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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‡
a   Graduate School of Science and Technology, Department of Agriculture, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan
,
Shu-hei Kobayashi‡
a   Graduate School of Science and Technology, Department of Agriculture, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan
,
Yasunao Hattori
b   Center for Instrumental Analysis, Kyoto Pharmaceutical University, Yamashina-ku, Kyoto 607-8412, Japan
,
Atsushi Kawamura∗
c   Department 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∗
a   Graduate School of Science and Technology, Department of Agriculture, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan
c   Department of Biomolecular Innovation, Institute for Biomedical Sciences, Interdisciplinary Cluster for Cutting Edge Research, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan
› Author AffiliationsThis work was supported in part by JSPS KAKENHI Grant Number 18K05454.
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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0041-1737457.
  • Supporting Information


Publication History

Received: 25 March 2022

Accepted after revision: 13 April 2022

Article published online:
09 May 2022

© 2022. Thieme. All rights reserved

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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.