Download PDF
Synlett 2021; 32(08): 817-821
DOI: 10.1055/a-1384-2931
letter

Glycosylation by Alkyne Activation of the 2-O-Substituted Propargyl Group in a β-Phenylthioglucoside with a 5 S 1 Conformation

Kazutada Ikeuchi  ∗
a   Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10, Nishi 8, Kita-ku, Sapporo, 060-0810, Japan
b   School of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
,
Shintaro Matsumoto
b   School of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
,
Daiki Ikuta
b   School of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
,
Hidetoshi Yamada 
b   School of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
› Author AffiliationsJSPS KAKENHI (Grants Nos. JP16H01163 in Middle Molecular Strategy, JP16KT0061, and JP19K15549) partly supported this work.
› Further Information
    Permissions and Reprints All articles of this category


Abstract

Generally, glycosylation reactions activate an anomeric substituent in a glycosyl donor to generate an oxocarbenium ion intermediate. Here we report a novel glycosylation reaction triggered by the activation of a 2-O-substituted propargyl group in a 3,6-O-1,1′-[(ethane-1,2-diyl)bibenzene-2,2′-bis(methylene)]-β-thioglucoside. This reaction proceeds through a cationic Au(I)-mediated intramolecular migration of the anomeric substituent onto the alkyne moiety of the propargyl group, followed by α-attack by the hydroxy group in the glycosyl acceptor on the oxocarbenium ion. The migration of the anomeric group occurs selectively through a 6-exo-dig pathway. The 2-(phenylsulfanyl)prop-2-en-1-yl group produced during the glycosylation is removable under conditions similar to those used for removing an allyl group. This reaction will be developed for further applications in orthogonal oligosaccharide synthesis.

Key words

glycosylation - stereoselectivity - propargyl group - gold catalysis - intramolecular migration

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1384-2931.
  • Supporting Information


Publication History

Received: 18 January 2021

Accepted after revision: 05 February 2021

Accepted Manuscript online:
05 February 2021

Article published online:
22 February 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References and Notes

  • 1 Handbook of Chemical Glycosylation: Advances in Stereoselectivity and Therapeutic Relevance. Demchenko AV. Wiley-VCH; Weinheim: 2008
    Google Scholar

      • Although a remarkable glycosylation has been recently reported, the reaction pathway is similar to that shown in Scheme [1a]; see:
    • 3a Xiao X, Zeng J, Fang J, Sun J, Li T, Song Z, Cai L, Wan Q. J. Am. Chem. Soc. 2020; 142: 5498
      CrossrefPubMed
    • 3b Meng L, Wu P, Fang J, Xiao Y, Xiao X, Tu G, Ma X, Teng S, Zeng J, Wan Q. J. Am. Chem. Soc. 2019; 141: 11775
      CrossrefPubMed
    • 3c Tanaka M, Nakagawa A, Nishi N, Iijima K, Sawa R, Takahashi D, Toshima K. J. Am. Chem. Soc. 2018; 140: 3644
      CrossrefPubMed
    • 3d Walk JT, Buchan ZA, Montgomery J. Chem. Sci. 2015; 6: 3448
      CrossrefPubMed
  • 4 Xia M.-j, Yao W, Meng X.-b, Lou Q.-h, Li Z.-j. Tetrahedron Lett. 2017; 58: 2389
    Crossref
  • 5 Ikuta D, Hirata Y, Wakamori S, Shimada H, Tomabechi Y, Kawasaki Y, Ikeuchi K, Hagimori T, Matsumoto S, Yamada H. Science 2019; 364: 674
    CrossrefPubMed
  • 6 Motoyama A, Arai T, Ikeuchi K, Aki K, Wakamori S, Yamada H. Synthesis 2018; 50: 282
    CrossrefPubMed
    • 7a Hu Z, Tang Y, Yu B. J. Am. Chem. Soc. 2019; 141: 4806
      CrossrefPubMed
    • 7b Chen X, Shen D, Wang Q, Yang Y, Yu B. Chem. Commun. 2015; 51: 13957
      CrossrefPubMed
    • 7c Yu J, Sun J, Niu Y, Li R, Liao J, Zhang F, Yu B. Chem. Sci. 2013; 4: 3899
      Crossref
    • 7d Yang F, Wang Q, Yu B. Tetrahedron Lett. 2012; 53: 5231
      Crossref
    • 7e Li Y, Yang X, Liu Y, Zhu C, Yang Y, Yu B. Chem. Eur. J. 2010; 16: 1871
      CrossrefPubMed
    • 7f Li Y, Yang Y, Yu B. Tetrahedron Lett. 2008; 49: 3604
      Crossref

      • For a review, see:
    • 7g Yu B. Acc. Chem. Res. 2018; 51: 507
      CrossrefPubMed

      Recently, a similar glycosylation reaction to that reported by Yu has also been reported, see:
    • 8a Shaw M, Thakur R, Kumar A. J. Org. Chem. 2019; 84: 589
      CrossrefPubMed
    • 8b Li X, Li C, Liu R, Wang J, Wang Z, Chen Y, Yang Y. Org. Lett. 2019; 21: 9693
      CrossrefPubMed
    • 8c Mishra B, Neralkar M, Hotha S. Angew. Chem. Int. Ed. 2016; 55: 7786
      CrossrefPubMed
  • 9 A gold(III)-mediated glycosylation through activation of the anomeric propargyl group has been reported, see: Hotha S, Kashyap S. J. Am. Chem. Soc. 2006; 128: 9620 DOI: ; corrigendum: J. Am. Chem. Soc. 2006, 128, 17153.
    Crossref
  • 10 Codée JD. C, Litjens RE. J. N, van den Bos LJ, Overkleeft HS, van der Marel GA. Chem. Soc. Rev. 2005; 34: 769
    CrossrefPubMed
    • 11a Thummala Y, Raju CE, Purnachandar D, Sreenivasulu G, Doddi VR, Karunakar GV. Eur. J. Org. Chem. 2020; 3560
    • 11b Kong X.-F, Zhan F, He G.-X, Pan C.-X, Gu C.-X, Lu K, Mo D.-L, Su G.-F. J. Org. Chem. 2018; 83: 2006
      CrossrefPubMed
    • 11c Naoe S, Saito T, Uchiyama M, Oishi S, Fujii N, Ohno H. Org. Lett. 2015; 17: 1774
      CrossrefPubMed
    • 11d Shibata T, Baba T, Takano H, Kanyiva KS. Adv. Synth. Catal. 2017; 359: 1849
      Crossref
    • 11e Nandakumar A, Kiruthika SE, Naveen K, Perumal PT. Org. Biomol. Chem. 2014; 12: 876
      CrossrefPubMed
  • 12 Dong X, Chen L, Zheng Z, Ma X, Luo Z, Zhang L. Chem. Commun. 2018; 54: 8626
    CrossrefPubMed
  • 13 In this investigation, β-19 was detected. See the Supporting Information (SI-5) for details.
  • 14 Glycoside 19; Typical Procedure (4-F3CC6H4)3PAuNTf2 (20 mM) in CH2Cl2 (200 μL, 4.0 μmol) was added to a stirred mixture of 13 (20.0 mg, 33.0 μmol), cyclohexylmethanol (5.9 mg, 51 μmol), and activated MS 4 Å (99 mg) in CH2Cl2 (1.3 mL) at 0 °C, and the mixture was stirred for 24 h at 0 °C. Sat. aq NaHCO3 and Et2O were added, and the mixture was filtered through a cotton–Celite pad to remove the MS. The aqueous filtrate was extracted with Et2O, and the combined organic layer was washed successively with H2O and brine. The combined organic layer was dried (Na2SO4), filtered, and concentrated, and the residue was purified by column chromatography [silica gel, hexane–EtOAc (15:1 to 9:1)] to give a colorless oil; yield: 20.0 mg (84%, 27.7 μmol, α-form only); [α]D 24 +34.5 (c 1.47, CHCl3). IR (ATR): 3063, 3024, 2922, 2853, 1647, 1452, 1323, 1071, 772 cm–1. 1H NMR (400 MHz, CDCl3, 24 °C): δ = 7.46–7.13 (m, 16 H), 7.06 (dd, J = 6.4, 2.8 Hz, 2 H), 5.66 (s, 1 H), 5.22 (s, 1 H), 4.85 (d, J = 3.4 Hz, 1 H), 4.58 (d, J = 10.1 Hz, 1 H), 4.51 (d, J = 11.2 Hz, 1 H), 4.40 (d, J = 11.2 Hz, 1 H), 4.35 (d, J = 11.9 Hz, 1 H), 4.27 (d, J = 10.1 Hz, 1 H), 4.25 (d, J = 14.2 Hz, 1 H), 4.20 (d, J = 11.9 Hz, 1 H), 4.18 (d, J = 14.2 Hz, 1 H), 4.13 (dd, J = 6.6, 3.7 Hz, 1 H), 4.01 (dd, J = 6.6, 3.7 Hz, 1 H), 3.95 (ddd, J = 6.6, 3.7, 2.3 Hz, 1 H), 3.77 (dd, J = 10.7, 3.7 Hz, 1 H), 3.69 (dd, J = 6.6, 3.4 Hz, 1 H), 3.67 (dd, J = 10.7, 2.3 Hz, 1 H), 3.47 (dd, J = 9.4, 6.6 Hz, 1 H), 3.11 (dd, J = 9.4, 6.6 Hz, 1 H), 3.04–2.84 (m, 4 H), 1.72–1.53 (m, 6 H), 1.22–1.01 (m, 3 H), 0.90–0.78 (m, 2 H). 13C NMR (101 MHz, CDCl3, 24 °C): δ = 141.8, 141.7, 140.3, 138.6, 136.2, 135.7, 133.0, 132.5 (2 C), 131.5, 131.0, 129.2 (2 C), 129.1, 129.0, 128.7, 128.4, 128.2 (2 C), 127.9 (2 C), 127.7, 127.4, 126.3, 126.2, 116.5, 96.6, 78.9, 75.1, 74.1, 72.9, 72.9, 72.5, 72.1, 71.5, 69.7, 66.4, 37.9, 33.5, 33.4, 30.1 (2 C), 26.7, 26.0, 25.9. HRMS (ESI): m/z [M + Na]+ calcd for C45H52NaO6S: 743.3382; found: 743.3379.
  • 15 Application of the established conditions to phenylsulfanyl 3,4,6-O-tribenzyl-2-O-proparygyl-β-d-glucopyranose resulted in almost no reaction, indicating that the presence of the EDB group is essential for this glycosylation reaction.
  • 16 See the Supporting Information (SI-8) for the yields of 24 and 25. In cases when 13 was recovered, its yield is also reported.
    • 17a Kaeothip S, Demchenko AV. J. Org. Chem. 2011; 76: 7388
      CrossrefPubMed
    • 17b Kanie O, Ito Y, Ogawa T. J. Am. Chem. Soc. 1994; 116: 12073
      Crossref