Preparation and characterization of NADP derivatives alkylated at 2′‐phosphate and 6‐amino groups

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Abstract
Reaction of NADP with 3-propiolactone at pH 6 gave new NADP derivatives carboxyethylated at the 2''-phosphate or 6-amino group, or both: 2''-O-(2-carboxyethyl)phosphono-NAD (I), N6-(2-carboxyethyl)-NADP (II), and 2''-O-(2-carboxyethyl)phosphono-N6-(2-carboxyethyl)-NAD (III). Their structures were assigned on the basis of UV, 1H-NMR and 31P-NMR spectra, and also treatment with nucleotide pyrophosphatase or alkaline phosphatase. Carbodiimide-promoted reaction of derivative I with 1,2-diaminoethane gave 2''-O-[N-(2-aminoethyl)carbamoylethyl]phosphono-NAD (IV); derivative III gave 2''-O-[N-(2-aminoethyl)carbamoylethyl]phosphono-N6-[N-(2-aminoethyl)carbamoylethyl]-NAD. The same reaction of derivative II, on the other hand, gave a mixture of N6-[N-(2-aminoethyl)carbamoylethyl]-NADP (Va) and its 3''-phosphate isomer. The mixture was converted to Va via the 2'',3''-cyclic derivative. Their structures were assigned on the basis of UV and 1H-NMR spectra, and also treatment with alkaline phosphatase or 3''-nucleotidase. All the NADP derivatives obtained in this work could be reduced with yeast glucose-6-phosphate dehydrogenase.