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Synlett 2023; 34(04): 347-352
DOI: 10.1055/a-1989-2541
letter

Transition-Metal-Free β-Selective C-Glycosylation of β-Glycosyl Boronates via Stereoretentive 1,2-Migration

Hiroki Yasutomi
a   Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
,
Daiki Takeda
a   Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
,
Makoto Yoritate∗
a   Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
,
Shuhei Higashibayashi
b   Faculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato-ku, Tokyo 105-8512, Japan
,
Takeshi Sugai
b   Faculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato-ku, Tokyo 105-8512, Japan
,
Go Hirai  ∗
a   Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
› Author AffiliationsThis study was partially supported by PRIME, BINDS, and SCARDA from the Japan Agency for Medical Research and Development (AMED), JSPS KAKENHI (grants nos. 22K14683, 21K19053, and 21H02070), the Mizutani Foundation for Glycoscience, and the Sumitomo Foundation.
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Abstract

C-Glycoside analogues of native glycans are useful molecular tools for medicinal chemistry and chemical biology due to their resistance to cellular glycoside hydrolases. We previously reported an α-selective direct C-glycosylation of 2-deoxy-β-glycosyl boronate through a Ni/photoredox-catalyzed stereoinvertive cross-coupling reaction. Here we report a complementary stereoretentive synthetic method for the preparation of β-C-glycosides from a similar boronate precursor through the addition of a C(sp2) anion followed by 1,2-migration of the glycosyl donor.

Key words

glycosides - boronates - 1,2-migration - Zweifel olefination - carbohydrates - cross-metathesis

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1989-2541.
  • Supporting Information


Publication History

Received: 08 November 2022

Accepted after revision: 29 November 2022

Accepted Manuscript online:
29 November 2022

Article published online:
03 January 2023

© 2022. Thieme. All rights reserved

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  • 35 C-Vinyl Glycoside 17 G-II catalyst (2.6 mg, 3.0 μmol, 10 mol%) was added to a mixture of 11e (12.6 mg, 30.0 μmol, 1.0 equiv), 16 (13.5 mg, 45.0 μmol, 1.5 equiv),8 and CuI (2.3 mg, 12.0 μmol, 40 mol%) in Et2O (300 μL), and the resulting mixture was heated to 40 °C for 12 h. The solution was then concentrated in vacuo and the residue was purified by column chromatography [silica gel, EtOAc–hexane (25% to 40%)] to give a colorless oil; yield: 9.0 mg (49%); [α]D 27 +16.1 (c 1.0, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 5.77 (ddd, J = 15.6, 5.2, 0.8 Hz, 1 H), 5.64 (ddd, J = 15.6, 6.3, 1.1 Hz, 1 H), 5.58 (d, J = 4.6 Hz, 1 H), 5.20 (dd, J = 3.7, 3.7 Hz, 1 H), 4.82 (d, J = 6.1 Hz, 1 H), 4.79 (d, J = 6.1 Hz, 1 H), 4.77 (d, J = 6.7 Hz, 1 H), 4.78–4.75 (m, 1 H), 4.73 (d, J = 6.7 Hz, 1 H), 4.32 (brdd, J = 9.5, 6.3 Hz, 1 H), 4.16 (dd, J = 4.6, 3.7 Hz, 1 H), 3.96 (dd, J = 11.3, 1.5 Hz, 1 H), 3.89 (dd, J = 11.3, 4.0 Hz, 1 H), 3.92–3.87 (m, 1 H), 3.67 (ddd, J = 11.6, 8.9, 4.9 Hz, 1 H), 3.54 (dd, J = 9.2, 8.9 Hz, 1 H), 3.42 (d, J = 5.2 Hz, 3 H), 3.40–3.38 (m, 3 H), 3.23 (ddd, J = 9.2, 4.0, 1.5 Hz, 1 H), 2.14 (ddd, J = 12.8, 4.9, 2.1 Hz, 1 H), 2.10 (s, 3 H), 2.04 (s, 3 H), 1.61 (s, 3 H), 1.42 (ddd, J = 12.8, 11.6, 11.6 Hz, 1 H), 1.35 (s, 3 H), 1.13–1.03 (m, 21 H). 13C NMR (125 MHz, CDCl3): δ = 169.86, 169.60, 134.36, 126.32, 109.68, 98.20, 96.76, 96.45, 80.16, 79.14, 75.77, 74.83, 73.98, 72.11, 71.38, 69.16, 63.11, 56.41, 55.63, 38.31, 26.73, 25.85, 21.00 (2 C), 18.16 (3 C), 18.14 (3 C), 12.19 (3 C). HRMS (ESI): m/z [M + Na]+ calcd for C33H58NaO13Si: 713.3544; found: 713.3511.
  • 36 Disaccharide 19 Rh/Al2O3 (5% Rh; 4.2 mg, 1.0 μmol, 17 mol%) was added to a solution of 17 (4.2 mg, 6.1 μmol, 1.0 equiv) in EtOAc (0.6 mL), and the mixture was purged with H2 gas then stirred for 16 h at r.t. The resulting mixture was filtered through a pad of Celite and concentrated. The residue was purified by column chromatography [silica gel, EtOAc–hexane (3:1)] to give a colorless oil; yield: 4.0 mg (95%); [α]D 27 +22.3 (c 0.4, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 5.54 (d, J = 4.9 Hz, 1 H), 5.13 (dd, J = 3.2, 3.2 Hz, 1 H), 4.81 (d, J = 6.1 Hz, 1 H), 4.79 (d, J = 6.1 Hz, 1 H), 4.76 (d, J = 6.7 Hz, 1 H), 4.73 (d, J = 6.7 Hz, 1 H), 4.67 (dd, J = 9.5, 3.2 Hz, 1 H), 4.15 (dd, J = 4.9, 3.2 Hz, 1 H), 3.94 (dd, J = 11.3, 1.5 Hz, 1 H), 3.87 (dd, J = 11.3, 3.7 Hz, 1 H), 3.76 (td, J = 9.5, 2.5 Hz, 1 H), 3.63 (ddd, J = 11.3, 9.2, 5.2 Hz, 1 H), 3.52 (dd, J = 9.2, 9.2 Hz, 1 H), 3.41 (d, J = 3.7 Hz, 3 H), 3.38 (d, J = 5.8 Hz, 3 H), 3.33–3.26 (m, 1 H), 3.15 (ddd, J = 9.2, 3.7, 1.5 Hz, 1 H), 2.09 (s, 3 H), 2.07 (s, 3 H), 2.10–2.04 (m, 1 H), 1.90–1.82 (m, 1 H), 1.78–1.70 (m, 1 H), 1.59 (s, 3 H), 1.47–1.31 (m, 3 H), 1.33 (s, 3 H), 1.12–1.02 (m, 21 H). 13C NMR (125 MHz, CDCl3): δ = 170.09, 169.56, 109.61, 98.16, 96.69, 96.34, 79.95, 79.22, 76.08, 75.09, 73.64, 72.92, 71.30, 68.51, 63.06, 56.39, 55.55, 38.51, 31.91, 29.21, 26.48, 25.72, 21.07, 21.02, 18.13 (3 C), 18.08 (3 C), 12.16 (3 C). HRMS(ESI): m/z [M + Na]+ calcd for C33H60NaO13Si: 715.3701; found: 715.3710