Copper© diphenylphosphinate

This reaction has been modified to occur efficiently under microwave irradiation. Besides copper (I) 2-thiophenecarboxylate, Cu(I)-3-methylsalicylate (CuMeSal) and copper diphenylphosphinate have also been developed as mediators. 

The coupling of secondary phosphines with aryl iodides was also extended to pyridines. 3-Iodopyridine and diphenylphosphine were coupled to give 3-diphenylphosphino-pyridine in 60% yield (7.80.), The catalyst in this reaction consisted of copper(I) iodide and N,N -dimethylethylenediamine and caesium carbonate was used again as base.102... 

Platinum Compounds Hydrogen hexachloroplatinate(IV)-Copper(II) chloride, 145 Hydrogen hexachloroplatinate(IV)-Diethoxymethylsilane, 76 Platinum-Titanium, 251 Rhodium Compounds [2,2 -Bis(diphenylphosphine)-l,T-binaphthyl](dimethanol)rhodium(I) perchlorate, 36... 

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). 

Allenes are activated by a diphenylphosphine oxide substituent towards nucleophilic substitution at the j3-carbon atom. Lithium dimethyl-cuprate adds quickly to the 1,2-bond to give, on hydrolysis, the olefin in 16-84% yield, according to the nature of the substituents (76). Optimum conditions were not reported. The intermediate a-copper compound resulting from the addition can be dimerized or reacted with methyl iodide [Eq. (106)]. Similar reactions involving methyllithium are complicated. 

Ethyl diphenylphosphinite, (CgHg)2P.OC2H5, is formed when diphenylchlorophosphine m ether solution is treated with sodium ethoxide. The product is a transparent hquid, B.pt. 179° C. at 14 mm., density 1-0896 at 0° C. It forms an additive compound with copper iodide, M.pt. 190° to 191° C. Under the catal3rtic influence of ethyl iodide at ordinary temperature it is transformed into ethyldiplienyl-phospliine oxide. During the preparation of the phosphinite some ethyl diphenylphosphinate, (CgH5)2PO(OC2H5), is obtained as a byproduct. 

Scheme 31 Proposed mechanism for copper-catalyzed anti-hydrophosphination of 1-alkynylphosphines with diphenylphosphine...

A copper-catalyzed arylation of diphenylphosphine oxide in the presence of A-methylpyrrolidine-2-carboxamide was described. An example is shown in Scheme 19. ... 

A direct approach to an a-aminophosphine oxide was developed by deprotonating methyl-diphenylphosphine oxide, and reacting the resulting Zn salt with benzoylo) morpholine in the presence of a copper catalyst (Scheme 47). ... 

Photoexcitation (X = 313 nm) of the charge-transfer adducts of N with CuBr(Py)(PPh3) or Cu[HB(Pz)3] in hexane (Py = pyridine, Pz = 1-pyrazolyl) gives rise to Q with = 0.37-0.65. The photorearrangement of the complexes of N with halo(ferrocenyl-diphenylphosphine)copper(I) tetramers... 

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