Diphenylphosphine anion

SCHEME 11.11 ONSH in p-fluoronitrobenzene with diphenylphosphine anion [22],... 

Phospinoxides continue to he examined as photoinitiators, known for the optimal cleavage even in rather thick layers. Un-activated al-kenes have been hydrophosphinylated in good yields by irradiation in the presence of diatylphosphine oxides and commercially available dyes as photocatalysts. Some heterohelicenes have been prepared by oxidative photocyclization of the corresponding phosphindole-benzophenan-threne. The SrnI reaction has been extended to the preparation of diphenylphosphinobenzoic acid by photostimulation of the chlorobenzoate ion in the presence of diphenylphosphine anion in liquid ammonia. Diphenylphosphines have been also prepared by photostimulated substitution of 7-bromonorbornadiene and derivatives. ... 

Aqueous HCI solutions hydrolyze the P-N bond to give the amine hydrochloride and R2P-OH, which then disproportionates and is oxidized to diphenylphosphinic acid. A free phosphinous amide anion, with the countercation complexed by a crown ether, has been shown to be hydrolyzed and oxidized to the corresponding phosphinite with unusual ease [119]. Formic acid in toluene can be utilized for converting P,P-disubstituted phosphinous amides into their respective phosphane oxides [30]. 

M. N., Jones, P.G. and Erdhruegger, C.F. (1989) (Diphenylphosphinomethyl) diphenylphosphine sulfide (Ph2PCH2PPh2S) and its methanide anion Ph2PCHPPh2S- as ligands in organogold chemistry. X-ray crystal structure of [(diphenylphosphino) (diphenylthiophosphinoyl)methanido-P, S]his(pentafluorophenyl)gold(l 11). 

An extension of the research on silver complexes with Lewis base-functionalized mono(A-heterocyclic carbene) ligands has been made toward the better-studied and stronger coordinating phosphine systems. The reaction of a diphenylphosphine-functionalized imidazolium salt with silver oxide in dichloromethane affords a trinuclear silver carbene complex 50, as confirmed by electrospray-ionization mass spectrometry.96,97 Metathesis reaction of 50 in methanol using silver nitrate gives 51 in 33% yield. The crystal structures of 51 were found to be different when different solvents were used during crystallization (Scheme 12).97 One NO3- anion was found to be chelated to... 

Further variations on the epoxyketone intermediate theme have been reported. In the first (Scheme 9A) [78], limonene oxide was prepared by Sharpless asymmetric epoxidation of commercial (S)-(-)- perillyl alcohol 65 followed by conversion of the alcohol 66 to the crystalline mesylate, recrystallization to remove stereoisomeric impurities, and reduction with LiAlH4 to give (-)-limonene oxide 59. This was converted to the key epoxyketone 60 by phase transfer catalyzed permanganate oxidation. Control of the trisubstituted alkene stereochemistry was achieved by reaction of the ketone with the anion from (4-methyl-3-pentenyl)diphenylphosphine oxide, yielding the isolable erythro adduct 67, and the trisubstituted E-alkene 52a from spontaneous elimination by the threo adduct. Treatment of the erythro adduct with NaH in DMF resulted... 

Diphenylphosphinic chloride reacts with the superoxide anion radical (Oi ) in CH3CN under mild conditions to form the diphenylphosphinic peroxy radical intermediate 77, which shows strong oxidizing abilities in the epoxidation of alkenes, oxidation of sulfoxides to sulfones, desulfurization of thioamides to amides and oxidation of triphenylphos-phines to triphenylphosphine oxide in good to excellent yields (equation 105). ... 

Stereoselective allylic alkylations have been carried out with the aid of palladium catalysts. The 17-(Z)-ethylidene groups of steroids (obtained from the ketones by Wittig olefination) form n-allyl palladium complexes in the presence of copper(n) salts (B.M. Trost, 1974, 1976). Their alkylation with dimethyl malonate anions in the presence of 1,2-ethane-diylbis[diphenylphosphine] (— diphos) gives a reaction exclusively at the side chain and only the (20S) products. If one starts with the endocyclic 16,17 double bond and replaces an (S)-20-acetoxy group by using tetrakis(triphenylphospbine)palladium,the substitution occurs with complete retention of configuration, resulting from two complete inversions (B.M. Trost, 1976). 

The reaction of alkyl isothiocyanates, RNCS, with diphenylphosphinic hydrazide (338) in benzene has been reported.308 The bis(diethylamino)[(methylthio)thiocarbon-yl]carbenium salts (339 X = I or BF4) display ambident reactivity and can react either at carbenium carbon (hard nucleophiles) or at the thiocarbonyl sulfur atom (soft nucleophiles).309 Electrochemically generated superoxide reacts with dithioic S,S -diesters (dicarbothiolates) (340 Ar = C5H3N or C6H4) to give the monocarboxylate anions in 100% yield before giving the dicarboxylate anions.310... 

A previous description of the synthesis of (CH3)3SiP(C6H5)2 in Inorganic Syntheses1 involves the initial preparation of sodium diphenylphosphide from diphenylphosphinous chloride. This method of preparation of the diphenylphosphide anion requires rigorous conditions and long reaction times. At least two other easier methods of preparation of the diphenylphosphide anion (lithium counterion) are known. One synthesis uses diphenyl-phosphine and n-butyllithium2 as reactants, whereas the second uses triphenylphosphine and elemental lithium.3,4 The second method is described here. 

F.namine synthesis u.sing the Homer-Wittig reaction. I. (Aminomethyl)diphenylphosphine oxides, new fonnyl anion equivalents. Re-cueil, 103, 305, 1984. 

Cyclohexene oxide and its 3-hydroxy derivatives have been opened regio- and stereospecifically with phosphodiesters. The mechanism of the reaction of oxiranes with sodium dialkyl phosphite and diphenylphosphines has been studied. Cyclopropanecarboxylic acid derivatives have been obtained from substituted oxiranes with triethylphosphonoacetate anion.The mechanism of formation of isomeric alkoxyalkylacetates from oxiranes with alkyl halides and mercuric acetate has been discussed. ... 

A new acyl anion equivalent derived from an aldehyde, a secondary amine and diphenylalkylphos-phine oxide, e.g. (N-morpholinomethyl)diphenylphosphine oxide, reacts with aldehydes or ketones to form enamines, which on acid hydrolysis afford aldehydes or ketones (Scheme 32). The usefulness of this acyl anion equivalent is demonstrated by the synthesis of dihydrojasmone and (Z)-6-henicosen-11-one. ... 

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