Zinc as reducing agent

These nickel- or palladium-catalyzed homocoupling reactions can also be conducted in the presence of zinc as reducing agent, leading usually to comparable results as shown recently in the palladium-catalyzed dimerisation of aryltrif-lates [30]. 

Unlike usual processes, the coupling reaction does not need any excess of halide (the carbonyl compound and the a-bromoester are used in the same molar ratio), or, most remarkably, any excess of zinc as reducing agent, which is also consumed stoichiometri-cally. 

Rusling et al. performed electrochemically and light mediated radical additions of alkyl iodides to cyclohexenone in conductive microemulsions catalyzed by 20 mol% of 247 in 14—81% yield [303]. Radical allylations of alkyl bromides 249 with allyl sulfides, sulfones, or phosphates catalyzed by 5 mol% of cobalt (iminate) complex 250 in the presence of zinc as reducing agent proceeded in 52-85% yield [304],... 

The metal is slowly oxidised by air at its boiling point, to give red mercury(II) oxide it is attacked by the halogens (which cannoi therefore be collected over mercury) and by nitric acid. (The reactivity of mercury towards acids is further considered on pp. 436, 438.) It forms amalgams—liquid or solid—with many other metals these find uses as reducing agents (for example with sodium, zinc) and as dental fillings (for example with silver, tin or copper). 

Most metal carbonyls are synthesized in nonaqueous media. Reactive metals, such as sodium (85), magnesium (105), zinc (106), and aluminum (107,108), are usually used as reducing agents. Solvents that stabilize low oxidation states of metals and act as electron-transfer agents are commonly employed. These include diethyl ether, tetrahydrofiiran, and 2-methoxyethyl ether (diglyme). 

Pyrroline-N-oxides (12) are sometimes isolated when using zinc-ammonium chloride (19,20), iron-sulfuric acid (14) or hydrazine-Raney nickel (21) as reducing agents. During the reduction, dimerization has been often observed (22). 

A modified procedure" uses activated zinc together with dry gaseous hydrogen chloride in an organic solvent, e.g. acetic acid, as reducing agent. Under those conditions the reaction occurs at lower temperatures as with the original procedure. 

Metallic elements taking part in redox reactions, such as zinc in the reaction above, commonly act as reducing agents they are oxidized to cations such as Zn2+. Other reducing agents include hydrogen gas, which can be oxidized to H+ ions ... 

Azo, azoxy, and hydrazo compounds can all be reduced to amines. Metals (notably zinc) and acids, and Na2S204, are frequently used as reducing agents. Borane reduces azo compounds to amines, though it does not reduce nitro compounds. " Lithium aluminum hydride does not reduee hydrazo compounds or azo compounds, though with the latter, hydrazo compounds are sometimes isolated. With azoxy compounds, LiAHLj gives only azo compounds (19-48). 

However, lithinm aluminum hydride or zinc metal and HCl (5) are required as reducing agents to reduce the thiocyanate to the thiol. These reducing agents are stoichiometric reagents and aren t environmentally acceptable at this time because of their hazardous properties and waste disposal problems on a large manufacturing scale. 

There has been an increasing number of reports of the utilization of zinc hydride complexes as precursors in organic transformations and as reducing agents. Zinc hydrides have been less well investigated than the other group 13 hydrides due to the formation of polymeric and oligomeric species that are difficult to characterize. 

Dithiazolium cations can be readily reduced to the stable mono- and diradicals. Reaction of the disalt 43 could be effected, on a milligram scale, by electrolysis in an acetonitrile solution at 50 pA onto Pt wire cathode <1997JA2633>. Larger quantities could be obtained by chemical reduction. Attempts to reduce cation 43 directly with silver or zinc powder were unsuccessful. The most successful approach involved the use of triphenylantimony as reducing agent and bis(triphenylphosphine)iminium chloride ((PPN)Cl Equation (5)). The product obtained (7) is remarkably stable in the solid state, in air, and in organic solutions. 

Hydrogen sulphide,3 cuprous chloride,4 and the last named along with powdered zinc,5 have been used as reducing agents, but are open to several objections. 

Metals like zinc, iron, and aluminium These are often used as reducing agents. Their action is due to the formation of ions, normally of their lowest oxidation state ... 

Coupling reactions are sometimes observed in the reduction of 1,3-dithiolium salts. Thus, use of sodium bis-diglyme-hexacarbonylvanadate( 1 —) as reducing agent of the parent compound 142 leads to the 2,2 -bis(l,3-dithiolyl). Better yields (up to 92%) are obtained by use of zinc dust in a mixture acetic acid-benzene-water. 

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