Synlett 2020; 31(18): 1809-1812
DOI: 10.1055/s-0040-1707257
letter

Regioselective Biomimetic Synthesis of Dimeric Oxyresveratrol Derivatives

Lu Ran
,
Hongpeng Li
,
Ge Chao
,
Xiaodong Kang
,
Tian Lei
,
Wenling Li
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P. R. of China
› Author Affiliations
This research work was financially supported by the National Natural Science Foundation of China (No. 21462024).


Abstract

Oxyresveratrol and its methylated derivative as coupling precursors were efficiently prepared in four steps, with Wittig reactions and subsequent isomerization reactions as the key steps. The coupling reactions of oxyresveratrol under various oxidative conditions gave a complex and inseparable mixture of coupling products. The oxidative dimerizations of methylated oxyresveratrols catalyzed by horseradish peroxidase–H2O2 or FeCl3·6H2O in an acetone system predominantly produced the 8–5-coupled and 8–10-coupled dihydrobenzofuran-type dimers, respectively. This regioselective biomimetic strategy might be useful in synthesizing other dimeric oxyresveratrol derivatives.

Supporting Information



Publication History

Received: 08 July 2020

Accepted: 03 August 2020

Article published online:
01 September 2020

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  • References and Notes

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  • 14 5-[(E)-2-(4-Hydroxy-2-methoxyphenyl)ethenyl]benzene-1,3-diol [(E)-15] Pale-yellow oil; yield: 1.77 g (91%). 1H NMR (500 MHz, acetone-d 6): δ = 3.85 (s, 3 H), 6.24 (t, J = 2.0 Hz, 1 H), 6.46 (dd, J = 8.5, 2.0 Hz, 1 H), 6.49 (d, J = 2.0 Hz, 1 H), 6.52 (d, J = 2.0 Hz, 2 H), 6.88 (d, J = 16.5 Hz, 1 H), 7.30 (d, J = 16.5 Hz, 1 H), 7.45 (d, J = 8.5 Hz, 1 H), 8.16 (br s, 2 H), 8.51 (br s, 1 H). 13C NMR (125 MHz, acetone-d 6): δ = 55.8, 99.8, 99.9, 102.4, 105.5 (2 C), 108.5, 118.7, 123.9, 126.8, 127.9, 141.5, 159.2, 159.5, 159.6. HRMS (ESI): m/z [M –H]+ calcd for C15H13O4: 257.08193; found: 257.08191.
  • 15 5-{(E)-2-[3-(3,5-Dihydroxyphenyl)-2-(4-hydroxy-2-methoxyphenyl)-6-methoxy-2,3-dihydro-1-benzofuran-5-yl]ethenyl}benzene-1,3-diol (16) Yellowish amorphous powder; yield: 31 mg (62%). 1H NMR (500 MHz, acetone-d 6): δ = 3.77 (s, 3 H), 3.94 (s, 3 H), 4.36 (d, J = 5.0 Hz, 1 H), 5.73 (d, J = 5.0 Hz, 1 H), 6.21 (d, J = 2.0 Hz, 2 H), 6.23 (t, J = 2.0 Hz, 1 H), 6.24 (t, J = 2.0 Hz, 1 H), 6.40 (dd, J = 8.5, 2.0 Hz, 1 H), 6.50 (d, J = 2.0 Hz, 2 H), 6.52 (d, J = 2.0 Hz, 1 H), 6.64 (d, J = 2.0 Hz, 1 H), 6.84 (d, J = 16.5 Hz, 1 H), 7.12 (d, J = 8.5 Hz, 1 H), 7.32 (d, J = 2.0 Hz, 1 H), 7.35 (d, J = 16.5 Hz, 1 H), 8.15 (br s, 2 H), 8.16 (br s, 2 H), 8.46 (br s, 1 H). 13C NMR (125 MHz, acetone-d 6): δ = 55.7, 56.2, 89.8, 94.3, 100.0, 102.0, 102.5, 105.5, 105.6 (2 C), 107.0, 107.1 (2 C), 107.6, 119.8, 121.2, 122.9 (2 C), 123.4, 123.9, 126.8, 128.1, 141.4, 147.2, 159.0, 159.1, 159.5, 159.6 (2 C), 162.2. HRMS (ESI): m/z [M – H]+ calcd for C30H25O8: 513.15549; found: 513.15547.
  • 16 5-{6-Hydroxy-2-(4-hydroxy-2-methoxyphenyl)-5-[(E)-2-(3-hydroxy-5-methoxyphenyl)ethenyl]-2,3-dihydro-1-benzofuran-3-yl}benzene-1,3-diol (18) Yellowish amorphous powder; yield: 15 mg (45%). 1H NMR (500 MHz, acetone-d 6): δ = 3.76 (s, 3 H), 3.83 (s, 3 H), 4.36 (d, J = 5.0 Hz, 1 H), 5.67 (d, J = 5.0 Hz, 1 H), 6.20 (dd, J = 8.5, 2.0 Hz, 1 H), 6.26 (d, J = 2.0 Hz, 2 H), 6.34 (dd, J = 8.0, 2.0 Hz, 1 H), 6.36 (d, J = 2.0 Hz, 2 H), 6.41 (d, J = 2.0 Hz, 1 H), 6.51 (d, J = 2.0 Hz, 1 H), 6.68 (d, J = 2.0 Hz, 1 H), 6.76 (d, J = 16.5 Hz, 1 H), 7.05 (d, J = 8.0 Hz, 1 H), 7.15 (d, J = 16.5 Hz, 1 H), 7.16 (d, J = 8.0 Hz, 1 H). 13C NMR (125 MHz, acetone-d 6): δ = 55.6, 55.7, 55.8, 89.1, 99.7, 99.8, 103.9, 107.0, 107.3, 108.3, 118.6, 120.1, 122.3, 123.8, 125.3, 125.6, 127.2, 127.8, 128.1, 128.4, 137.2, 148.1, 151.9, 158.5 (2 C), 159.3 (2 C), 159.5, 162.8 (2 C). HRMS (ESI): m/z [M – H]+ calcd for C30H25O8: 513.15549; found: 513.15546.