13954-38-6Relevant articles and documents
Synthesis of N6,N6-dialkyladenine nucleosides using hexaalkylphosphorus triamides produced in situ
Lakshman, Mahesh K.,Choudhury, Asad,Bae, Suyeal,Rochttis, Eliezer,Pradhan, Padmanava,Kumar, Amit
, p. 152 - 159 (2009)
Reactions between secondary amines and phosphorus trichloride (PCl 3) leads to the formation of the corresponding tris(dialkylamino) phosphanes or hexaalkylphosphorus triamides [HAPTs: (R2N) 3P]. Treatment of silyl-protected 2′-deoxyinosine and acetyl-protected inosine with the HAPTs produced in situ, together with iodine (I2), leads to the formation of N6,N6- dialkyladenosine and -2′-deoxyadenosine. In some cases the stoichiometry of the amine is important, as is the use of a tertiary amine base. The effect of amine stoichiometry on the reaction between HAPT and I2 has been studied by 31P{1H} NMR spectroscopy. Wiley-VCH Verlag GmbH & Co. KGaA, 2009.
Mizoroki-Heck reactions catalyzed by palladium dichloro-bis(aminophosphine) complexes under mild reaction conditions. the importance of ligand composition on the catalytic activity
Oberholzer, Miriam,Frech, Christian M.
, p. 1678 - 1686 (2013/10/01)
Dichloro-bis(aminophosphine) complexes of palladium with the general formula [(P{(NC5H10)3-n(C6H 11)n})2Pd(Cl)2] (where n = 0-2) are easily accessible, cheap and air stable, highly active and universally applicable C-C cross-coupling catalysts, which exhibit an excellent functional group tolerance. The ligand composition of amine-substituted phosphines (controlled by the number of P-N bonds) was found to effectively determine their catalytic activity in the Heck reaction, for which nanoparticles were demonstrated to be their catalytically active form. While dichloro{bis[1, 1′,1′′-(phosphinetriyl)tripiperidine]}palladium (1), the least stable complex (towards protons) within the series of [(P{(NC5H 10)3-n(C6H11)n}) 2Pd(Cl)2] (where n = 0-3), is a highly active Heck catalyst at 100 °C and, hence, a rare example of an effective and versatile Heck catalyst that efficiently operates under mild reaction conditions (100 °C or below), a significant successive drop in activity was noticed for dichloro-bis(1,1′-(cyclohexylphosphinediyl)dipiperidine)palladium (2, with n = 1), dichloro-bis(1-(dicyclohexylphosphinyl)piperidine)palladium (3, with n = 2) and dichloro-bis(tricyclohexylphosphine)palladium (4, with n = 3), of which the latter is essentially inactive (at least under the reaction conditions applied). This trend was explained by the successively increasing complex stability and its ensuing retarding effect on the (water-induced) generation of palladium nanoparticles thereof. This interpretation was experimentally confirmed (initial reductions of 1-4 into palladium(0) complexes of the type [Pd(P{(NC5H10)3-n(C6H 11)n})2] (where n = 0-3) were excluded to be the reason for the activity difference observed as well as molecular (Pd 0/PdII) mechanisms were excluded to be operative) and thus demonstrates that the catalytic activity of dichloro-bis(aminophosphine) complexes of palladium can-in reactions where nanoparticles are involved-effectively be controlled by the number of P-N bonds in the ligand system.
Hydrolysis of ammonia borane catalyzed by aminophosphine-stabilized precursors of rhodium nanoparticles: Ligand effects and solvent-controlled product formation
Fetz, Marco,Gerber, Roman,Blacque, Olivier,Frech, Christian M.
supporting information; experimental part, p. 4732 - 4736 (2011/07/08)
Releasing hydrogen: Aminophosphine complexes of rhodium are excellent systems for the hydrolysis of H3N-BH3. The release of H2 in THF/H2O mixtures generates NH3 and B(OH)3 and is based on the sequential catalytic dehydrogenation of H3N-BH3-n(OH)n and hydrolysis of H 2N=BH2-n(OH)n (n=0-2, see scheme). Copyright
