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

Masayuki Shigeta; Tomohiko Hakamata; Yukie Watanabe; Kei Kitamura; Yoshio Ando; Keisuke Suzuki; Takashi Matsumoto

doi:10.1055/s-0030-1258766

LETTER

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

Masayuki Shigeta^a,b, Tomohiko Hakamata^a,b, Yukie Watanabe^a,b, Kei Kitamura^a,b, Yoshio Ando^a,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;

Abstract

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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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Referenzen

References and Notes

For the first isolation, see:

<A NAME="RU07210ST-1A">1a</A> Maeda K. Takeuchi T. Nitta K. Yagishita K. Utahara R. Osato T. Ueda M. Kondo S. Okami Y. Umezawa H. J. Antibiot., Ser. A 1956, 9: 75

<A NAME="RU07210ST-1B">1b</A> For the first structure determination, see: Furukawa M. Hayakawa I. Ohta G. Iitaka Y. Tetrahedron 1975, 31: 2989

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For the O→C-glycoside rearrangement, see:

<A NAME="RU07210ST-4C">4c</A> Matsumoto T. Katsuki M. Suzuki K. Tetrahedron Lett. 1988, 29: 6935

<A NAME="RU07210ST-4D">4d</A> Matsumoto T. Hosoya T. Suzuki K. Synlett 1991, 709

<A NAME="RU07210ST-4E">4e</A> Ben A. Yamauchi T. Matsumoto T. Suzuki K. Synlett 2004, 225

<A NAME="RU07210ST-5">5</A> Resorcylic ester 3 was synthesized as shown below (Scheme 9). For the preparation of the intermediate 24, see: Hadfield A. Schweitzer H. Trova MP. Green K. Synth. Commun. 1994, 24: 1025

Vancosaminyl acetate 4 was synthesized as shown below (Scheme 10).

<A NAME="RU07210ST-6A">6a</A> For the preparation of the intermediate 25, see: Hsu D.-S. Matsumoto T. Suzuki K. Synlett 2006, 469

<A NAME="RU07210ST-6B">6b</A> For the selective alcoholysis of a benzoate by using Mg(OMe)₂, see: Xu Y.-C. Bizuneh A. Walker C. Tetrahedron Lett. 1996, 37: 455

<A NAME="RU07210ST-7">7</A> Angolosaminyl acetate 6 was synthesized as shown below (Scheme 11). For the preparation of the intermediate 27, see: Bartner P. Boxler DL. Brambilla R. Mallams AK. Morton JB. Reichert P. Sancilio FD. Surprenant H. Tomalesky G. J. Chem. Soc., Perkin Trans. 1 1979, 1600

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

<A NAME="RU07210ST-9A">9a</A> Hosoya T. Ohashi Y. Matsumoto T. Suzuki K. Tetrahedron Lett. 1996, 37: 663

Also see reference 4e.

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.

<A NAME="RU07210ST-11">11</A> Hey H. Arpe H.-J. Angew. Chem., Int. Ed. Engl. 1973, 12: 928

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] ).

For determination of the regiochemistry, see Supporting Information.

<A NAME="RU07210ST-14">14</A> Hendrickson JM. Bergeron R. Tetrahedron Lett. 1973, 14: 4607

<A NAME="RU07210ST-15A">15a</A> Gray M. Andrews IP. Hook DF. Kitteringham J. Voyle M. Tetrahedron Lett. 2000, 41: 6237

<A NAME="RU07210ST-15B">15b</A> For a review on the Suzuki-Miyaura reaction, see: Miyaura N. Suzuki A. Chem. Rev. 1995, 95: 2457

<A NAME="RU07210ST-16A">16a</A> Leeper FJ. Staunton J. J. Chem. Soc., Chem. Commun. 1978, 406

<A NAME="RU07210ST-16B">16b</A> Dodd JH. Weinreb SM. Tetrahedron Lett. 1979, 20: 3593

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For recent applications to natural product synthesis, see:

<A NAME="RU07210ST-16D">16d</A> Donner CD. Tetrahedron Lett. 2007, 48: 8888

<A NAME="RU07210ST-16E">16e</A> Sperry J. Brimble MA. Synlett 2008, 1910

Iodoresorcinol 15 was synthesized as shown below (Scheme 14). For the preparation of the intermediate 33, see:

<A NAME="RU07210ST-17A">17a</A> Hamura T. Hosoya T. Yamaguchi H. Kuriyama Y. Tanabe M. Miyamoto M. Yasui Y. Matsumoto T. Suzuki K. Helv. Chim. Acta 2002, 85: 3589

<A NAME="RU07210ST-17B">17b</A> Tsujiyama S. Suzuki K. Org. Synth. 2007, 84: 272

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

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.

<A NAME="RU07210ST-20A">20a</A> Matsumoto T. Hosoya T. Katsuki M. Suzuki K. Tetrahedron Lett. 1991, 32: 6735

<A NAME="RU07210ST-20B">20b</A> For the generation and cycloadditions of the benzynes containing C-glycoside moieties, see: Matsumoto T. Hosoya T. Suzuki K. J. Am. Chem. Soc. 1992, 114: 3568

<A NAME="RU07210ST-20C">20c</A> Matsumoto T. Yamaguchi H. Suzuki K. Tetrahedron 1997, 53: 16533

<A NAME="RU07210ST-20D">20d</A> Futagami S. Ohashi Y. Imura K. Hosoya T. Ohmori K. Matsumoto T. Suzuki K. Tetrahedron Lett. 2000, 41: 1063

<A NAME="RU07210ST-20E">20e</A> Matsumoto T. Yamaguchi H. Hamura T. Tanabe M. Kuriyama Y. Suzuki K. Tetrahedron Lett. 2000, 41: 8383

Zusatzmaterial

Supporting Information (PDF) (opens in new window)