Ability of different biomaterials to enantioselectively catalyze oxidation and reduction reactions.
We studied the ability of different biomaterials to enantioselectively catalyze oxidation or reduction reactions with the help of substrate rac-1-m or p-ArCH(OH)Me and the 1-o-ArC(O)Me derivatives. Apoenzyme (NAD(P)(+)-dependent secondary alcohol dehydrogenase(NAD(P)-E)) and cofactor (NAD(P)(+)) were activated by preincubating immobilized aqueous plant leaf (e.g., young wheat leaves), cereal tissue (wheat bran), vegetable (e.g., carrot), and seaweed (e.g., wakame seaweed) solutions, and the NAD(P)-E oxidized only (R)-isomers highly enantioselectively. Thus, greater than 99% ee(s) of (S)-isomers (1m-5m and 1p-5p) can be obtained from corresponding rac-1-m or p-ArCH(OH)Me. Further, immobilized chlorella cells and immobilized baker's yeast can reduce highly stereoselectively; greater than 99% ee(s) of (S)-isomers (1o-5o) can be obtained from corresponding 1-o-ArC(O)Me. Specific use of each isomer ((S)-6 and (R)-6) with greater than 99% ee(s) of racemic-1-2-NpCH(OH)Me becomes possible through selective use of NAD(P)-E eluted from artemisia vulgaris indica leaves and young wheat leaves. We suggest that the pH of the reaction media can determine not only the direction of NAD(P)-E, toward enantioselectively catalyzed oxidation (pH > 7.0) or reduction reaction (pH < 7.0), but also the regioselective reactivity of NAD(P)-E to the substrate o- (pH < 7.0), m-, and p-substituted groups (pH > 7.0). Thus, in comparison to current biocatalysts, several biomaterials can serve as asymmetric reagent bases, providing easily obtained, low-cost natural catalysts with stereoselectivity, regioselectivity, and substrate specificity that work under mild conditions for asymmetric synthesis of organic compounds.
Nagaoka
Hiroyuki
H
Sanyo Shokuhin Co., Ltd., R & D, 555-4 Asakura, Maebashi, Gunma 371-0811, Japan. nagaoka1@sea.plala.or.jp
D000438:Alcohols / Q000138:chemical synthesis*; D019306:Artemisia / Q000737:chemistry*; D001672:Biocompatible Materials / Q000737:chemistry*; D002384:Catalysis; D001467:Hordeum / Q000737:chemistry*; D007536:Isomerism; D007700:Kinetics; D008422:Materials Testing; D009249:NADP / Q000737:chemistry*; D010084:Oxidation-Reduction; D010936:Plant Extracts / Q000737:chemistry*; D018515:Plant Leaves / Q000737:chemistry; D011208:Powders; D013379:Substrate Specificity; D014908:Triticum / Q000737:chemistry*
D000438:Alcohols; D001672:Biocompatible Materials; D010936:Plant Extracts; D011208:Powders; D009249:NADP