N.M.R. STUDIES OF D-RIBOSYLAMINES IN SOLUTION: DERIVATIVES OF PRIMARY AMINES

Article abstract of DOI:10.1016/0008-6215(83)88214-7

N.m.r. spectroscopy (1H, 13C) has been used to show that primary amines condense with D-ribose to give mainly D-ribopyranosylamines in which the α anomer in the ¹C₄ conformation preponderates; the β anomer assumes mainly the ⁴C₁ conformation.Thus, it is possible to deduce the structures of N-phenyl-D-ribosylamines and to correlate some of the literature data.For 2,3-O-isopropylidene-D-ribofuranosylamine derivatives, the Δδ values for 13C-n.m.r. signals of the isopropylidene methyl groups can be used to establish the anomeric configuration.

Full text of DOI:10.1016/0008-6215(83)88214-7

2
c. CHAVIS, C. DE GOURCY, F. DUMONT, J.-L. IMBACH
We now report a general study of the products of the direct condensation of
primary aliphatic or aromatic amines and D-ribose.
Ribosylamine6 is an intermediate in the preparation ofpyrimidine and imidazole
nucleosides, phenylethylamine and tryptamine are present in living organisms and
their glucosyl derivatives are known7, 13 (as many steroidal amines s) is active on
the central nervous system, and 14 is an intermediate in the biosynthesis of purine
nucleotides 9.
RESULTS AND DISCUSSION
The following amines were investigated: aniline (6), ammonia (7), benzyl-
amine (8), phenylethylamine (9), tryptamine (10), 2,2-diethoxyethylamine (11),
cyclohexylamine (12), 17/~-amino-3/~-hydroxyandrost-5-ene (13), and 5-amino-4-
carbamoylimidazole (14).
Each of these amines was condensed with D-ribose (1), with an alcohol as
solvent (Schemes 1 and 2) at room temperature in order to avoid the MaiUard degrada-
tion reaction10. The time necessary for completion of reaction ranged from a few
to 24 h. Acyclic, furanoid, and pyranoid products are possible. Reference furanoid
compounds were obtained by the reaction of 6--14 (Scheme 2) with 2,3-O-isopropyli-
dene-o-ribofuranose (2), since the presence of a five-membered ring strongly favors
the formation of a second, fused, five-membered ring tl. In these condensations with
CH2OH
CH2OH
%,o
-
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N
H
D-Ribose (1)
~ EtOH ,78o
NH2
-~
NH
-
-
0
MeOH , 65°
HO
OH
CMez
1
EtOH
CH2OAc
O
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O
OH
4
NH
A¢20
E t O H , 5o"
EtOH
5
*
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N
H
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At20
ACO
OAC
AcO
OAc
HO
OH
1
6¢XP
160[P
+
16~P
150tF
+
15~F
S.Cherne

6
c . C H A V I S , C. D E G O U R C Y , F. D U M O N T , J . - L . I M B A C H
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