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 Affiliations
This 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.


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.

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

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
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  • 30 C-Vinylglycosides 11a and 11e; General Procedure A 1.0 M solution of vinylmagnesium bromide in THF (1.5 equiv) was added dropwise to a 0.1 M solution of the appropriate boronic ester 7 (1.0 equiv) in anhyd THF at –78 °C. The resulting mixture was stirred at –78 °C for 30 min, then warmed to r.t. and stirred for a further 30 min. The mixture was cooled to –78 °C and a 0.2 M solution of I2 (1.5 equiv) in MeOH was added dropwise from a cannula. The resulting mixture was stirred at –78 °C for 30 min, then warmed to r.t. and stirred for a further 30 min. The mixture was again cooled to –78 °C, and a 0.4 M solution of NaOMe (3.0 equiv) in MeOH was added. The mixture was then allowed to warm to r.t. and stirred for an additional 1 h. It was then diluted with EtOAc (20 mL) and washed with 1 M aq Na2S2O3 (10 mL) and sat. aq NH4Cl (10 mL). The aqueous layer was extracted with EtOAc (2 × 20 mL) and the combined organic layers were dried (MgSO4), filtered, and concentrated in vacuo. The residue was purified by column chromatography (silica gel). 11a: Prepared by following the general procedure from 7a (80.5 mg, 0.152 mmol) as a colorless oil; yield: 30.3 mg (47%); [α]D 16 –14.2 (c 2.0, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 5.79 (ddd, J = 17.4, 10.5, 5.8 Hz, 1 H), 5.24 (dt, J = 17.4, 1.2 Hz, 1 H), 5.13 (dt, J = 10.5, 1.2 Hz, 1 H), 4.15 (dd, J = 10.1, 4.9 Hz, 1 H), 3.96 (ddddd, J = 11.9, 5.8, 2.4, 1.2, 1.2 Hz, 1 H), 3.86 (dd, J = 10.1, 10.1 Hz, 1 H), 3.67 (ddd, J = 11.0, 8.2, 5.2 Hz, 1 H), 3.61 (dd, J = 8.9, 8.2 Hz, 1 H), 3.36 (ddd, J = 10.1, 8.9, 4.9 Hz, 1 H), 1.91 (ddd, J = 13.4, 5.2, 2.4 Hz, 1 H), 1.54 (ddd, J = 13.4, 11.9, 11.0 Hz, 1 H), 1.05 (s, 9 H), 1.00 (s, 9 H), 0.90 (s, 9 H), 0.12 (s, 3 H), 0.10 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 137.56, 116.14, 79.23, 76.73, 75.01, 73.36, 67.03, 40.54, 27.72 (3 C), 27.21 (3 C), 25.95 (3 C), 22.86, 20.08, 18.29, –4.15, –4.60. HRMS (ESI): m/z [M + Na]+ calcd for C22H44NaO4Si2: 451.2676; found: 451.2673. 11e: Prepared by following the general procedure from 7e (76.5 mg, 148 μmol) as a colorless oil; yield: 49.0 mg (79%); [α]D 16 +34.3 (c 1.0, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 5.81 (ddd, J = 17.4, 10.7, 5.2 Hz, 1 H), 5.24 (ddd, J = 17.4, 1.5, 1.5 Hz, 1 H), 5.07 (ddd, J = 10.7, 1.5, 1.5 Hz, 1 H), 4.82 (d, J = 6.1 Hz, 1 H), 4.80 (d, J = 6.1 Hz, 1 H), 4.77 (d, J = 6.7 Hz, 1 H), 4.75 (d, J = 6.7 Hz, 1 H), 3.99 (dd, J = 11.3, 1.5 Hz, 1 H), 3.91 (dd, J = 11.3, 3.7 Hz, 1 H), 3.91–3.86 (m, 1 H), 3.69 (ddd, J = 11.6, 8.9, 4.9 Hz, 1 H), 3.56 (dd, J = 9.2, 8.9 Hz, 1 H), 3.41 (s, 3 H), 3.38 (s, 3 H), 3.26 (ddd, J = 9.2, 3.7, 1.5 Hz, 1 H), 2.14 (ddd, J = 12.8, 4.9, 1.5 Hz, 1 H), 1.48–1.41 (ddd, J = 12.8, 11.6, 11.0 Hz, 1 H), 1.11–1.05 (m, 21 H). 13C NMR (125 MHz, CDCl3): δ = 138.05, 114.92, 98.19, 96.33, 80.08, 79.15, 75.85, 75.81, 63.12, 56.39, 55.57, 38.19, 18.14 (3 C), 18.10 (3 C), 12.19 (3 C). HRMS (ESI): m/z [M + Na]+ calcd for C21H42NaO6Si: 441.2648; found: 441.2643.
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  • 33 Addition of 2 equivalents of MeMgBr appeared to afford a dimethylborane intermediate, but the desired product was not obtained; instead, a 1-OH hemiacetal was detected. It is probable that the intermediate underwent bromination to form the 1-bromo sugar, which was then converted into the hemiacetal S10 by hydrolysis. For details, see the Supporting Information.
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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