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On the structure of variose

โœ Scribed by Hitoshi Takai; Hidetaka Yuki; Kiyoshi Takiura


Book ID
104224483
Publisher
Elsevier Science
Year
1975
Tongue
French
Weight
180 KB
Volume
16
Category
Article
ISSN
0040-4039

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โœฆ Synopsis


Variose is a constituent of an antibiotic, variamycin, and its structure was presented by Lokshin et al. as 2,6-dideoxy-4-01methyl-D-ribo-hexose (l).l Their structure determination depends mostly on analysis of p.m.r. spectrum of methyl varioside (II) which was isolated from a natural product. First, 0 they assumed formula IIa or IIb from identification of one O>CH-CH2 (T 7.85, Z-proton m and 4.84, l-proton q), three 0-CH (r ca.6, 3-proton m), one Ca,-CH$ (T 8.7, 3-proton d), two 0-CH3 (r 6.56 and 6.5, f-proton s), and one OH (T 7.99, l-proton s) groups by measurement of p.m.r. spectrum and molecular formula of CgH1604 obtained by mass spectrum. The basic structure was then assigned to IIa from decoupling p.m.r. spectrum of methyl benzoyl varioside (ID). Position of OCH3 group was decided to C-4 from its negative periodate reaction excluding C-4,C-5 diol structure. Finally, they concluded the structure of II to be methyl 2,6-dideoxy-4-O-methyl-a-D_ribo-hexopyranoside (VII). However, it seemed to be doubtful in the following points; i) the proton signal at C-5 is shifted to unusually low magnetic field (~'4.8), ii) the signal pattern of protons at C-2 is analogous to those of other t-deoxy sugars having furanoside structure rather than pyranoside, iii) a possible structure IIc is cH30+oH CH 0' 3 O CH3 CH ,~~~'-3 3 C., OmC,_CH


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