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Synlett 2023; 34(15): 1795-1798
DOI: 10.1055/s-0042-1751457
letter

Synthesis of the A-Ring of Goniodomin A via Radical Cyclization with Vinyl Sulfoxide

Yuto Masuzawa
a   Graduate School of Agriculture, Tokyo University of Agriculture, 1–1–1 Sakuragaoka, Setagaya-ku, Tokyo 156–8502, Japan
,
Arata Yajima
b   Department of Chemistry for Life Sciences and Agriculture, Faculty of Life Sciences, Tokyo University of Agriculture, 1–1–1 Sakuragaoka, Setagaya-ku, Tokyo 156–8502, Japan
,
Armen Zakarian∗
c   Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA
,
Tatsuo Saito  ∗
b   Department of Chemistry for Life Sciences and Agriculture, Faculty of Life Sciences, Tokyo University of Agriculture, 1–1–1 Sakuragaoka, Setagaya-ku, Tokyo 156–8502, Japan
› InstitutsangabenThis work was supported by the Japan Society for the Promotion of Science (JSPS) KAKENHI (18K06571 and 22K05467).
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Abstract

A short synthesis of the A-Ring of Goniodomin A was developed via radical cyclization using vinyl sulfoxide. We found that optically inactive sulfoxides are applicable to the cyclization and Pummerer rearrangement with high stereoselectivity.

Key words

radical cyclization - Pummerer rearrangement - cyclic ether - goniodomin A

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0042-1751457.
  • Supporting Information


Publikationsverlauf

Eingereicht: 24. März 2023

Angenommen nach Revision: 25. April 2023

Artikel online veröffentlicht:
30. Mai 2023

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  • References and Notes

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  • 13 Synthesis of 10a: Tributyltin hydride (2.76 mL, 10.2 mmol) was added to a solution of 7 (1.95 g, 5.10 mmol) and AIBN (419 mg, 2.55 mmol) in toluene (170 mL) at r.t. After stirring for 2 h at 90 °C, the solution was cooled to r.t. and concentrated in vacuo. The residue was purified by flash column chromatography (SiO2; n-hexane/EtOAc = 4:1) to give vinyl stannane 10a (2.38 g, 3.53 mmol, 69% yield) as a colorless oil and vinyl ether 11 (124 mg, 510 μmol, 10% yield) as a colorless oil. 10a: [α]D 23 –79.0 (c 1.1, CHCl3). IR (neat): 3036, 2953, 2922, 2870, 2852, 1606, 1101, 1045 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.58 (d, J = 7.8 Hz, 2 H), 7.53–7.48 (m, 2 H), 7.41–7.35 (m, 5 H), 5.79 (s, 0.4 H), 5.61 (s, 0.6 H), 5.55 (s, 0.6 H), 5.52 (s, 0.4 H), 4.50 (d, J = 10.1 Hz, 0.6 H), 4.42 (d, J = 5.1 Hz, 0.6 H), 4.24 (dd, J = 11.4, 4.1 Hz, 0.4 H), 3.78–3.65 (m, 2 H), 3.60–3.48 (m, 1.4 H), 3.34 (ddd, J = 9.7, 9.7, 4.6 Hz, 0.4 H), 3.19 (d, J = 12.9 Hz, 0.6 H), 3.11 (dd, J = 13.3, 3.2 Hz, 0.4 H), 2.88 (t, J = 12.4 Hz, 0.6 H), 2.69–2.56 (m, 1.6 H), 2.44–2.37 (m, 3.4 H), 1.55–1.37 (m, 6 H), 1.35–1.23 (m, 6 H), 0.94–0.85 (m, 15 H). 13C NMR (100 MHz, CDCl3): δ = 149.7, 141.7, 141.6, 137.4, 130.2, 129.3, 128.5, 126.3, 126.24, 126.16, 125.8, 124.6, 124.0, 102.0, 101.9, 79.6, 79.2, 77.3, 75.6, 74.5, 73.8, 73.6, 69.4, 69.2, 61.6, 59.8, 41.5, 41.2, 29.3, 29.2, 29.1, 27.6, 27.4, 27.1, 21.63, 21.56, 13.8, 10.4. HRMS: m/z [M + Na]+ calcd for C34H50O4NaSSn: 697.2344; found: 697.2351.
  • 14 Synthesis of 17 from 12: 2,6-Lutidine (605 μL, 5.20 mmol) and TFAA (735 μL, 5.20 mmol) were added to a solution of 12 (1.00 g, 2.60 mmol) in CH2Cl2 (26.0 mL) at 0 °C. After stirring for 30 min at that temperature, MeOH (26.0 mL) and NaBH4 (984 mg, 26.0 mmol) were added. After stirring for 3 h, NaBH4 (984 mg, 26.0 mmol) was additionally added. The solution was diluted with CH2Cl2, and the organic layer was washed with brine. The solution was dried over MgSO4 and concentrated in vacuo. The residue was purified by flash column chromatography (SiO2; n-hexane/EtOAc = 2:1) to give methylene alcohol 17 (557 mg, 2.13 mmol, 82% yield) as a white solid. 17: mp 118–120 °C; [α]D 26 –36.3 (c 1.0, CHCl3). IR (neat): 3291, 2964, 2870, 1645, 1382, 1329, 1101, 908 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.52–7.48 (m, 2 H), 7.40–7.34 (m, 3 H), 5.56 (s, 1 H), 5.02 (s, 1 H), 4.87 (s, 1 H), 4.35 (dd, J = 10.5, 4.6 Hz, 1 H), 4.04–4.01 (m, 1 H), 3.96 (dd, J = 11.5, 3.2 Hz, 1 H), 3.84 (dd, J = 11.5, 7.3 Hz, 1 H), 3.73 (dd, J = 10.5, 10.5 Hz, 1 H), 3.64–3.54 (m, 2 H), 2.77 (dd, J = 12.9, 4.6 Hz, 1 H), 2.48 (br dd, J = 11.5, 11.5 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 140.6, 137.3, 129.1, 128.4 (2C), 126.1 (2C), 111.4, 101.6, 78.6, 78.4, 73.2, 69.2, 62.5, 38.8. HRMS: m/z [M + Na]+ calcd for C15H18O4Na: 285.1097; found: 285.1088.