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Synlett 2020; 31(10): 1007-1010
DOI: 10.1055/s-0037-1610757
DOI: 10.1055/s-0037-1610757
letter
A Versatile, Diels–Alder Reaction-Based Approach to Prenyleudesmane Diterpenoids: A Concise Total Synthesis of Sinupol
Weitere Informationen
Publikationsverlauf
Received: 12. Februar 2020
Accepted after revision: 21. Februar 2020
Publikationsdatum:
20. März 2020 (online)
![](https://www.thieme-connect.de/media/synlett/202010/lookinside/thumbnails/st-2020-u0087-l_10-1055_s-0037-1610757-1.jpg)
Abstract
Herein, a concise strategy designed to provide general and diversifiable access to various prenyleudesmane terpenoids is described and utilized in the asymmetric synthesis of a biologically active prenyleudesmane diterpenoid, sinupol, which is accomplished in a seven-step procedure.
Key words
prenyleudesmane diterpenoid - sinupol - PTP1B inhibitor - Diels–Alder reaction - total synthesisSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610757.
- Supporting Information
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References and Notes
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- 18 (R)-4-Benzyl-3-((2S,4aS,8aS)-4a,8-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalene-2-carbonyl)oxazolidin-2-one (2): BHT (65.4 mg, 0.297 mmol) was added to a solution of triene 3 (1.09 g, 2.97 mmol) in mesitylene (29.7 mL) in a sealed tube. The solution was degassed and heated at 220 °C for 168 h. The reaction mixture was cooled to ambient temperature over a period of 1 h, concentrated in vacuo, and the residue was filtered through a thin pad of silica gel. Concentration of the filtrate followed by flash column chromatography on silica gel (hexane/EtOAc = 5:1) gave trans-fused decalin 2 (959 mg, 88% yield) as an amorphous solid along with an unidentified diastereomeric mixture (87.2 mg, 8% yield). Rf 0.25 (hexane/EtOAc = 4:1); [α] d 25 –52.6 (c 0.81, CHCl3); IR (KBr): 2913, 2847, 1780, 1698, 1386, 1212 cm–1. 1H NMR (CDCl3, 400 MHz): δ = 7.36–7.24 (m, 3 H), 7.24–7.19 (m, 2 H), 5.34 (m, 1 H), 4.68 (ddt, J = 7.4, 9.4, 3.2 Hz, 1 H), 4.21 (dd, J = 7.4, 9.0 Hz, 1 H), 4.18 (dd, J = 3.2, 9.0 Hz, 1 H), 3.57 (tt, J = 3.9, 12.1 Hz, 1 H), 3.27 (dd, J = 3.2, 13.4 Hz, 1 H), 2.81 (dd, J = 9.4, 13.4 Hz, 1 H), 2.13 (m, 1 H), 2.05 (m, 1 H), 2.02 (m, 1 H), 1.98 (m, 1 H), 1.89 (dq, J = 4.0, 13.4 Hz, 1 H), 1.70 (m, 1 H), 1.64 (s, 3 H), 1.50 (ddd, J = 2.8, 4.0, 13.2 Hz, 1 H), 1.44 (d, J = 11.9 Hz, 1 H), 1.41–1.34 (m, 2 H), 1.28 (dt, J = 4.2, 13.4 Hz, 1 H), 0.87 (s, 3 H). 13C NMR (CDCl3, 100 MHz): δ = 176.4 (C), 153.0 (C), 135.3 (C), 134.3 (C), 129.4 (CH)×2, 128.9 (CH)×2, 127.3 (CH), 121.3 (CH), 66.0 (CH2), 55.3 (CH), 45.9 (CH), 43.2 (CH), 39.1 (CH2), 38.0 (CH2), 37.7 (CH2), 32.2 (C), 26.4 (CH2), 23.8 (CH2), 22.8 (CH2), 21.0 (CH3), 15.5 (CH3). MS (ESI-TOF): m/z (%) = 390 (100) [M + Na]+. HRMS (ESI-TOF): m/z [M + Na]+ calcd for C23H29NO3Na: 390.2045; found: 390.2038