Stannous phosphite

Among the reductive methods of preparing azoxy compounds is the reduction of aliphatic nitroso compounds with stannous chloride. Triethyl phosphite has been used for the bimolecular reduction of fully fluorinated aromatic nitroso compounds. 

Stannous triflate in acetonitrile as solvent at -40 °C catalyzes the glycosylation of the phosphite donor 7 with the acceptor 10. As result an tt-selective linkage takes place. 

Starting with phosphite 59 stannous triflate catalyzes the formation of an oxenium ion 60, which is stabilized by the solvent (61). The complex 61 is more favored than 63, justified by the reverse anomeric effect until now. But as it is shown there is no possibility for 61 to react in an SN2 reaction to 62. The intermediate 63 can be attacked by the alcohol functionality of the glycosyl acceptor, and with MeCN as leaving group you get 64. Ultimately the equilibrium between 61 and 63 shifts completely to 63. This kind of stereocontrol during a glycosylation is known as the nitrile effect.28... 

The released TfOH reacts with the trivalent stannoyl phosphite and gives the hydrogen phosphite 65.31 Stannous triflate acts as catalyst. 

During reduction of the nitro derivatives 261 (with stannous chloride in hydrochloric acid, - with hydrogen over Raney nickel in ethanol, with iron powder in 50% acetic acid, - or with triethyl phosphite - at 170-1 SOX), the resulting amino derivatives 262 sometimes underwent spontaneous cyclization and gave the linearly annelated tricyclic compounds 263. Cyclization of the amino derivatives 262 was effected ther-mally or by the action of phosphoryl chloride. - ... 

Iriniethoxyborohydridc. Stannous bromide. Stannous chloride. Teltamethylammonium borohydride. Thioglycolic acid. Tin. Titanium tetrachloride. Tri-/-butylaluminum. Tri-n-butyltin hydride. Triethylene glycol (see Zinc). Triethyl phosphite. Trimethylamine borane. Trimethylammonium formate. Trimethylsilane (indirect). Triphenyltin hydride. Tris-(tripbenylphosphine)chlor(X hodium. Zinc. Zinc amalgam. Zinc-Copper couple. Zinc hydrosulfide. 

Olefins, synthesis -Butyllithium. 1,3-Dibenzyl-2-methyl-l, 3,2-diazaphospholidine. Dimethyl methylphosphonothioate. Diphenylsulfonium isopropylide. N-Methanesulfinyl-p-toluidine. Methylphosphoric acid bis(dimethylamide). Phosphoryl chloride-Stannous chloride-Pyridine. p- Toluenesulfonylhydrazine. Triphenyl phosphite. 

Reducing agents Aluminum hydride. Bis-3-methyl-2-butylborane. n-Butyllithium-Pyridine. Calcium borohydride. Chloroiridic acid. Chromous acetate. Chromous chloride. Chromous sulfate. Copper chromite. Diborane. Diborane-Boron trifluoride. Diborane-Sodium borohydride. Diethyl phosphonate. Diimide. Diisobutylaluminum hydride. Dimethyl sulfide. Hexamethylphosphorous triamide. Iridium tetrachloride. Lead. Lithium alkyla-mines. Lithium aluminum hydride. Lithium aluminum hydride-Aluminum chloride. Lithium-Ammonia. Lithium diisobutylmethylaluminum hydride. Lithium-Diphenyl. Lithium ethylenediamine. Lithium-Hexamethylphosphoric triamide. Lithium hydride. Lithium triethoxyaluminum hydride. Lithium tri-/-butoxyaluminum hydride. Nickel-aluminum alloy. Pyridine-n-Butyllithium. Sodium amalgam. Sodium-Ammonia. Sodium borohydride. Sodium borohydride-BFs, see DDQ. Sodium dihydrobis-(2-methoxyethoxy) aluminate. Sodium hydrosulflte. Sodium telluride. Stannous chloride. Tin-HBr. Tri-n-butyltin hydride. Trimethyl phosphite, see Dinitrogen tetroxide. 

Attempts to convert the sulfones back into PASHs have been successful with a number of agents such as various metals (zinc, tin, magnesium, aluminum, iron, and nickel) in acetic acid, palladium on carbon with hydrazine, stannous chloride, lithium triethylborohydride, diphenylsi-lane, sodium borohydride, boron trifluoride, dicyclohexylcarbodiimide, triethyl phosphite, dimethyl dichlorosUane with lithium aluminum hydride, diphenylsilane, and triphenyl phosphine with iodine. However, none of them cleanly effect this conversion. 

Tetrachloropalladate(II) ion catalyzes the interconversion of 1- and 2-butenes in aqueous solutions containing chloride and hydronium ions. Sodium tetrachloropalladate(II) catalyzes the conversion of allylbenzene to propenyl-benzene in acetic acid solutions. Tetrakis(ethylene))Lt,/x -dichlororhodium(l) catalyzes butene isomerization in methanolic hydrogen chloride solutions . Cyclooctadienes isomerize in benzene-methanol solutions of dichlorobis-(triphenylphosphine)platinum(11) and stannous chloride. Chloroplatinic acid-stannous chloride catalyzes the isomerization of pentenes. Coordination complexes of zero-valent nickel with tris(2-biphenylyl)phosphite or triphenyl-phosphine catalyze the isomerization of cis-1,2-divinylcyclobutane to a mixture of c/5,m-l, 5-cyclooctadiene and 4-vinylcyclohexene . Detailed discussions of reaction kinetics and mechanisms appear in the papers cited. 

Reaction (36) was discovered by Arbuzov more than a century ago (not with PVC). It reflects the strength of P(iii) as a reducing agent, the product, P(v) bearing a P=0 bond. This is the primary color retention contribution of the phosphite component. Reaction (36) is catalyzed by zinc and cadmium salts, and probably by stannous compounds. 

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