Enantioselective reactions biological reduction

This reaction is completely enantioselective. For example, reduction of pyruvic acid with NADH catalyzed by lactate dehydrogenase affords a single enantiomer of lactic acid with the S configuration. NADH reduces a variety of different carbonyl compounds in biological systems. The configuration of the product (/ or S) depends on the enzyme used to catalyze the process. 

To date, synthetically useful enantioselective hydroalumination is limited to the asymmetric reductive ring-opening reaction of bicycHc ethers. In spite of the fact that further studies are necessary to get a detailed understanding of the reaction mechanism, this reaction provides a new route to various cycloalkenol derivatives, which are useful intermediates in the preparation of biologically active compounds. 

Reactions using catecholborane proceed smoothly in toluene (Scheme 16) (40). The utility of catalytic hydroboration of ketones has been demonstrated by the efficient enantioselective synthesis of a series of biologically active compounds (41). Scheme 17 shows some compounds prepared by using this method. Enantioselective reduction of trichloro-methyl ketones is a general route to a-amino acids and a-hydroxy esters it also allows ready synthesis of a precursor to the carbonic anhy-drase inhibitor MK-0417 (42). 

The pioneering studies by Itsuno [1] and Corey [2] on the development of the asymmetric hydroboration of ketones using oxazaborolidines have made it possible to easily obtain chiral secondary alcohols with excellent optical purity [3]. Scheme 1 shows examples of Corey s (Corey-Bakshi-Shibata) CBS reduction. When oxazaborolidines 1 were used as catalysts (usually 0.01-0.1 equiv), a wide variety of ketones were reduced by borane reagents with consistently high enan-tioselectivity [2]. The sense of enantioselection was predictable. Many important biologically active compounds and functional materials have been synthesized using this versatile reaction [2-4]. 

Recent employment of optically active fluorinated compounds for biologically active substances (7-2) or ferroelectric liquid crystals (3-5) has emphasized the versatility of these chiral molecules, while few methods have been reported for the preparation of such materials in a highly diastereo- as well as enantioselective manner. On the other hand, recent investigations in this field have opened the possibility for the introduction of chirality via asymmetric reduction or optical resolution by employing biocatalysts such as baker s yeast (6-75) or hydrolytic enzymes (16-20), respectively (27-23), along with the conventional chemical methodology (24-27). Chiral materials thus obtained may also be utilized in diastereoselective reactions which create new chiral centers (77). In this paper, the authors would like to discuss our recent progress in the preparation of optically active fluorinated compoounds and the effect of fluorine atom(s) on the reactivity and selectivity. 

Peroxidases are foimd in nature in plants, microorganisms, and higher organisms. Common peroxidases and their various biological fimctions are shown in Table 2 [24]. Peroxidases are able to catalyze the oxidation of aromatic compounds, the oxidation of heteroatoms, epoxidation, and the enantioselective reduction of racemic hydroperoxides [12,16-20,22,24,35]. Typical reactions catalyzed by peroxidases are listed in Table 3 [24]. 

The asymmetric organocatalytic enantioselective conjugate hydrogen transfer reaction is clearly inspired by the mode of action in biological processes, in which reductions are accomplished by enzymes using hydride reduction cofactors like NADH. 

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