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Synlett 2010(17): 2654-2658  
DOI: 10.1055/s-0030-1258766
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient Bis-C-Aminoglycosylation toward the Synthesis of the Pluramycins

Masayuki Shigetaa,b, Tomohiko Hakamataa,b, Yukie Watanabea,b, Kei Kitamuraa,b, Yoshio Andoa,b, Keisuke Suzuki*a,b, Takashi Matsumoto*b,c
a Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro, Tokyo, 152-8551, Japan
b Japan Science and Technology Agency (JST), SORST, O-okayama, Meguro, Tokyo, 152-8551, Japan
c School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, Horinouchi, Hachioji, Tokyo, 192-0392, Japan
Fax: +81(42)6763257; e-Mail: tmatsumo@toyaku.ac.jp;
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Publication History

Received 4 August 2010
Publication Date:
01 October 2010 (online)

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Abstract

Two bis-C-aminoglycosyl arenes containing the angolosamine and the vancosamine moieties, which are potentially useful as the D-ring fragments of the pluramycin-type antibiotics, were efficiently synthesized by the O→C-glycoside rearrangement based strategy.

Key words

natural product synthesis - pluramycin-type antibiotics - amino sugar - bis-C-glycoside - O→C-glycoside rearrangement

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8

The anomeric configurations in 5 and 11 (Figure  [²] ) were determined by the coupling constants of ¹H NMR spectra and NOE measurements. For details, see Supporting Information.

Figure 2

10

It is interesting to note that vancosaminyl acetate 4 upon reaction with excess resorcylic ester 29 (3 molar amounts) gave mono-C-glycoside 10 and bis-C-glycoside 30 in high combined yield without formation of the two-fold arylation product (Scheme  [¹²] ). In contrast, the reaction of angolosaminyl acetate 6 with 29 (2 molar amounts) gave none of the bis-C-glycoside but yielded mono-C-glycoside 31 (28% yield), the two-fold arylation product 32 (12%), and many other unidentified products of higher molecular weights. It is therefore obvious that the angolosamine moiety is much more apt to undergo the two-fold arylation, as compared with the vancosamine moiety. We surmise the steric congestion at the C(3) position in the vancosamine moiety makes it resistant to this unfavorable reaction.

12

Actually, treatment of bis-C-glycoside 11 with excess amounts of diol 29 under the Sc(OTf)3-Drierite conditions led to the complete recovery of 11 (Scheme  [¹³] ).

13

For determination of the regiochemistry, see Supporting Information.

18

The anomeric configurations in 16 and 18 (Figure  [³] ) were determined by the coupling constants of ¹H NMR and NOE measurements. For details, see Supporting Information.

Figure 3

19

So far, we have never encountered the two-fold arylation in the C-glycosylation of various 2-iodoresorcinol derivatives, regardless of the glycosyl donors (see references 4, 20b-d). Furthermore, it turned out that mono-C-glycosides 19 and 20 possessing the angolosamine moieties were recovered intact even after treatment with two molar amounts of diol 29 under the conditions with excess Sc(OTf)3 (Scheme  [¹5] ). These results, setting the reason aside, imply that susceptibility of the C-glycoside moiety to the two-fold arylation depends on the C(2)-substituent of the resorcinol moiety, in addition to the structure of the sugar moiety as described in reference 10.