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

Hiroki Yasutomi; Daiki Takeda; Makoto Yoritate; Shuhei Higashibayashi; Takeshi Sugai; Go Hirai

doi:10.1055/a-1989-2541

Synlett, Inhaltsverzeichnis

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

^aGraduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan

,

Daiki Takeda

^aGraduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan

,

Makoto Yoritate∗

^aGraduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan

,

Shuhei Higashibayashi

^bFaculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato-ku, Tokyo 105-8512, Japan

,

Takeshi Sugai

^bFaculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato-ku, Tokyo 105-8512, Japan

,

Go Hirai ∗

^aGraduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan

› Institutsangaben

Abstract

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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

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Referenzen

References and Notes
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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

Zusatzmaterial

Supporting Information