Benzenesulfinyl Morpholine: A New Promoter for One-Pot Oligosaccharide Synthesis Using Thioglycosides by Pre-Activation Strategy

Changning Wang; Haisheng Wang; Xuefei Huang; Li-He Zhang; Xin-Shan Ye

doi:10.1055/s-2006-950247

RSS-Feed abonnieren

Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.

https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000083.xml

Teilen / Bookmarken

Facebook X Linkedin Weibo

PDF herunterladen

Synlett 2006(17): 2846-2850
DOI: 10.1055/s-2006-950247

LETTER

Benzenesulfinyl Morpholine: A New Promoter for One-Pot Oligosaccharide Synthesis Using Thioglycosides by Pre-Activation Strategy

Changning Wang^a, Haisheng Wang^a, Xuefei Huang^b, Li-He Zhang^a, Xin-Shan Ye*^a
^a The State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd 38, Beijing 100083, P. R. of China
Fax: +86(10)62014949; e-Mail: xinshan@bjmu.edu.cn;
^b Department of Chemistry, University of Toledo, 2801 W. Bancroft Street, MS 602, Toledo, OH 43606, USA

Weitere Informationen

Publikationsverlauf

Received 26 July 2006
Publikationsdatum:
09. Oktober 2006 (online)

Abstract
Volltext
Referenzen

Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Benzenesulfinyl morpholine (BSM) has been applied as a new promoter for the activation of thioglycosides. This proceeds by the in situ reaction of BSM with trifluoromethanesulfonic anhydride, which subsequently activates thioglycosides for glycosylations. Importantly, this reagent works well in our pre-activation one-pot oligosaccharide assembly strategy.

Key words

benzenesulfinyl morpholine - promoter - thioglycoside - pre-activation - one-pot oligosaccharide assembly

References and Notes

1a Danishefsky SJ. Bilodeau MT. Angew. Chem., Int. Ed. Engl. 1996, 35: 1380

Crossref PubMed Google Scholar
1b Seeberger PH. Danishefsky SJ. Acc. Chem. Res. 1998, 31: 685

Crossref PubMed Google Scholar
1c Plante OJ. Palmacci ER. Seeberger PH. Science 2001, 291: 1523

Crossref PubMed Google Scholar
1d Plante OJ. Palmacci ER. Seeberger PH. Adv. Carbohydr. Chem. Biochem. 2003, 58: 35

Crossref PubMed Google Scholar
1e Seeberger PH. Haase WC. Chem. Rev. 2000, 100: 4349

Crossref PubMed Google Scholar
2a Kanie O. Ito Y. Ogawa T. J. Am. Chem. Soc. 1984, 116: 12073

Crossref Google Scholar
2b Demchenko AV. De Meo C. Tetrahedron Lett. 2002, 43: 8819

Crossref Google Scholar
2c Chang GX. Lowary TL. Org. Lett. 2000, 2: 1505

Crossref Google Scholar
2d Paulsen H. Angew. Chem., Int. Ed. Engl. 1995, 34: 1432

Crossref Google Scholar
2e Demchenko AV. Lett. Org. Chem. 2005, 2: 580

Crossref Google Scholar
3a Yamago S. Yamada T. Maruyama T. Yoshida J.-I. Angew. Chem. Int. Ed. 2004, 43: 2145

Google Scholar
3b Yamago S. Yamada T. Hara O. Ito H. Mino Y. Yoshida J.-I. Org. Lett. 2001, 3: 3867

Google Scholar
3c Nguyen HM. Poole JL. Gin DY. Angew. Chem. Int. Ed. 2001, 40: 414

Google Scholar
3d Friesen RW. Danishefsky SJ. J. Am. Chem. Soc. 1989, 111: 6656

Google Scholar
3e Yamago S. Yamada T. Ito H. Chem. Eur. J. 2005, 11: 6159

Google Scholar
4a Codee JDC. van den Bos LJ. Litjens REJN. Overkleeft HS. van Boeckel CAA. van Boom JH. van der Marel GA. Tetrahedron 2004, 60: 1057

Crossref Google Scholar
4b Lahmann M. Oscarson S. Can. J. Chem. 2002, 80: 889

Crossref Google Scholar
4c Zhu T. Boons G.-J. Org. Lett. 2001, 3: 4201

Crossref Google Scholar
5a Mong TK.-K. Lee H.-K. Duron SG. Wong C.-H. Proc. Natl. Acad. Sci. U.S.A. 2003, 100: 797

Google Scholar
5b Ritter TK. Mong TK.-K. Liu H. Nakatani T. Wong C.-H. Angew. Chem. Int. Ed. 2003, 42: 4657

Google Scholar
5c Mong TK.-K. Wong C.-H. Angew. Chem. Int. Ed. 2002, 41: 4087

Google Scholar
5d Lee J.-C. Wu C.-Y. Apon JV. Siuzdak G. Wong C.-H. Angew. Chem. Int. Ed. 2006, 45: 2753

Google Scholar
5e Ye X.-S. Wong C.-H. J. Org. Chem. 2000, 65: 2410

Google Scholar
5f Zhang Z. Ollmann IR. Ye X.-S. Wischnat R. Baasov T. Wong C.-H. J. Am. Chem. Soc. 1999, 121: 734

Google Scholar
5g Wang Y. Huang X. Zhang L.-H. Ye X.-S. Org. Lett. 2004, 6: 4415

Google Scholar
5h Wang Y. Yan Q. Wu J. Zhang L.-H. Ye X.-S. Tetrahedron 2005, 61: 4313

Google Scholar
5i Tanaka H. Adachi M. Tsukamoto H. Ikeda T. Yamada H. Takahashi T. Org. Lett. 2002, 4: 4213

Google Scholar
5j Douglas NL. Ley SV. Lucking U. Warriner SL. J. Chem. Soc., Perkin Trans. 1 1998, 51

Google Scholar
5k Ley SV. Priepke HWM. Angew. Chem., Int. Ed. Engl. 1994, 33: 2292

Google Scholar
5l Raghavan S. Kahne D. J. Am. Chem. Soc. 1993, 115: 1580

Google Scholar
5m Yamada H. Harada T. Takahashi T. J. Am. Chem. Soc. 1994, 116: 7919

Google Scholar
5n Wang Y. Zhang L.-H. Ye X.-S. Comb. Chem. High Throughput Screening 2006, 9: 63

Google Scholar
6 Huang X. Huang L. Wang H. Ye X.-S. Angew. Chem. Int. Ed. 2004, 43: 5221

Crossref Google Scholar
7a Oscarson S. In Carbohydrates in Chemistry and Biology Vol. 1: Ernst B. Hart GW. Sinay P. Wiley-VCH; Weinheim: 2000. p.93-116

Crossref Google Scholar
7b Codee JDC. Litjens REJN. van den Bos LJ. Overkleeft HS. van der Marel GA. Chem. Soc. Rev. 2005, 34: 769

Crossref Google Scholar
8a Veenenman GH. van Boom JH. Tetrahedron Lett. 1990, 31: 275

Crossref Google Scholar
8b Konradsson P. Udodong UE. Fraser-Reid B. Tetrahedron Lett. 1990, 31: 4313

Crossref Google Scholar
9 Fugedi P. Garegg PJ. Carbohydr. Res. 1986, 149: C9

Crossref Google Scholar
10 Dasgupta F. Garegg PJ. Carbohydr. Res. 1988, 177: C13

Crossref Google Scholar
11 Ito Y. Ogawa T. Tetrahedron Lett. 1988, 29: 1061

Crossref Google Scholar
12 Crich D. Smith M. Org. Lett. 2000, 2: 4067

Crossref Google Scholar
13 Crich D. Smith M. J. Am. Chem. Soc. 2001, 123: 9015

Crossref PubMed Google Scholar
14a Garcia BA. Poole JL. Gin DY. J. Am. Chem. Soc. 1997, 119: 7597

Crossref Google Scholar
14b Codee JDC. Litjens REJN. den Heeten R. Overkleeft HS. van Boom JH. van der Marel GA. Org. Lett. 2003, 5: 1519

Crossref Google Scholar
15 Duron SG. Polat T. Wong C.-H. Org. Lett. 2004, 6: 839

Crossref Google Scholar
16a Crich D. Sun S. Tetrahedron 1998, 54: 8321

Crossref Google Scholar
16b Crich D. Cai W. J. Org. Chem. 1999, 64: 4926

Crossref Google Scholar
16c Martichonok V. Whitesides GM. J. Org. Chem. 1996, 61: 1702

Crossref Google Scholar
For the preparation of BSM, see:
18a Kice JL. Liu CCA. J. Org. Chem. 1979, 44: 1918

Crossref Google Scholar
18b Harpp DN. Back TG. Tetrahedron Lett. 1972, 13: 5313

Crossref Google Scholar
19 Burkart MD. Zhang Z. Hung S.-C. Wong C.-H. J. Am. Chem. Soc. 1997, 119: 11743

Crossref Google Scholar
20 Garegg PJ. Pure. Appl. Chem. 1984, 56: 845

Crossref Google Scholar
23 Debelder AN. Adv. Carbohydr.Chem. 1965, 20: 219

Google Scholar

17

Other compounds such as methyl phenyl sulfoxide, 2-(phenylthio)quinoline, 2-(phenylthio)thiophene, N-phenylsulfanyl phthalimide, N-benzenesulfenyl succinimide were examined, but all these compounds did not give better results than BSM.

21

General Procedure for Oligosaccharide Assembly.
To a solution of 1 (100.0 mg, 0.155 mmol), and BSM (49.1 mg, 0.233 mmol) in CH₂Cl₂ (4 mL) was added 4 Å MS (40 mg), and the mixture was cooled down to -70 °C, and then Tf₂O (26.2 mg, 0.093 mmol) was added, after 5 min, 1 was consumed completely. After addition of the acceptor 2 (66.7 mg, 0.140 mmol) to the preactivated donor, the mixture was stirred for 15 min. Then the reaction mixture was warmed up to r.t. for 15 min. The mixture was cooled down to -70 °C again, Tf₂O (43.7 mg, 0.155 mmol) was added, after 5 min, and the new formed disaccharide was consumed completely. After addition of the acceptor 11 (71.9 mg, 0.155 mmol) to the preactivated donor, the mixture was stirred for 15 min. Then the reaction mixture was warmed up to r.t. for 15 min. The course of the reaction was monitored by TLC. Then, Et₃N (0.5 mL) was then added to the mixture. The precipitate was filtered off and the filtrate was concentrated. The residue was purified by column chromatography on silica gel to give 12 (126.9 mg, 52%). ¹H NMR (500 MHz, CDCl₃): δ = 2.97 (s, 1 H), 3.16 (dd, 1 H, J = 6.0, 9.0 Hz), 3.22-3.28 (m, 2 H), 3.39 (t, 1 H, J = 7.5 Hz), 3.46-3.48 (m, 5 H), 3.60-3.68 (m, 4 H), 3.73 (d, 1 H, J = 11.0 Hz), 3.79 (dd, 1 H, J = 3.5, 10.0 Hz), 3.84 (t, 1 H, J = 6.5 Hz), 3.88-3.91 (m, 1 H), 3.94-3.97 (m, 1 H), 4.11-4.26 (m, 6 H), 4.35 (t, 2 H, J = 12.0 Hz), 4.42-4.53 (m, 4 H), 4.58-4.63 (m, 2 H), 4.69 (d, 1 H, J = 6.0 Hz), 4.77-4.86 (m, 4 H), 5.04 (d, 1 H, J = 3.5 Hz, H-1′′), 5.10 (d, 1 H, J = 11.0 Hz), 5.32 (s, 1 H), 5.61 (dd, 1 H, J = 8.5, 10.0 Hz), 7.06-7.38 (m, 40 H), 7.48-7.50 (m, 3 H), 7.97-7.99 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 56.95, 66.60, 68.36, 68.73, 68.80, 69.84, 71.37, 72.13, 72.26, 73.09, 73.14, 73.22, 74.41, 74.64, 74.68, 74.92, 75.26, 75.48, 75.84, 77.64, 78.58, 81.96, 83.03, 95.55, 100.95, 101.20, 104.48, 126.39, 127.09, 127.29, 127.37, 127.45, 127.49, 127.58, 127.65, 127.81, 127.91, 127.99, 128.09, 128.15, 128.23, 128.34, 128.41, 128.70, 129.76, 129.85, 133.01, 137.77, 138.16, 138.46, 138.60, 138.65, 138.78, 139.07, 164.69. HRMS (ESI): m/z calcd for C₈₂H₈₈NO₁₇ [M + NH₄]⁺: 1358.6047; found: 1358.6053.

22

Preparation of Trisaccharide 13.
To a solution of compound 12 (80.0 mg, 0.060 mmol) in MeOH (10 mL) was added MeONa/MeOH (30 wt%, 0.4 mL), and the reaction mixture was stirred for 8 h at r.t. The mixture was neutralized (H⁺ resin, weak acid), filtered and concentrated. The resulting residue was dissolved in THF-AcOH-H₂O (2:2:1, 10 mL) and then Pd/C (10.0 mg) was added. The reaction mixture was stirred under 1 atm of H₂ for 24 h. The Pd/C was filtered off and the filtrate was concentrated. The product was purified by C-18 reverse-phase column chromatography to give 13 (28.0 mg, 90%). ¹H NMR (500 MHz, D₂O): δ = 3.29-3.30 (m, 1 H), 3.58 (s, 3 H), 3.61-3.63 (m, 1 H), 3.65-3.68 (m, 3 H), 3.71-3.87 (m, 8 H), 3.94-4.02 (m, 3 H), 4.18-4.21 (m, 2 H), 4.41 (d, 1 H, J = 8.0 Hz, H-1), 4.52 (d, 1 H, J = 7.5 Hz, H-1′), 5.14 (d, 1 H, J = 4.0 Hz, H-1′′). ¹³C NMR (125 MHz, D₂O): δ = 57.98, 60.88, 61.68, 61.74, 65.56, 68.95, 69.89, 70.03, 70.33, 71.59, 73.52, 75.21, 75.49, 75.80, 77.96, 79.38, 96.19, 103.60, 103.83. HRMS (ESI): m/z calcd for C₁₉H₃₄O₁₆Na [M + Na]⁺: 541.1739; found: 541.1748.

24

Data for Compound 16. ¹H NMR (500 MHz, CDCl₃): δ = 1.28 (s, 3 H), 1.31 (s, 3 H), 1.43 (s, 3 H), 1.47 (s, 3 H), 3.20-3.24 (m, 2 H), 3.32-3.40 (m, 3 H), 3.47-3.53 (m, 3 H), 3.64 (dd, 1 H, J = 7.5, 10.0 Hz), 3.69 (dd, 1 H, J = 3.0, 10.0 Hz), 3.82-3.89 (m, 2 H), 3.95-4.04 (m, 5 H), 4.12 (d, 1 H, J = 7.5 Hz), 4.18 (d, 1 H, J = 9.0 Hz), 4.22-4.30 (m, 5 H), 4.33 (d, 1 H, J = 10.5 Hz, H-1′), 4.36 (d, 1 H, J = 11.5 Hz), 4.42-4.58 (m, 7 H), 4.62 (d, 1 H, J = 11.0 Hz, H-1′′), 4.67 (t, J = 11.5 Hz, 2 H), 4.78 (d, 1 H, J = 11.0 Hz), 4.86 (d, 1 H, J = 11.5 Hz), 5.00 (d, 1 H, J = 11.0 Hz), 5.09 (d, 1 H, J = 4.0 Hz, H-1′′′), 5.39 (s, 1 H), 5.53 (d, 1 H, J = 5.0 Hz, H-1), 5.73 (dd, 1 H, J = 8.5, 10.0 Hz), 7.09-7.31 (m, 38 H, ArH), 7.36-7.41 (m, 3 H), 7.52 (d, 2 H, J = 8.0 Hz), 7.97 (d, 2 H, J = 8.0 Hz). ¹³C NMR (125 MHz, CDCl₃): δ = 24.47, 25.02, 26.01, 26.03, 66.40, 66.68, 67.29, 68.80, 69.04, 69.69, 69.84, 70.07, 70.48, 70.74, 71.35, 72.08, 72.19, 73.16, 73.26, 74.26, 74.61, 74.69, 74.94, 75.02, 75.31, 75.86, 78.56, 81.40, 84.38, 95.23, 96.33, 100.99 (2 C), 104.30, 108.51, 109.28, 126.39, 127.18, 127.26, 127.33, 127.36, 127.42, 127.47, 127.55, 127.71, 127.80, 127.98, 128.07, 128.10, 128.13, 128.19, 128.21, 128.26, 128.29, 128.61, 128.81, 129.86, 129.99, 132.72, 137.65, 138.23, 138.60, 138.68, 138.77, 138.81, 164.74. HRMS (ESI): m/z calcd for C₉₃H₁₀₄NO₂₂ [M + NH₄]⁺: 1586.7045; found: 1586.7039.