Unactivated carboxylic acids and amines undergo organocatalytic Ph3P/CCl4-mediated amide bond formation by employing in situ reduction of triphenylphosphine oxide to triphenylphosphine in the presence of diethoxymethylsilane and bis(4-nitrophenyl)phosphate.

Simultaneous structuro-kinetic information obtained via time resolved stopped-flow/UV-Vis spectroscopy/dispersive EXAFS (EDE) experiments elucidated a two-step process for the addition of iodobenzene to [(Ph3P)2Pd(dba)].

Enantiomerically pure (S)-tributylstannyl[D1]methanol and (R)- and (S)-tributylstannyl[D1]methyl benzoates were Stille-coupled with bromobenzene and benzoyl chloride in 1,4-dioxane and toluene using [(Ph3P)4Pd] or [(Ph3P)2PdCl2] either alone or in combination with CuCN as cocatalyst at temperatures up to 80 °C. The products were found to be enantiomerically pure. (R)- and (S)-N-(tributylstannyl...

A key intermediate, difluoromethylene phosphobetaine, in the Wittig reaction of ClCF2CO2Na-Ph3P with aldehydes was synthesized and characterized, which confirmed the reaction mechanism. The decarboxylation of this stable intermediate was a convenient approach for Wittig difluroolefination. Its reactivity could be adjusted by the modification of the substituent on the phosphorus.

Reactions of chloro bridged complexes with R-3-(3-pyridyl)alanine afford the chelate complexes LnM[NH2CH(CO2)CH2C5H4NH+]Cl− (LnM = Ph3P(Cl)Pd, (tol3P)(Cl)Pd, (Ph-pyridyl)2Ir, Cp∗(Cl)Rh, Cp∗(Cl)Ir, (p-Cymol)(Cl)Ru) with protonated pyridine substituents. An analogous Cp∗Rh complex with 3-(2-pyridyl)alaninate was also obtained. Addition of base (NaOMe) to these complexes gives dimeric and trimeric...

Difluoromethylation of the activated X-H bond (X = N, O and S) and aliphatic thiols, and gem-difluorocyclopropenation of alkynes with difluorocarbene generated in situ from difluoromethylene phosphobetaine (Ph3P(+)CF2CO2(-)) by decarboxylation occurred smoothly without the presence of any base or other additives.

Treatment of P4 with in situ generated [Na][SnPh3] leads to the formation of the sodium monophosphide [Na][P(SnPh3)2] and the Zintl salt [Na]3[P7]. The former was isolated in 46% yield as the crystalline salt [Na(benzo-15-crown-5)][P(SnPh3)2] and used to prepare the homoleptic phosphine P(SnPh3)3, isolated in 67% yield, as well as the indium derivative (XL)2InP(SnPh3)2 (XL = S(CH2)2NMe2), isola...

The tridentate ligands E(CH2CH2OPiPr2)2 (E = NH 1, E = S 2) were employed in the synthesis of a number of ruthenium complexes. Reaction of these ligands with (Ph3P)3RuCl2 afforded the dimers [Ru(HN(CH2CH2OPiPr2)2)Cl(μ-Cl)]2 (3) and [(Ru(E(CH2CH2OPiPr2)2))2(μ-Cl)3][X] (E = NH, X = PF64, E = S, X = Cl 5), respectively. Using (Ph3P)3RuHCl in reactions with 1 gave Ru(NH(CH2CH2OPiPr2)2)(PPh3)HCl (6)...

an efficient three-component reaction of dialkyl acetylendicarboxylates and 2-pyrrolidin in the presence of triphenylphosphine produces dialkyl 2-(2-pyrrolidin-n-yl)-3-(triphenylphosphanylidene)succinate. these phosphoranes undergo mild intramolecular wittig reaction to produce dialkyl (e)-2-(4,5-dihydro-3h-pyrrol-2-yl)fumarate in excellent yields.