5995-07-3Relevant articles and documents
Addition of a Cyclophosphine to Nitriles: An Inorganic Click Reaction Featuring Protio, Organo, and Main-Group Catalysis
Chitnis, Saurabh S.,Sparkes, Hazel A.,Annibale, Vincent T.,Pridmore, Natalie E.,Oliver, Alex M.,Manners, Ian
, p. 9536 - 9540 (2017)
The addition of a cyclotriphosphine to a broad range of nitriles gives access to the first examples of free 1-aza-2,3,4-triphospholenes in a rapid, ambient temperature, one-pot, high-yield protocol. The reaction produces electron-rich heterocycles (four lone pairs) and features homoatomic σ-bond heterolysis, thereby combining the key features of the 1,3-dipolar cycloaddition chemistry of azides and cyclopropanes. Also reported is the first catalytic addition of P?P bonds to the C≡N bond. The coordination chemistry of the new heterocycles is explored.
Phosphenium-insertion and chloronium-addition reactions involving the cyclo-phosphanes (t-BuP)n (n≤3, 4)
Holthausen, Michael H.,Knackstedt, Dane,Burford, Neil,Weigand, Jan J.
, p. 1155 - 1162 (2013/10/22)
The transfer of a Ph2P+-moiety provided by Ph2PCl and chloronium-addition with PCl5 or PhICl2 to the cyclo-phosphanes (t-BuP)n (n≤3 (4), 4 (5)) were investigated. The reactions strongly depend on the presence of GaCl3 or Me3SiOTf as a halide abstracting reagent. The reaction of 4 with Ph2PCl and GaCl3 quantitatively yields cation [Ph2P(t-BuP)3]+ (6+) as a GaCl4 - salt. Using Me3SiOTf as a halide abstracting reagent leads to the ring expansion of (t-BuP)3 (4) to tetrameric (t-BuP)4 (5) and cation 6+ is only formed as a minor product. Chloronium addition employing the PCl5/GaCl3 or PhICl2/Me3SiOTf systems as Cl+-sources to 4 gives complex reaction mixtures. In contrast, the Cl+-addition to 5 gives cation [Cl(t-BuP)4]+ (8+) quantitatively when the system PCl5/GaCl3 is used. Utilising PhICl2 in the presence of Me3SiOTf gives t-BuPCl2 as the main product.
Ditelluride-promoted diphosphene transfer from a cyclotriphosphane to 2,3-dimethylbutadiene: characterization of di(aryltelluro)diphosphanes
Meyer, H. U.,Severengiz, T.,Mont, W. W. du
, p. 691 - 694 (2007/10/02)
The cleavage of tri-tert-butylcyclotriphosphane 1 with di(4-methylphenyl)ditelluride 2 leads to 1,2-di-tert-butyl-1.2-di(4-methylphenyltelluro)diphosphane 3 and tetra-tert-butylcyclotetraphosphane.When 1 is heated with 2 in the presence of 2,3-dimethylbutadiene, the diphosphene trapping product 1,2-di-tert-butyl-4,5-dimethyl-1,2-diphosphacyclohex-4-ene 5 can be detected.The salt elimination reaction of tert-butyldichlorophosphane with 4-methylphenyltellurotelluromagnesium bromide leads mainly to 3 and ditelluride 2.Tellurophosphane 6 and 1,2-di-tert-butyl-1,2-di(aryltelluro)diphosphanes 3. 7 (7 : aryl = 2,4,6-triisopropylphenyl) are available in fair yields from di-tert-butylchlorophosphane or 1,2-di-tert-butyl-1,2-dichlorodiphosphane with metal tellurolates.At 90 deg C with 2,3-dimethylbutadiene, 7 acts as a source of 1,2-di-tert-butyldiphosphene trapped as cycloadduct 5. - Keywords: cyclophosphanes / phosphorus-carbon heterocycles / cleavage of phosphorus-phosphorus bonds / di(aryltelluro) diphosphanes / diphosphene transfer.
