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Stereochemical Course in the Reduction with PNPH

As mentioned above, it is reasonable to consider that the reduction by a 1,4-dihydropyridine derivative catalyzed by metal ions proceeds via a ternary complex as shown in Fig. 3. In the reduction by PNPH, the factor which determines the stereochemistry of the product is the mode of approach of the substrate to PNPH. Namely, the relative orientation between the 1,4-dihydropyridine ring and the substrate in the ternary complex is important. There are many possibilities for the molecular arrangement in the ternary complex as well as for the fashion of the coordination of Mg(II) to PNPH. Here we will discuss what kind of complexation and approach should be considered in order to understand the magnitude and direction of the induced chirality, or the mechanism of chirality induction. [Pg.24]

2 Reduction with a Model Which Contains Chirality at the 4 Pos ition [Pg.26]

There are two main characteristic features in the present reduction. First of all, as can be seen from the result that methyl benzoylformate can be reduced without Mg(II), Me2PNPH exhibits a high [Pg.26]

The reason why such a high degree of enantioface differentiation toward methyl benzoylformate was achieved is that the direction from [Pg.26]

In the abbreviation of JJ-Me2PNPH, X represents the configuration at the 4 position and 7 represents that of benzylic [Pg.26]


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