With diphenylphosphane

Reaction of perfluorooctanonitrile (5) with diphenylphosphane gives one of two products, depending on the reaction conditions a primary adduct 6 and the reduced adduct 7 formation of the latter is prevented by the presence of water. - ... 

Thus. 1,2-dichlorohexafIuorocycIopentene (1) reacts smoothly with diphenylphosphane to give only the monosubstituted derivative in good yield. In the case of the more nucleophilic dicyclohexylphosphanc, the formation of the mono- and disubstituted derivatives 3 and 4, respectively, is observed.22... 

A powerful variation of the iron acetyl enolate aldol reaction utilizes the cnolate of complex 8 which bears a (pentafluorophenyl)diphenylphosphane ligand in place of the more usual triphenylphosphane47. The enolate species 9. prepared by treatment of 8 with lithium diiso-propylamide, reacts at — 78 °C with benzaldehyde to produce the aldol adduct 10 with a d.r. of 98.5 1.5. 

As shown in Scheme 18, the reaction of 3-azido-2,3-dideoxynucleoside 36 with polystyryl diphenylphosphane resin (37) affords iminophosphorane 38, which gives amine 39 after hydrolysis. Dioxane or pyridine is used as a solvent, and the purity of the products obtained is identical with those obtained by the normal method (94S789). 

Diphenyl-2-mercaptoacetate ligand, 40 29 Diphenylphosphane, reaction with hexa-... 

Ligands with trimethylammonium groups can be prepared by the regio-selective addition of diphenylphosphane to conjugated alkenes with good yields. For example, the alkene CH2=CHC(0)0CH2CH2NMe3l , an acrylic ester, has been used (45). The authors did not report the water solubility. 

Sugar derivatives of phosphanes can be made by reaction of ethylene glycol derivatives with sugar diacetonides to form monoallyl ethers, which can be brominated at the double bond. These compounds react with phenyl-and diphenylphosphanes to yield ligands with a sugar function in the side chain (57). Phosphinated glucopyranosides were prepared by Oehme and... 

Faure et al92 reported the first enzymatic resolution of phosphane-borane complex. Thus, the borane adduct of (2-hydroxypropyl)diphenylphosphane 107 was resolved using the lipase CAL-B and vinyl acetate as acyl donor in organic solvent. The remaining unreacted substrate (.S )-107 was recovered with 91 % ee. 

Action of tetrachloromethane on trimethylsilyl-substituted methyl-diphenylphosphanes causes quantitative chloroform elimination with formation of trimethylsilylated (TMS) methylenechloro-diphenylphosphoranes. Heating the bistrimethylsilyl substituted... 

A brominated polystyrene is reacted with sodium diphenylphosphan to form the polymeric Wittig reagent. Reaction with a halide and a base form the ylid which reacts with the carbonyl compound to the olefin. Wittig olefination can be made stereoselective (33). The formation of cis-olefins is accomplished in salt-free solu-... 

The primary addition product from HFA and diphenylphosphane (32b) has been unambiguously characterized by several groups (97, 755). It is easily oxidized by atmospheric oxygen and dinitrogen tetroxide (97, 755) to form phosphonous acid ester 33b via phosphane oxide 36 (755), which can also be synthesized from HFA and diphenylphosphane oxide. Kinetics of the base-catalyzed rearrangement have been studied (754). Further action of HFA on 32b yields difluorophosphorane 37 (755). A dipolar intermediate with tetra-coordinated phosphorus has been postulated by Stockel (260) in the formation of 33b and 33c (R = c-CgHu). 

A second access to these four-membered ring systems is the action of alkyl halides on the adduct of diphenylphosphane with HFA (32b) [Eq. (53)] (96). 

Rychnovsky and his group have recently developed new synthetic methods that lead to the total syntheses of the polyene macrolides roxaticin [2], roflamycoin [3], and filipin III [4]. The polyol chains of all three natural products were constructed by iterative, stereoselective alkylation of lithiated cyanohydrin acetonides and subsequent reductive decyanation, illustrated here by the synthesis of the polyol framework of filipin III (1) (Scheme I). The bifunctional cyanohydrin acetonide 2, prepared by ruthenium/BINAP catalyzed enantioselective hydrogenation of the corresponding ) -keto ester (BINAP = [ 1,1 -binaphthyl]-2,2 -diylbis(diphenylphosphane)), is deprotonated with LiNEt2 and alkylated with 2-benzyloxy-l-iodoethane. The alkylation product 3 is converted by a Finkelstein reaction into the iodide 4, which is used to alkylate a second... 

A radical diphosphanylation of alkynes using tetraorganodiphosphanes as precursors for phosphanyl radicals has been applied to the synthesis of a doubly phosphinated diene 200 (Scheme 2.37)7 Tetraphenyldiphosphane was generated in situ from diphenylphosphane with an excess of chlorodiphenylphosphane in the presence of triethylamine. Addition of the phosphanyl radical to one C = C triple bond in the dialkyne 199 leads to vinyl radical 201, which undergoes a 5-exo cyclization (out of a Z-configured vinyl radical to minimize sterical hindrance in the cyclization) to give vinyl radical intermediate 202. The latter is trapped by a second phosphine moiety in a radical substitution step. The radical cyclization product is ultimately isolated as bis-phosphane sulfide 200 after treatment of the intermediate phosphane 203 with sulfur. 

Replacement of bis(l,2-diphenylphosphino)ethane by chiral phosphanes such as (— )-(25, 3 5)-bis(diphenylphosphino)butane or (- -)-(/ )- ,2-bis(diphenylphosphino)propane allows a highly enantioselective cobalt-catalyzed homo-Diels-Alder reaction (maximum 91% ee) between norbornadiene and monosubstituted alkynes. Similarly, the reaction of norbornadiene with phenylacetylene in the presence of catalytic amounts of tris(acetylacetonato)cobalt and (-l-)-bicyclo[2.2.1]hept-5-ene-2,3-diylbis(diphenylphosphane) leads quantitatively to the homo-Diels-Alder adduct with an ee of 98.4%. ... 

Diphenylphosphane (5.58 g, 30 mmol) was added dropwise to a stirred solution of t-BuOK (3.37 g, 30 mmol) in DMSO (50 mL) under Nj. The flask was immersed in a bath of cold water during both the addition and the subsequent steps. After 15 min of stirring, 7,7-dichlorobicyclo[4.1.0]heptane (3.30 g, 20 mmol) was added dropwise, and the mixture was allowed to stir for 1 h. After this time, it was poured into HjO (100 mL) and extracted with pentane (2 x 25 mL). The combined extracts were washed several times with water and dried. The dried extracts were concentrated through a Vigreux column (15 cm), and the residue was distilled with a short-path apparatus to afford 1.98 g (76%) of the product as a 6 94 mixture of the endo- and exo-isomers bp 60-61 °C/10Torr. 

The reaction of cyclopropylidenetriphenylphosphorane (1) with water yields cyclopropyl-diphenylphosphane oxide by the extrusion of benzene. ... 

Copper(I) complexes [Cu(L)(Tpx)] (L = 4-(diphenylphosphane) benzoic acid, Tpx = Tp, pzTp, or Tp ) have been synthesized and characterized by FT-IR in the solid state, and by NMR (3H and 31P 1H ) spectroscopy, ESI MS, and conductivity measurements in solution. The solution data are in accordance with partial dissociation of the sterically hindered complexes due to breaking of Cu-P and Cu-N... 

Cu(TpMe)2] prepared from the reaction of CuCl2 with K(TpMe) has been characterized by magnetic susceptibilities, fast atom bombardment and IR spectrometry, and X-ray single-crystal study.1 Cop-per(I) complexes containing water soluble phosphines, [Cu(TpMe)(L)] (L = 4- or 2-(diphenylphosphane)benzoic acid), have been characterized by IR in the solid state, and by NMR (JH and 31P 1H ) and electrospray mass spectroscopy in solution. Chemiluminescence technique was used to evaluate their superoxide scavenging activity.2... 

A highly active catalytic system for direct arylation reactions of nonactivated arenes relied on a homobimetallic rhodium complex. Thus, treatment of [bis(2-pyridyl) amino]diphenylphosphane (109) with [Rh(cod)Cl]2 led to the formation of a complex 108, which, according to X-ray crystal structure analysis, consisted of [Rh(cod) Cl2] anion and a rhodium cation stabilized by two P,N-ligands (Scheme 9.34) [73]. This bimetallic rhodium complex (108) allowed the direct arylation of benzene (87) with the aryl chloride 106 with a turnover number (TON) of 780 under comparably mild reaction conditions. 

A novel chiral ligand type for asymmetric hydroformylation with rhodium and platinum complexes11 125,1 54,156 is the hydroxyproline derived (2S,4>S)-l-(/err-butoxycarbonyl)-4-(diphenylphosphino)-2-[(diphenylphosphino)methyl]pyrrolidine [(-)-BPPM]2-6. As with other diphosphane systems, modifications of BPPM by exchange of either one or both of the different diphenylphosphane groups with dibenzophosphole (DBP) units [BPPM-2DBP, BPPM-4DBP and BPPM-(DBP)2] have been studied158. 

Asymmetric induction in the palladium-catalyzed hydroesterification of z-methylstyrene, styrene and other alkenes in the presence of ligands with rigid 5//-dibenzophospholyl units linked to chiral cyclobutane, dioxolane or cyclohexane skeletons (CBDBP, DIPHOL, CHDBP) is compared with the effect of the analogous diphenylphosphane ligands18 23. 

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