 12425 (2015/10/12)
Unprecedented catalytic reactivity of actinide coordination complexes toward heterocumulenes, such as carbodiimides, isocyanates, and isothiocyanates is reported. The mono(imidazolin-2-iminato) thorium(IV) complex [Th(ImDippN){N(SiMe3)2}3] (1) was applied as a precatalyst for the addition of E-H (E=N, P, S) bonds to the Y≡C≡X core (Y=R2N; X=NR2, O, S) of carbodiimides, isocyanates, and isothiocyanates. The respective insertion products were obtained in high yields under mild reaction conditions, with complex 1 displaying high tolerance toward functional groups and heteroatoms. New reactivity: The mono(imidazolin-2-iminato) thorium complex [Th(ImDippN){N(SiMe3)2}3] was successfully applied as an active catalyst for the addition of E-H (E=N, P, S) bonds across the central Y≡N≡C≡X linkage of carbodiimides, isocyanates and isothiocyanates, yielding the respective insertion products in high yields and under mild reaction conditions.
Insertion reactions and catalytic hydrophosphination of heterocumulenes using α-metalated N, N-dimethylbenzylamine rare-earth-metal complexes
Behrle, Andrew C.,Schmidt, Joseph A. R.
, p. 1141 - 1149 (2013/05/09)
The reactivity of homoleptic α-metalated dimethylbenzylamine lanthanide complexes (α-Ln(DMBA)3; Ln = La, Y; DMBA = α-deprotonated dimethylbenzylamine) was probed through a series of stoichiometric insertion and catalytic hydrophosphination reactions. Both rare-earth-metal species inserted 3 equiv of various carbodiimides to form the corresponding homoleptic amidinates. α-La(DMBA)3 was also found to be a useful precatalyst for the room-temperature hydrophosphination of heterocumulenes to form phosphaguanidines, phosphaureas, and phosphathioureas in moderate to excellent isolated yields. Furthermore, through a series of stepwise stoichiometric protonation and insertion reactions, a plausible mechanism for the hydrophosphination catalysis was investigated.
