Total Syntheses of Dysidealactams E and F and Dysidealactone B, Drimane-Type Sesquiterpenes Derived from a Dysidea sp. of Marine Sponge

Yuhao Chen; Ping Lan; Lorenzo V. White; Weiguang Yang; Martin G. Banwell

doi:10.1055/a-2002-8680

Synlett, Table of Contents

Synlett 2023; 34(12): 1529-1533
DOI: 10.1055/a-2002-8680

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Special Issue Honoring Masahiro Murakami’s Contributions to Science

Total Syntheses of Dysidealactams E and F and Dysidealactone B, Drimane-Type Sesquiterpenes Derived from a Dysidea sp. of Marine Sponge

Yuhao Chen

^aGuangdong Key Laboratory for Research and the Development of Natural Drugs, The Marine Biomedical Research Institute, Guangdong Medical University, Zhanjiang, Guangdong, 524023, P. R. of China

,

Ping Lan

^bInstitute for Advanced and Applied Chemical Synthesis, College of Pharmacy, Jinan University, Guangzhou, Guangdong 510632, P. R. of China

,

Lorenzo V. White

^bInstitute for Advanced and Applied Chemical Synthesis, College of Pharmacy, Jinan University, Guangzhou, Guangdong 510632, P. R. of China

,

Weiguang Yang∗

^aGuangdong Key Laboratory for Research and the Development of Natural Drugs, The Marine Biomedical Research Institute, Guangdong Medical University, Zhanjiang, Guangdong, 524023, P. R. of China

,

Martin G. Banwell ∗

^aGuangdong Key Laboratory for Research and the Development of Natural Drugs, The Marine Biomedical Research Institute, Guangdong Medical University, Zhanjiang, Guangdong, 524023, P. R. of China

^bInstitute for Advanced and Applied Chemical Synthesis, College of Pharmacy, Jinan University, Guangzhou, Guangdong 510632, P. R. of China

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Abstract

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Dedicated to Professor Masahiro Murakami (Kyoto University) in recognition of his profound and ingenious contributions to so many aspects of chemical synthesis.

Abstract

Dysidealactams E and F and dysidealactone B are recently reported marine natural products. Their syntheses from β-cyclocitral are detailed here. The preparation of certain derivatives and analogues of these compounds is also described and single-crystal X-ray analyses of two of these, as well as that of (±)-dysidealactam F, are reported.

Key words

cycloaddition - drimanes - marine natural products - sesquiterpenes - total synthesis

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References

References and Notes

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16 (±)-[(5aS,9aS)-6,6,9a-Trimethyl-1,3-dioxo-1,3,4,5,5a,6,7,8,9,9a-decahydro-2H-benzo[e]isoindol-2-yl]acetic acid [(±)-4] A Schlenk tube equipped with a magnetic stirrer bar was charged with compound (±)-8 (500 mg, 2.01 mmol), glycine (1.51 g, 20.1 mmol), and 1:1 MeCN–H₂O (6.0 mL). The tube was sealed and the contents were heated at 105 °C (oil-bath temperature) for 8 h. The cooled mixture was then diluted with H₂O (10 mL) and the separated aqueous phase was extracted with EtOAc (3 × 25 mL). The combined organic phases were dried (Na₂SO₄), filtered, and concentrated under reduced pressure and the resulting residue was subjected to flash chromatography [silica gel, EtOAc–PE (1:3 + 1% AcOH)] to afford, after concentration of the appropriate fractions, a clear yellow oil; yield: 331 mg (54%); R_f = 0.3 (1:3 EtOAc–PE +1% AcOH). FTIR (ATR): 2930, 1703, 1420, 1391, 1233, 1207, 1117, 937, 735 cm^–1. ¹H NMR (400 MHz, CD₃OD): δ = 4.13 (s, 2 H), 2.50 (d, J = 14.0 Hz, 2 H), 2.25 (m, 1 H), 1.97 (m, 1 H), 1.76 (m, 1 H), 1.63–1.45 (complex m, 3 H), 1.38–1.25 (complex m, 3 H), 1.23 (s, 3 H), 0.96 (s, 3 H), 0.93 (s, 3 H); COOH proton not observed. ¹³C{¹H} NMR (100 MHz, CD₃OD): δ = 171.8, 171.5, 170.9, 151.4, 141.5, 53.2, 42.9, 39.2, 37.6, 36.3, 34.4, 33.9, 23.0, 22.0, 21.1, 19.5, 19.0. HRMS (TOF ESI, +): m/z [M + H]⁺ calcd for C₁₇H₂₄NO₄: 306.1705; found: 306.1714.
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