Hydrogenolysis dissolving metals

Ethers may be removed commonly by acid, with the THE derivative 1.79 reacting more rapidly than the tert-hutyl ether. Benzyl ethers may be removed under a variety of conditions such as hydrogenolysis, dissolving metal reduction (Na in NH3) and HBr (mild). Methyl ethers are cleaved by refluxing with EtSNa and DME tert-Butyl ethers can be cleaved with trifluroacetic acid (CE3COOH) at 25°C. 

The dissolving metal reduction is not suitable, because it effects a cleavage ol the benzylic C-N bond. b The cleavage of the N-N bond by hydrogenolysis is affected by some racemization. 

Removal of the 9-phenylfluoren-9-yl group has been accomplished by three different procedures acidolysls with trifluoroacetlc acid,2 8 10 12 catalytic hydrogenolysis,3 7 9 14 15 and dissolving metal reduction.15... 

Hydrogenolysis of the C-S bond can be achieved both by dissolving metal systems (sodium in liquid ammonia) or by catalytic methods, particularly with a finely divided reactive form of nickel known as Raney nickel. When the latter is combined with dithioacetal formation, using either ethanedithiol or propane-1,3-dithiol, the result is a mild method for reducing a carbonyl group to a methylene group. 

Aromatic ketones represent a rather special case in dissolving metal reductions. Under many conditions pinacol formation is the predominent reaction path (see Volume 3, Chapter 2.6). Also, the reduction potentials of aromatic carbonyl compounds are approximately 1 V less negative than their aliphatic counterparts. The reductions of aromatic ketones by metals in ammonia are further complicated by the fact that hydrogenolysis of the carbon-oxygen bond can take place (Chapter 1.13, this volume) and Birch reduction may intervene (Chapter 3.4, this volume). 

A potentially useful chemoselective dissolving metal reagent for the reduction of aromatic ketones in the presence of other functional groups is the combination Zn-DMSO and aqueous potassium hydroxide. In three examples (benzophenone, fluorenone and 4-benzoylpyridine), the yields of secondary alcohols were over 90%. Two other ketones (xanthone and thioxanthone) gave mixtures of alcohol and the hydrocarbon obtained by hydrogenolysis of a carbon-oxygen bond. ... 

Hydrogenolysis ofAllyl and Benzyl Halides and Related Compounds 4.7.4 DISSOLVING METAL REDUCTIONS... 

Electrochemical hydrogenolysis of allylic and benzylic centers can be achieved, but application of this reduction has not been either widely used or acclaimed. It is less convenient experimentally than the comparable method using dissolving metals and control of selectivity is more difficult to achieve than with other methods. Only limited applications are found. Generally electroreduction is carried out using cathodes of metals of high overvoltage such as copper, cadmium, lead and mercury, with anodes of platinum. 

Benzylic amines are particularly susceptible to hydrogenolysis by catalytic hydrogenation or dissolving metal reduction. " Note that the Wolff-Kishner reduction in 19-61 involved formation of a hydrazone and deprotonation by base led to loss of nitrogen and reduction. Ceric ammonium nitrate in aqueous acetonitrile has also been shown to reductively cleave the V-benzyl group. Primary amines have been reduced to RH with hydroxylamine-O-sulfonic acid and... 

In order to accomplish a total dehalogenation to hydrocarbons, dissolving metal reductions are most commonly employed. Cyclopropyl chlorides and bromides are satisfactorily reduced by alkali metal in alcohoF or in liquid ammonia. However, the fluorides are usually resistant to the hydrogenolysis. gem-Difluorides have been... 

Na or Li and ammonia, excellent yields. This is a very good method to remove a benzyl group from an amide and will usually work when hydrogenolysis does not. A dissolving metal reduction can be effected without cleavage of a sulfur-carbon bond. Note also the unusual selectivity in the cleavage illustrated below. This was attributed to steric compression. Primary benzyl amides are not cleaved under these conditions. ... 

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