Reduction biochemical

Several other electron-transfer reagents have been tested with arenediazonium ions, for example, A-benzyl-l,4-dihydronicotinamide, which is a model for biochemical reductions by NAD(P)H, the reduced form of NADP+ (nicotinamide adenine cfinucleotide phosphate) (Yasui et al., 1984). 

Neuberg, Carl, Biochemical Reductions at the Expense of Sugars, IV, 75-117... 

In practice, both postulated mechanisms are probably at work, especially if the concept of sohd/liquid equilibrium be extended to encompass equilibria governing the production of odorous compounds by chemical and biochemical reduction. 

NMN is basically half of the NAD+ molecule nicotinamide ribose phosphate. NADP+ is NAD+ bearing a phosphate group at C3 of the ribose group attached to the adenine. The redox chemistry is the same in all three forms of the coenzymes. NAD+ is the form most frequently employed for biochemical oxidation reactions in catabohsm and NADP+ (in its reduced form NADPH) is the form usually employed for biochemical reduction reactions in anabohsm. NMN is employed infrequently. 

Biochemical reduction of a,/3-unsaturated ketones using microorganisms (best Beauveria sulfurescens) takes place only if there is at least one hydrogen in the /3-position and the substituents on a-carbons are not too bulky. The main product is the saturated ketone, while only a small amount of the saturated alcohol is formed, especially in slightly acidic medium (pH 5-5.5). The carbonyl is attacked from the equatorial side. Results of biochemical reduction of 5-methylcyclohex-2-en-l-one are illustrative of the biochemical reduction by incubation with Beauveria sulfurescens after 24 hours 74% of the enone was reduced to 3-methylcyclohexanone and 26% to 3-methylcy-clohexanol containing 55% of cis and 45% of trans isomer. After 48 hours the respective numbers were 70% and 30%, and 78% and 22%, respectively [878]. 

Reduction of diketones to either hydroxy ketones or diols can be accomplished by different biochemical reductions [327, 834] Procedure 50, p. 218). 

The biochemical reduction of a, -unsaturated -haloaliphatic acids by means of Clostridium kluyveri yielded halogen-free satmated acids. The same products were obtained from saturated -halo acids. However, the same microorganism converted ix, -unsaturated a-halo acids to saturated a-halo acids with R configuration. Yields of reduction of a-fluoro-, a-chloro- and a-bromocrotonic acid ranged from 30% to 100% [330]. 

Metal amalgams may be used for reduction of the keto groups in keto esters provided the medium does not cause hydrolysis of the ester. Because of that aluminum amalgam in ether is preferable to sodium amalgam in aqueous solutions. Diethyl oxalacetate was reduced to diethyl malate by sodium amalgam in 50% yield and with aluminum amalgam in 80% yield [148], Stereospecific reduction of a- and fi-keto esters to optically pure hydroxy esters was achieved by biochemical reduction in moderate to good yields. Saccharomyces cerevisiae converted methyl 2-keto-2-phenylacetate to methyl... 

Hahn. Reasoning from the observation that proteins and other substances which contain sulfhydryl groups produce hydrogen sulfide on addition of sulfur, Heffter denied that a biochemical reduction process took place at all. As a generalization this negation seems definitely unjustified (see pp. 93 and 95). 

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