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CC BY 4.0 · SynOpen 2024; 08(01): 39-46
DOI: 10.1055/a-2236-0803
DOI: 10.1055/a-2236-0803
letter
Synthesis of a Propellane-Type 5/5/6-Tricyclic System by Tandem-Metathesis: A New Approach to a Quadranoid Skeleton
Abstract
We disclose a useful synthetic method for preparing the propellane-type 5/5/6-tricyclic system that is present in diquinane-based natural products such as quadrone, terrecyclic acid A, or terrecyclol. The method involves an LDA-mediated regio- and stereoselective allylation and a tandem metathesis as key steps. The target molecules were assembled in just two steps starting from a readily available building block, a 3β-vinyl tricyclic ketone prepared from endo-dicyclopentadiene-1-one. All the compounds prepared were characterized by NMR analyses and/or chemical methods. The synthetic methods demonstrated here are useful in syntheses of quadranoid-type natural products.
Keywords
allylation - olefin metathesis - diquinanes - tricyclic compounds - dicyclopentadienone - natural productsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2236-0803.
- Supporting Information
Publication History
Received: 22 October 2023
Accepted after revision: 04 December 2023
Accepted Manuscript online:
28 December 2023
Article published online:
17 January 2024
© 2024. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)
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- 21 (1S,2R,4S,5S,6S)-2,4-Divinyltricyclo[4.3.2.01,5]undec-7-en-10-one (14) A stirred solution of compound 15 (50 mg, 0.233 mmol) in CH2Cl2 (50 mL) was purged sequentially with N2 gas and ethylene gas for 10 min each. G-II catalyst (20 mg, 0.023 mmol; 10 mol%) was added in one portion at rt under an ethylene atmosphere, and purging was continued for another 5–10 min. The mixture was then stirred at rt under ethylene for 8 h. When the reaction was complete (TLC), the volatiles were removed under reduced pressure, and the crude product was purified by column chromatography (silica gel, 1.0–1.5% EtOAc–PE) to give a colorless liquid; yield: 44 mg (88%); Rf = 0.61 (silica gel-coated 4.0 × 2.0 cm glass TLC plate, 2.0% EtOAc–PE; double run). IR (neat): 3074, 3026, 2923, 2877, 1737, 1636, 1454, 1429, 1412, 1325, 1156, 1098, 1070, 995, 955, 911, 775, 752, 721, 700, 676, 521 cm–1. 1H NMR (400 MHz, CDCl3): δ = 6.25 (tdd, J = 17.83, 11.78, 8.52 Hz, 1 H), 6.12–6.08 (m, 1 H), 5.99 (ddd, J = 16.81, 10.58, 6.00 Hz, 1 H), 5.52 (ddd, J = 9.31, 3.77, 2.58 Hz, 1 H), 5.09–5.04 (m, 4 H), 3.04–2.95 (m, 1 H), 2.77 (t, J = 5.94 Hz, 1 H), 2.62 (d, J = 11.99 Hz, 1 H), 2.52–2.45 (m, 1 H), 2.39–2.31 (m, 2 H), 2.18 (dq, J = 17.70, 2.48 Hz, 2 H), 2.04 (ddd, J = 13.16, 7.61, 5.92 Hz, 1 H), 1.45 (dd, J = 23.92, 12.70 Hz, 1 H). 13C{1H} NMR (100 MHz, CDCl3): δ = 223.2 (CO), 139.1 (CH), 137.4 (CH), 136.4 (CH), 126.1 (CH), 115.5 (CH2), 115.4 (CH2), 61.2 (C), 54.1 (CH), 51.8 (CH), 49.3 (CH2), 41.1 (CH), 38.4 (CH2), 38.3 (CH2), 34.3 (CH). HRMS (ESI, Q-ToF): m/z [M + K]+ calcd for C15H18KO: 253.0989; found 253.0989.