Concise Synthesis of Procyanidin B2 3,3′′-Digallate Using Yb(OTf)3-Mediated Self-Condensation

Yuuri Tanaka; Shu-hei Kobayashi; Yasunao Hattori; Atsushi Kawamura; Hidefumi Makabe

doi:10.1055/s-0041-1737457

Synlett, Table of Contents

Synlett 2022; 33(11): 1071-1074
DOI: 10.1055/s-0041-1737457

letter

Concise Synthesis of Procyanidin B2 3,3′′-Digallate Using Yb(OTf)₃-Mediated Self-Condensation

Yuuri Tanaka‡

^aGraduate School of Science and Technology, Department of Agriculture, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan

,

Shu-hei Kobayashi‡

^aGraduate School of Science and Technology, Department of Agriculture, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan

,

Yasunao Hattori

^bCenter for Instrumental Analysis, Kyoto Pharmaceutical University, Yamashina-ku, Kyoto 607-8412, Japan

,

Atsushi Kawamura∗

^cDepartment of Biomolecular Innovation, Institute for Biomedical Sciences, Interdisciplinary Cluster for Cutting Edge Research, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan

,

Hidefumi Makabe∗

^aGraduate School of Science and Technology, Department of Agriculture, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan

^cDepartment of Biomolecular Innovation, Institute for Biomedical Sciences, Interdisciplinary Cluster for Cutting Edge Research, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan

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Abstract

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Abstract

Lewis acid mediated self-condensation of epicatechin gallate derivative was examined. We found that Yb(OTf)₃ afforded good yield of the dimeric epicatechin gallate derivative. The condensed product was applied to the synthesis of procyanidin B2 3,3′′-digallate.

Key words

procyanidin - Lewis acid - condensation - epicatechin gallate - natural products

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References

References and Notes
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16 Typical Experimental Procedure To a solution of 4 (50 mg, 0.043 mmol) in CH₂Cl₂ (4.3 mL) was added Yb(OTf)₃ (80 mg, 0.13 mmol). The resulting mixture was stirred for 18 h. After the reaction had been completed, water (20 mL) was added to the mixture. The mixture was extracted with EtOAc (3 × 20 mL). EtOAc layer was washed with water, brine, and dried with anhydrous Na₂SO₄. The solvents were evaporated, and the residue was purified with PTLC (hexane/EtOAc/CH₂Cl₂, 10:1:5) to afford 3 (36 mg, 74%) as a colorless oil. [α]¹⁶ _D –42 (c 1.00, CHCl₃). IR (film): 3088, 3062, 3031, 2926, 2867, 1718, 1592, 1541, 1498, 1454, 1428, 1372, 1328, 1264, 1201, 1027, 736 cm^–1. ¹H NMR (400 MHz, CDCl₃, 55:45 rotational isomer): δ = 7.45–6.50 (m, 80 H), 6.30–6.08 (m, 3 H), 5.83–5.25 (m, 4 H), 5.15–4.32 (m, 28 H), 4.30–3.45 (m, 8 H), 1.25 (t, J = 6.8 Hz, 1.35 H), 1.17 (t, J = 6.8 Hz, 1.65 H). ¹³C NMR (100 MHz, CDCl₃, 55:45 rotational isomer): δ = 165.8, 165.74, 165.71, 164.1, 164.0, 163.7, 163.6, 163.5, 163.3, 158.7, 158.6, 158.5, 158.4, 157.95, 157.93, 157.88, 157.1, 156.0, 155.9, 155.8, 155.7, 155.2, 154.9, 154.8, 154.3, 152.9, 152.8, 152.4, 152.3, 152.25, 152.19, 152.10, 152.08, 149.4, 149.3, 149.1, 148.9, 148.8, 148.72, 148.68, 148.6, 148.5, 148.4, 143.4, 143.3, 142.8, 142.7, 142.5, 142.4, 142.3, 142.1, 137.8, 137.74, 137.67, 137.62, 137.56, 137.53, 137.50, 137.44, 137.40, 137.36, 137.25, 137.18, 137.1, 137.0, 136.93, 136.89, 136.8, 136.7, 136.6, 136.54, 136.51, 136.45, 132.0, 131.7, 131.5, 130.8, 130.6, 130.5, 128.8-126.9, 126.3, 126.0, 125.50, 125.46, 125.4, 125.35, 125.41, 124.6, 124.4, 120.35, 120.30, 120.26, 120.14, 120.12, 120.06, 119.8, 119.4, 114.8, 114.6, 114.3, 114.2, 114.11, 114.08, 114.00, 113.98, 113.44, 113.40, 113.38, 113.34, 113.33, 113.1, 113.0, 112.7, 110.6, 110.4, 110.1, 110.0, 109.8, 109.6, 109.3, 109.0, 108.6, 105.3, 105.2, 105.0, 104.9, 103.7, 103.6, 103.3, 95.0, 94.2, 94.0, 92.0, 91.7, 75.9, 75.6, 75.2, 75.12, 75.05, 74.8, 74.6, 74.4, 74.3, 73.6, 73.4, 73.0, 71.7, 71.5, 71.4, 71.3, 71.1, 70.9, 70.8, 70.7, 70.6, 70.5, 70.0, 69.94, 69.87, 69.8, 35.2, 34.1, 33.8, 32.0, 29.8, 29.5, 22.8, 15.5, 15.4, 14.2. HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₁₄₆H₁₂₆O₂₂Na: 2253.8633; found: 2253.8624.

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