Synthesis of isosteric analogues of nicotinamide adenine dinucleotide containing C-nucleotide of nicotinamide or picolinamide

J Med Chem. 1993 Jun 25;36(13):1855-9. doi: 10.1021/jm00065a008.

Abstract

Two isosteric analogues of nicotinamide adenine dinucleotide, C-NAD (11) and C-PAD (12), in which the nicotinamide riboside portion is replaced by a C-nucleoside, were synthesized from 5-(beta-D-ribofuranosyl)nicotinamide (7) and 6-(beta-D-ribofuranosyl)picolinamide (8), respectively. Nucleoside 7 was prepared from the 2,3-O-isopropylidene-5-O-(tetrahydropyranyl)-D-ribonolactone (13) and 3-cyano-5-lithiopyridine as reported earlier. Nucleoside 8 was obtained by conversion of the bromo function of the 6-(2,3:4,5-di-O-isopropylidene-D-altro-pentitol-1-yl)-2-bromopyrid ine (14) into a carboxamido group followed by mesylation of the anomeric hydroxyl group to give derivative 18. Treatment of 18 with CF3COOH/CHCl3 caused deisopropylidenation with simultaneous cyclization into the desired 6-(beta-D-ribofuranosyl)picolinamide (8). NAD analogues, C-NAD (11) and C-PAD (12), were synthesized by imidazole-catalyzed coupling of the corresponding 5'-monophosphates of 7 and 8 with the adenosine-5'-monophosphate. Dinucleotide 11 was found to inhibit the proliferation of L1210 cells (IC50 = 7 microM) and to be a good competitive inhibitor of inosine monophosphate dehydrogenase (IMPDH, ID50 = 20 microM) as well as bovine glutamate dehydrogenase (GDH, Ki = 15 microM). Interestingly, C-NAD (11) caused extremely potent noncompetitive inhibition of horse liver alcohol dehydrogenase (ADH, Ki = 1.1 nM), whereas C-PAD (12) was found to be a much less potent competitive inhibitor (Ki = 20 microM) of ADH.

Publication types

  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Alcohol Dehydrogenase / antagonists & inhibitors
  • Animals
  • Antimetabolites, Antineoplastic / chemical synthesis*
  • Antimetabolites, Antineoplastic / pharmacology*
  • Cattle
  • Glutamate Dehydrogenase / antagonists & inhibitors
  • Horses
  • IMP Dehydrogenase / antagonists & inhibitors*
  • Leukemia L1210 / drug therapy
  • Leukemia L1210 / enzymology
  • Liver / enzymology
  • Mice
  • NAD / analogs & derivatives*
  • NAD / chemical synthesis
  • Niacinamide / analogs & derivatives*
  • Niacinamide / chemistry
  • Picolinic Acids / chemistry*
  • Ribonucleosides / chemistry*

Substances

  • Antimetabolites, Antineoplastic
  • Picolinic Acids
  • Ribonucleosides
  • NAD
  • 5-ribofuranosylnicotinamide
  • 6-(beta-ribofuranosyl)picolinamide
  • Niacinamide
  • Alcohol Dehydrogenase
  • IMP Dehydrogenase
  • Glutamate Dehydrogenase