Cycloalkylation of compounds in the series of phosphorus-substituted derivatives of acetic acid

2,5,8-Tris(diphenylphosphoryl)- and 2,5,8-tris(diphenylthiophosphoryl)-2,3,4,5,6,7,8,9-octahydro-1H-cyclopent[e]-asym-indacene-2,5,8-tricarbonitriles as a novel type of polycondenced systems

“…2 A similar approach was also used to produce gemdisubstituted functionalised phosphorylated cycloalkanes [3][4][5][6][7][8][9][10][11] using organometallic compounds as bases [3][4][5][6] and phase-transfer 7 or PTC [8][9][10][11] conditions. In particular, we determined 8,9 that corresponding gem-disubstituted cyclopropanes, butanes and pentanes can be easily produced in high yields from phosphoryl and thiophosphorylacetic acid nitriles and esters using the heterophase system K 2 CO 3 /DMSO at 20 °C. Marr et al 4 reported that other heterophase systems [NaH/THF-DMSO (80:20, v/v) at 20 °C and K 2 CO 3 /MeCN at 80 °C] give similar products.…”

Novel functionalised P-ligands: advances and application

“…The precursors were obtained by cycloalkylation of phosphorylacetonitriles 13a,b with a,x-and a,w-dihaloalkanes under phase transfer catalysis conditions (Scheme 5). The reaction with a,x-dihaloalkanes was carried out according to procedure elaborated by us earlier [19]. Despite in the case of a,w-dihaloalkanes one could expect the formation of reaction products as statistic mixture of cis-and trans-isomers, unexpectedly such reaction of phosphoryl and thiophosphorylacetonitriles turned out to proceed in a diastereoselective way, yielding only trans-isomer with the identical configuration of asymmetric carbon atoms ðC Ã R C Ã R Þ.…”

“…To a mixture of benzenecarbonitrile 19 or 20 (0.63 mmol) and triethoxysilane (0.70 ml; 3.79 mmol) in 10 ml of benzene 46.5 l of Ti(O i Pr) (0.16 mmol) was added. The resulting suspension was refluxed for either 1 h (19) or 2 h (20) until the light green clear solution was formed. The mixture was evaporated to dryness and phosphines 21 and 22 correspondingly having the purity over 95% was used in subsequent complexation reactions without further purification.…”

Complexation of (1-diphenylphosphino)cyclopropanecarbonitrile with palladium(II)

“…(6H, o-H, p-H in Ph), 7.53-7.58 (4H, m-H in Ph) 13. C NMR (100.68 MHz, CDCl 3 ) d: 5.64 (d, P-C-CN, 1 J ‡ (1-Diphenylphosphoryl)cyclopropanecarbonitrile 2 was obtained by the cycloalkylation of diphenylphosphorylacetonitrile by 1,2-dibromoethane under phase-transfer catalysis conditions 13.…”

“…(6H, o-H, p-H in Ph), 7.53-7.58 (4H, m-H in Ph) 13. C NMR (100.68 MHz, CDCl 3 ) d: 5.64 (d, P-C-CN, 1 J ‡ (1-Diphenylphosphoryl)cyclopropanecarbonitrile 2 was obtained by the cycloalkylation of diphenylphosphorylacetonitrile by 1,2-dibromoethane under phase-transfer catalysis conditions 13. Selected data for 2: yield 61%, mp 168-169 °C (EtOH-acetone).1 H NMR (400.26 MHz, CDCl 3 ) d: 1.60-1.65 (m, 2H, CH 2 ), 1.81-1.86 (m, 2H, CH 2 ), 7.52-7.54, 7.61-7.66, 7.83-7.89 (10H, Ph).…”