Deuterium isotope effects in the intramolecular hydrogen transfer reactions of some 1-alkyl substituted cyclopropenes

1986 ◽  
Vol 51 (19) ◽  
pp. 3738-3739 ◽  
Author(s):  
Albert Padwa ◽  
Lenny W. Terry
Keyword(s):  
Hydrogen Transfer ◽  
Isotope Effects ◽  
Transfer Reactions ◽  
Deuterium Isotope Effects ◽  
Intramolecular Hydrogen ◽  
Hydrogen Transfer Reactions

Nicotinamide coenzyme regeneration. The rates of some 1,4-dihydropyridine, pyridinium salt, and flavin mononucleotide hydrogen-transfer reactions

1976 ◽  
Vol 54 (19) ◽  
pp. 2974-2980 ◽  
Author(s):  
J. Bryan Jones ◽  
Keith E. Taylor
Keyword(s):  
Hydrogen Transfer ◽  
Isotope Effects ◽  
Pyridinium Salt ◽  
Transfer Reactions ◽  
Flavin Mononucleotide ◽  
Pyridinium Salts ◽  
Significant Extent ◽  
Redox Couples ◽  
Donor Acceptor ◽  
Deuterium Isotope Effects

The rates of H-transfer between various 1,4-dihydropyridines and pyridinium salts (including NADH and NAD+), and from 1,4-dihydropyridines to FMN, have been measured. The reactions are found to be sufficiently slow for H-transfer to be rate-determining to a significant extent when such Systems are applied for nicotinamide coenzyme recycling purposes. The rates of H-transfer parallel the magnitudes of the donor–acceptor redox potential differences (ΔE0′); ΔE0′ values may therefore be used as qualitative guides in formulating and selecting redox couples of NAD/H recycling value. On the basis of deuterium isotope effects, it is concluded that formation of a complex prior to H-transfer is not rate determining for 1,4-dihydropyridine–NAD+ reactions. This behavior is in contrast to that of other model alcohol dehydrogenase Systems.

Sign in / Sign up

Export Citation Format

Share Document