Asymmetric Reduction with Bis(NADH) Model Compounds

Hoshide, Fumitoshi; Ohi, Satoshi; Baba, Naomichi; Oda, Jun’ichi; Inouye, Yuzo

doi:10.1080/00021369.1982.10865408

Cited by 4 publications

(7 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Inouye reported bridged chiral bis-NAD(P)H model compound 5 (Figure 4), which carries L-prolinamide as the chiral center, and obtained good stereoselectivity (98% ee). [32][33][34] Only one specific face of the dihydronicotinamide…”

Section: Figure 2 Nad(p)h Modelmentioning

confidence: 99%

See 1 more Smart Citation

Progress on Chiral NAD(P)H Model Compounds

Chen

Wang

Xing

et al. 2016

Synlett

View full text Add to dashboard Cite

NAD(P)H and NAD + have a significant role in biochemistry, and many NAD(P)H models received particular attention. Research in NADH models mainly focuses on asymmetric reduction and life sciences. Over the past few decades, a particularly large number of new chiral NAD(P)H models have appeared, and there have been significant developments in this area. We summarized advanced research in chiral NAD(P)H models in this paper. These models not only show very good performance in asymmetric reduction, but also have excellent fluorescence features. In addition, we present a discussion about some recent studies on the asymmetric reduction of NAD(P)H-dependent dehydrogenase, and we open a new door on research into NAD(P)H models. At last, some advances focused on the fluorescence phenomenon of some chiral NAD(P)H models have also been summarized.

show abstract

Section: Figure 2 Nad(p)h Modelmentioning

confidence: 99%

“…model was approachable to the substrates. [32][33][34] Thus, it controlled the steric course of the hydrogen transfer in the reaction.…”

Section: Account Syn Lettmentioning

confidence: 99%

Progress on Chiral NAD(P)H Model Compounds

Chen

Wang

Xing

et al. 2016

Synlett

View full text Add to dashboard Cite

show abstract

“…Coenzyme NADH, a cofactor of l -lactate dehydrogenase, functions as an enantioselective agent that reduces pyruvate to l -lactate during anaerobic glycolysis. During the past several decades, efforts have been made to create model compounds mimicking the activity of the NAD + −NADH redox couple. − The introduction of an optically active N -substituent in the amide of 1-alkylated 1,4-dihydronicotinamides, e.g., 1 , can induce modest to moderate chirality transfer toward carbonyl compounds (Figure ). , Furthermore, Ohno and co-workers have improved considerably chirality transfer by the additional introduction of methyl groups at C2 and C4 in the NADH model, e.g., compound 2 . The new chiral center at C4 controls the mode of hydride transfer.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Properties, and NAD⁺-NADH-Type Redox Ability of 14-Substituted 1,3-Dimethyl-5,10-methanocycloundeca[4,5]pyrrolo[2,3-d]pyrimidine-2,4(1,3H)-dionylium Tetrafluoroborates and Their Hydride Adducts

et al. 2006

View full text Add to dashboard Cite

A synthesis of 14-substituted 1,3-dimethyl-5,10-methanocycloundeca[4,5]pyrrolo[2,3-d]pyrimidine-2,4(1,3H)-dionylium tetrafluoroborates 11a,b(+).BF4- was accomplished by the methylation of 5,10-methanocycloundeca[4,5]pyrrolo[2,3-d]pyrimidine-2,4(1,3H)-dione derivatives with MeI and following anion-exchange reaction by treatment with 42% aq HBF(4). Compound 11b(+).BF4- was synthesized alternatively by the reaction of 1,6-methano[11]annulenylium tetrafluoroborate with 6-phenylamino-1,3-dimethyluracil and following oxidative cyclization reaction. Remarkable structural characteristics of 11a,b(+)were clarified on inspection of the UV-vis and NMR spectral data as well as X-ray crystal analyses. The stability of cations 11a,b(+)() is expressed by the pK(R+) values which were determined spectrophotometrically as 9.8 and 9.7, which are smaller by 1.4 and 1.2 pH units than those of the corresponding seven-membered ring cations, respectively; however, the values are larger by 3.6 and 3.5 pH units than that of the parent 1,6-methano[11]annulenylium ion (pK(R+) = 6.2). The feature is rationalized on the basis of the perturbation derived from the bond fixation of the parent cation and the electron-donating ability of pyrrolopyrimidine. The electrochemical reduction of 11a,b(+).BF4- exhibited reduction potential at -0.58 and -0.52 (V vs Ag/AgNO3) upon cyclic voltammetry (CV). Reaction of 11a(+).BF4- with hydride afforded mixures of the C13- and C11-adducts in a ratio with hydride afforded, on the other hand, the C13-adduct as a single product. In both cations, the methano-bridge seemed to control the nucleophilic attack to the C13 favorably with exo-selectivity. The photoinduced autorecycling oxidation reactions of 11a,b(+).BF4- toward some amines under aerobic conditions were carried out to give the corresponding imines (isolated by converting to the corresponding 2,4-dinitrophenylhydrazones) with the recycling number of 1.1 to 32.2. Furthermore, as an example of the NAD+-NADH models, the reduction of a pyruvate analogue and some carbonyl compounds with the hydride adducts of 11a,b+.BF4- was accomplished for the first time to give the corresponding alcohol derivatives.

show abstract

“…Coenzyme NADH, a cofactor of l -lactate dehydrogenase, functions as an enantioselective agent that reduces pyruvate to l -lactate during anaerobic glycolysis. During several decades, efforts have been made to create model compounds mimicking the activity of the NAD + -NADH redox couple. − The introduction of an optically active N -substituent in the amide of 1-alkylated 1,4-dihydronicotinamides, e.g., 1 , can induce a modest to moderate chirality transfer toward carbonyl compounds (Figure ). , Furthermore, Ohno and co-workers have improved considerably a chirality transfer by the additional introduction of methyl groups at the C2 and C4 in the NADH model, e.g., compound 2 . The new chiral center at the C4 controls the mode of hydride transfer.…”

Section: Introductionmentioning

confidence: 99%

Novel Synthesis, Properties, and NAD⁺-NADH Type Redox Ability of 1,3-Dimethylcyclohepta[4,5]pyrrolo[2,3-d]pyrimidine- 2,4(1,3H)-dionylium Ions Annulated with Additional Pyrrolo[2,3-d]pyrimidine-1,3(2,4H)-dione and Furan Analogue, and Their Hydride Adducts

2005

View full text Add to dashboard Cite

[reaction: see text] A convenient preparation of novel cations 11a,b+ x BF4(-) and 12a,b+ x BF4(-), which are derived from annulation of the 1,3-dimethylcyclohepta[4,5]pyrrolo[2,3-d]pyrimidine-2,4(1,3H)-dionylium ion with additional pyrrolo[2,3-d]pyrimidine-1,3(2,4H)-dione and a furan analogue, was accomplished by a novel oxidative cyclization of 1,7-dihydro-7-[1',3'-dimethyl-2',4'(1',3'H)-dioxo-6'-(phenylamino)-pyrimidin-5'-yl]-1,3-dimethyl-10-phenylcyclohepta[4,5]pyrrolo[2,3-d]pyrimidine-2,4(1,3H)-dione 9 and its furan-analogue by using DDQ or photoirradiation under aerobic conditions. Structural characteristics of 11a,b+ and 12a,b+ were clarified on inspection of the UV-vis and NMR spectral data as well as X-ray crystal analyses. The stability of cations 11a,b+ and 12a,b+ is expressed by the pK(R+) values that were determined spectrophotometrically to be 10.7-12.6. The electrochemical reduction of 11a,b+ x BF4(-) and 12a,b+ x BF4(-) exhibited reduction potential at -0.93 to -1.00 (V vs Ag/AgNO3). The first reduction potential of 11a+ was reversible due to steric hindrance of two phenyl groups. The photoinduced oxidation reaction of 11a,b+ x BF4(-) and 12a,b+ x BF4(-) toward some amines under aerobic conditions was carried out to give the corresponding imines (isolated by converting to the corresponding 2,4-dinitrophenylhydrazones) with the recycling numbers of 0.6-30.3. Furthermore, as an example of the NAD+-NADH models, the reduction of a pyruvate analogue and some carbonyl compounds with the hydride-adduct of 11a+ x BF4(-) was accomplished for the first time to give the corresponding alcohol derivatives.

show abstract

Asymmetric Reduction with Bis(NADH) Model Compounds

Cited by 4 publications

References 0 publications

Progress on Chiral NAD(P)H Model Compounds

Progress on Chiral NAD(P)H Model Compounds

Synthesis, Properties, and NAD⁺-NADH-Type Redox Ability of 14-Substituted 1,3-Dimethyl-5,10-methanocycloundeca[4,5]pyrrolo[2,3-d]pyrimidine-2,4(1,3H)-dionylium Tetrafluoroborates and Their Hydride Adducts

Novel Synthesis, Properties, and NAD⁺-NADH Type Redox Ability of 1,3-Dimethylcyclohepta[4,5]pyrrolo[2,3-d]pyrimidine- 2,4(1,3H)-dionylium Ions Annulated with Additional Pyrrolo[2,3-d]pyrimidine-1,3(2,4H)-dione and Furan Analogue, and Their Hydride Adducts

Contact Info

Product

Resources

About

Asymmetric Reduction with Bis(NADH) Model Compounds

Cited by 4 publications

References 0 publications

Progress on Chiral NAD(P)H Model Compounds

Progress on Chiral NAD(P)H Model Compounds

Synthesis, Properties, and NAD+-NADH-Type Redox Ability of 14-Substituted 1,3-Dimethyl-5,10-methanocycloundeca[4,5]pyrrolo[2,3-d]pyrimidine-2,4(1,3H)-dionylium Tetrafluoroborates and Their Hydride Adducts

Novel Synthesis, Properties, and NAD+-NADH Type Redox Ability of 1,3-Dimethylcyclohepta[4,5]pyrrolo[2,3-d]pyrimidine- 2,4(1,3H)-dionylium Ions Annulated with Additional Pyrrolo[2,3-d]pyrimidine-1,3(2,4H)-dione and Furan Analogue, and Their Hydride Adducts

Contact Info

Product

Resources

About

Synthesis, Properties, and NAD⁺-NADH-Type Redox Ability of 14-Substituted 1,3-Dimethyl-5,10-methanocycloundeca[4,5]pyrrolo[2,3-d]pyrimidine-2,4(1,3H)-dionylium Tetrafluoroborates and Their Hydride Adducts

Novel Synthesis, Properties, and NAD⁺-NADH Type Redox Ability of 1,3-Dimethylcyclohepta[4,5]pyrrolo[2,3-d]pyrimidine- 2,4(1,3H)-dionylium Ions Annulated with Additional Pyrrolo[2,3-d]pyrimidine-1,3(2,4H)-dione and Furan Analogue, and Their Hydride Adducts