Alcohols, as reducing agents

Gitis, D. Mukhopadhyay, S. Rothenberg, G. Sasson, Y. Solid/liquid Pd-catalyzed coupling of haloaryls using alcohols as reducing agents kinetics and process optimization. Org. Process Res. Dev. 2003, 7, 109-114. 

However, the use of sodium/alcohol as reducing agent suffers from several disadvantages fl) The reduction does not stop at the enolate or the saturated ketone stage. 

Process 5, the conversion of hydroperoxides to alkoxy and hydroxyl radicals, can be interrupted by incorporation of a secondary antioxidant such as phosphites (e.g. Irgafos 168) or thioesters (e.g. Evanstab 12). These materials act as reducing agents, converting hydroperoxides to alcohols and themselves being converted to phosphates or sulfoxides, respectively (see Fig. 16). 

Carbinolamines, 87 Carbodiimides, 205-222 reaction with alcohols, 170 Carbon monoxide, as reducing agent, 336 a-Carbonyl azo compounds, 324, 326 Caro s add (permonosulfuric add), 408 oxidation with, 409 preparation of, 409 Chloramine T, 377 Chloroacetylenes 120-122 4-Chloro-l, 2-butadiene, 33 Chlorocyclohexenyl acetylene, 121 1 -Chloro-2-JV,N-diphenylaminoacetylene, 128-129... 

Alcoholic potassium hydroxide and sodium alcoholate in the presence of alcohols such as benzyl alcohol have been used as reducing agents for aromatic nitro compounds. 

While the demercuration of (3-acyloxymercurials has not received much attention, sodium borohydride or alkaline sodium borohydride have been most widely employed for this task. Hydrolysis to the corresponding alcohol or reversion to alkene are significant side reactions, however, and they are sensitive to the solvent used.4991500 Sodium amalgam and tri-n-butyltin hydride501 have also been utilized as reducing agents. 

Lithium aluminum hydride as reducing agent permits formation of alcohol 40 in the first step. This is then convened to iodide 41. Another reduction with a nucleophilic boron reagent produces an ethyl group at C-13 and thus structure 12. 

Dialkyl and diaryl ditellurium compounds are easily reduced to tellurols and tellurolates. Alkali metals in liquid ammonia or in an inert organic solvent, sodium borohydride in methanol, ethanol, alcohol/benzene, THF, DMF, or in a basic aqueous medium, lithium aluminum hydride in dioxane or THF/hexamethylphosphoric triamide, and thiourea dioxide in THF/50% aqueous sodium hydroxide have been used as reducing agents (p. 164). The tellurolates are easily oxidized in air. For this reason they are almost always used in situ. 

---