Naomichi Baba

Role of hydroxyl groups in the stereochemistry of hydrogen transfer from chiral NAD(P)H model to carbonyl

Abstract Asymmetric reduction of α-ketoester with a chiral dihydronicotinamide was significantly affected by chiral aromatic additives, capable of exerting an attractive interaction with dihydropyridine ring, which was further consolidated through with magnesium.

Asymmetric reduction of ethyl benzoylformate with chiral NADH model systems: Mechanistic and stereochemical consideration of the reactions based on the complexation properties of the model compounds

Abstract Asymmetric reductions of ethyl benzoylformate were conducted by use of NADH model compounds with C1 or C2 symmetry in the presence of magnesium perchlorate. It was found that NADH model compounds which form 2 : 1 chelation complexes with the magnesium ion showed the dependence of optical yield on the reaction conversion. The stereochemical behaviors of the model compounds were classified into three reaction types on the basis of the component ratio in the chelation complex between the reductants and the magnesium ion.

NADH Model Reaction: Asymmetric Reduction of Non-activated Carbonyl Compounds with N-Anionized Hantzsch Ester

As model compounds for NADH coenzymes, three chiral Hantzsch ester-type dihydro-pyridines were prepared. By their use and 2,6-dimethyl-3,5-dicarbo-( — )-menthoxy-1,4-dihydropyridine that had already been prepared, asymmetric reductions of unactivated prochiral ketones were conducted under the action of alkali metal derivatives at room temperature in a non-polar solvent, and the alcohol product were obtained in a 36~80% chemical yield and 30~60% enantiomeric excess.