Solid-Phase Synthesis of a Phytoalexin Elicitor-Active Tetraglucosyl Glucitol

Abstract

A solid-phase synthesis of pentasaccharide 1 that has phytoalexin elicitor activity for rice is described. Efficient block-type synthesis by β-selective glycosylation with thioglycosides A ₃ and B ₂ at the 3-position of the polymer-supported glycosyl acceptor has been demonstrated.

glycosylations - oligosaccharides - phytoalexin elicitor activity - solid-phase synthesis - thioglycosides

References

<A NAME="RY05002ST-1">1</A> Yamaguchi T. Yamada A. Hong N. Ogawa T. Ishii T. Shibuya N. The Plant Cell  2000,  12:  817 

<A NAME="RY05002ST-2">2</A> Taylor CM. In Combinatorial Chemistry   Wilson SR. Czarnik AW. John Wiley and Sons, Inc.; New York: 1997.  p.207 

<A NAME="RY05002ST-3A">3a</A> Yamada H. Harada T. Takahashi T. J. Am. Chem. Soc.  1994,  116:  7919 

<A NAME="RY05002ST-3B">3b</A> Nicolaou KC. Winssinger N. Pastor J. DeRoose F. J. Am. Chem. Soc.  1997,  119:  449 

<A NAME="RY05002ST-3C">3c</A> Nicolaou KC. Watanabe N. Li J. Pastor J. Winssinger N. Angew. Chem. Int. Ed.  1998,  37:  1559 

<A NAME="RY05002ST-3D">3d</A> Geurtsen R. Côté F. Hahn MG. Boons G.-J. J. Org. Chem.  1999,  64:  7828 

<A NAME="RY05002ST-3E">3e</A> Plante OJ. Palmacci ER. Seeberger PH. Science (Washington D.C.)  2001,  291:  1523 

<A NAME="RY05002ST-3F">3f</A> Yamada H. Takimoto H. Ikeda T. Tsukamoto H. Harada T. Takahashi T. Synlett  2001,  1751 

<A NAME="RY05002ST-4A">4a</A> Du Y. Zhang M. Kong F. Org. Lett.  2000,  2:  3797 

<A NAME="RY05002ST-4B">4b</A> Yang G. Kong F. Synlett  2000,  1423 

<A NAME="RY05002ST-5">5</A> Amaya T. Tanaka H. Yamaguchi T. Shibuya N. Takahashi T. Tetrahedron Lett.  2001,  42:  9191 

<A NAME="RY05002ST-6">6</A> In Solid Support Oligosaccharide Synthesis and Combinatorial Carbohydrate Libraries   Seeberger PH. John Wiley and Sons, Inc.; New York: 2001. 

Recent reports utilizing an ester linker in solid-phase glycosylation:

<A NAME="RY05002ST-7A">7a</A> Zhu T. Boons G.-J. Angew. Chem. Int. Ed.  1998,  37:  1898 

<A NAME="RY05002ST-7B">7b</A> Egusa K. Fukase K. Nakai Y. Kusumoto S. Synlett  2000,  27 

<A NAME="RY05002ST-7C">7c</A> Roussel F. Knerr L. Grathwohl M. Schmidt RR. Org. Lett.  2000,  2:  3043 

<A NAME="RY05002ST-8">8</A> Deng S. Yu B. Hui Y. Yu H. Han X. Carbohydr. Res.  1999,  317:  53 

<A NAME="RY05002ST-9">9</A> Ek M. Garegg PJ. Hultberg H. Oscarson S. J. Carbohydr. Chem.  1983,  2:  305 

Preparation of 2-O-benzoyl derivative instead of 2-O-(4-methyl)benzoyl one was reported. See:

<A NAME="RY05002ST-10A">10a</A> Garegg PJ. Hällgren C. J. Carbohydr. Chem.  1992,  11:  425 

<A NAME="RY05002ST-10B">10b</A> Ekelöf K. Oscarson S. J. Org. Chem.  1996,  61:  7711 

<A NAME="RY05002ST-11A">11a</A> Mootoo DR. Konradsson P. Udodong U. Fraser-Reid B. J. Am. Chem. Soc.  1988,  110:  5583 

<A NAME="RY05002ST-11B">11b</A> Fraser-Reid B. Udodong U. Wu Z. Ottosson H. Merritt JR. Rao CS. Roberts C. Madsen R. Synlett  1992,  927 

<A NAME="RY05002ST-12">12</A>

Compound 7 was prepared from 2 by deprotection of TBS (see ref. [3b] ) and glycosidation of the corresponding 3,6-hydroxy free phenyl thioglucoside with excess benzyl alcohol (NIS-TfOH, CH₂Cl₂, MS 4 Å, 0 °C, 52%).

<A NAME="RY05002ST-13">13</A>

Commercially available from Argonaut Technologies, San Carlos, California: http://www.argotech.com

<A NAME="RY05002ST-14">14</A> Valerio RM. Bray AM. Maeji NJ. Int. J. Peptide Protein Res.  1994,  44:  158 ; Mimotopes Pty Ltd, 11 Duerdin Street, Clayton Victoria 3168 Australia:http://www.mimotopes.com.au

<A NAME="RY05002ST-15">15</A> Kaiser E. Colescott RL. Bossinger CD. Cook PI. Anal. Biochem.  1970,  34:  595 

<A NAME="RY05002ST-16">16</A> Veenemam GH. van Leeuwen SH. van Boom JH. Tetrahedron Lett.  1990,  31:  1331 

<A NAME="RY05002ST-17">17</A> Bunin BA. The Combinatorial Index   Academic Press; San Diego: 1998.  p.219 

<A NAME="RY05002ST-18">18</A> Fukase K. Nakai Y. Egusa K. Porco JA. Kusumoto S. Synlett  1999,  1074 

<A NAME="RY05002ST-19A">19a</A>

Spectral data of all compounds shown in this manuscript are in good agreement. β-Orientation of the glycosyl linkage was assisted by anchoring effect of the benzoate group at the 2-position and was determined by the chemical shifts of ¹³C NMR of anomeric carbons.

<A NAME="RY05002ST-19B">19b</A> Kotowycz G. Lemieux RU. Chem. Rev.  1973,  73:  669 

<A NAME="RY05002ST-20">20</A>

Spectral data of B ₂ : ¹H NMR (400 MHz, CDCl₃): δ = -0.22 (s, 3 H), -0.11 (s, 3 H), 0.72 (s, 9 H), 1.08 (dd, 3 H, J = 7.2, 7.2 Hz), 2.39 (s, 3 H), 2.49 (dq, 1 H, J = 7.2, 12.5 Hz), 2.59 (dq, 1 H, J = 7.2, 12.5 Hz), 3.41 (dd, 1 H, J = 8.7, 9.7 Hz), 3.45-3.57 (m, 2 H), 3.63 (dd, 1 H, J = 5.3, 11.1 Hz), 3.72-3.88 (m, 5 H), 4.12 (brd, 1 H, J = 10.6 Hz), 4.37 (d, 1 H, J = 10.2 Hz), 4.45 (d, 1 H, J = 11.6 Hz), 4.53-4.59 (m, 4 H), 4.64 (d, 1 H, J = 12.1 Hz), 4.65 (d, 1 H, J = 11.1 Hz), 4.71 (d, 1 H, J = 11.1 Hz), 4.80 (d, 1 H, J = 11.1 Hz), 5.13 (dd, 1 H, J = 9.2, 9.7 Hz), 5.31 (dd, 1 H, J = 8.2, 8.2 Hz), 7.09-7.39 (m, 22 H), 7.42 (dd, 2 H, J = 7.3, 7.7 Hz), 7.55 (t, 1 H, J = 7.3 Hz), 7.89 (d, 2 H, J = 7.7 Hz), 8.01 (d, 2 H, J = 7.3 Hz); ¹³C NMR (99.6 MHz, CDCl₃): δ = -4.4, -4.1, 14.8, 17.7, 21.6, 23.4, 25.6, 67.9, 68.8, 73.0, 73.6, 74.6, 75.0, 75.3, 77.9, 78.5, 79.1, 82.9, 83.1, 101.1, 127.2, 127.4, 127.6, 127.8, 128.0, 128.2 × 2, 128.4, 129.1, 129.9, 130.4, 132.9, 137.9, 138.0, 138.2, 143.6, 165.0, 165.3; MS (FAB): 1105 [M + Na]⁺.

<A NAME="RY05002ST-21">21</A>

Spectral data of 21: [α]_D ²⁷ +22.6 (c 0.400 in CHCl₃); ¹H NMR (400 MHz, CDCl₃): δ = 3.18-3.78 (m, 27 H), 3.85 (dd, J = 9.2, 9.2 Hz, 1 H), 3.96 (d, J = 9.7 Hz, 1 H), 4.05 (brd, J = 7.25 Hz, 1 H), 4.25 (d, J = 12.1 Hz, 1 H), 4.30 (d, J = 12.1 Hz, 1 H), 4.38-4.81 (m, 18 H), 4.86 (d, J = 12.1 Hz, 1 H), 4.89 (d, J = 11.6 Hz, 1 H), 5.00 (d, J = 11.1 Hz, 1 H), 5.07 (d, J = 11.1 Hz, 1 H), 5.15 (d, J = 11.1 Hz, 1 H), 7.15-7.35 (m, 50 H); ¹³C NMR (99.6 MHz, CDCl₃): δ = 61.8, 68.2, 68.3, 68.9, 71.5, 73.1, 73.3, 73.4, 73.7, 74.4, 74.6, 74.7, 74.8, 74.9, 75.0, 75.2, 75.3, 75.4, 76.0, 77.6, 84.4, 84.6, 85.5, 86.6, 87.9, 101.4, 103.4, 103.6, 104.9, 105.5, 127.5, 127.6, 127.7, 127.8, 127.9 × 2, 128.0, 128.1, 128.2, 128.3, 128.5, 128.8, 130.1, 133.5, 137.0, 137.8, 137.9, 138.1 × 2, 138.2, 138.3, 138.4 × 2, 138.5, 138.8, 138.9; MS (ESI-TOF): 1752 [M + Na]⁺.