Darstellung Von β-D-Olivosyl(1→3)-D-olivosiden Aus Mithramycin
Titel:
Darstellung Von β-D-Olivosyl(1→3)-D-olivosiden Aus Mithramycin
Auteur:
Thiem, Joachim Gerken, Manfred
Verschenen in:
Journal of carbohydrate chemistry
Paginering:
Jaargang 1 (1982) nr. 3 pagina's 229-249
Jaar:
1982-01-01
Inhoud:
The benzyl glycoside 4 obtained from 2-bromo-2-deoxy-α-0-quinovosyl bromide 1, readily accessible by the dibromomethyl methyl ether reaction of 2, is deformylated to give the monohydroxy compound 5 which is used in glycosidation reactions. Treatment of 3 with dibromomethyl methyl ether results in the formation of the labile β-furanosyl bromide 7 and the cyrstalline pyranosyl bromide 8 in a ratio of 1:2, both of which are further characterized by their methyl glycosides 10 and 11, respectively. Action of dibromomethyl methyl ether at room temperature on the benzyl ether 6, conventionally prepared from 3, is shown to proceed initially to the glycosyl bromide 9. Compound 9 is cleaved to the 4-formyl-blocked pyranosyl bromide 12, and only after prolonged reaction time gives the pyranosyl halide 8. The glycosidation of the glycosyl bromide 1 with benzyl-4-0-benzyl-α-D-olivoside 13 in the presence of silver carbonate and silicate is a sluggish reaction and gives rather low yields of the β-and the α, l-3-linked disaccharides 15 and 16 in the ratio 3-4:1. With silver triflate the yield is improved to the 61% and the ratio 6:1 in favour of 15. Further transformations lead to both the syrupy olivosyl olivosides 17. and 18. In a more favourable reaction sequence 1 is condensed with the alcohol component 5 and silver triflate as promoter and yields the crystalline β-(19) and the α, 1→3-linked disaccharides (20) in 92% and a ratio of 6.5: 1. By subsequent transformations the protected title tetradeoxy disaccharide 21 is obtained.
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