Synlett 2023; 34(12): 1529-1533
DOI: 10.1055/a-2002-8680
cluster
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
a   Guangdong 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
b   Institute for Advanced and Applied Chemical Synthesis, College of Pharmacy, Jinan University, Guangzhou, Guangdong 510632, P. R. of China
,
Lorenzo V. White
b   Institute for Advanced and Applied Chemical Synthesis, College of Pharmacy, Jinan University, Guangzhou, Guangdong 510632, P. R. of China
,
Weiguang Yang
a   Guangdong 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
,
a   Guangdong 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
b   Institute for Advanced and Applied Chemical Synthesis, College of Pharmacy, Jinan University, Guangzhou, Guangdong 510632, P. R. of China
› Author Affiliations
We thank the National Natural Science Foundation of China (Grant Nos. 22250410258 and 22250410259), the Science and Technology Planning Program of Zhanjiang (Grant. No. 2021A05247) and the Ministry of Science and Technology of the People’s Republic of China for financial support.


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.

Supporting Information



Publication History

Received: 06 December 2022

Accepted after revision: 21 December 2022

Accepted Manuscript online:
21 December 2022

Article published online:
13 February 2023

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  • 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%); Rf = 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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  • 22 For a chiral-auxiliary-based method leading to the formation of homochiral Diels–Alder adducts of diene 10, see: Hendersen JR, Parvez M, Keay BA. Org. Lett. 2009; 11: 3178