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Synlett 2014; 25(16): 2260-2264
DOI: 10.1055/s-0034-1378897
DOI: 10.1055/s-0034-1378897
cluster
Tandem Diels–Alder [4+2] Cycloadditions and Intramolecular [3+2] Cross-Cycloadditions of Dienylcyclopropane 1,1-Diesters
Further Information
Publication History
Received: 12 May 2014
Accepted after revision: 30 July 2014
Publication Date:
09 September 2014 (online)
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Abstract
A novel tandem reaction by combination of Diels–Alder [4+2] cycloaddition and [3+2] IMCC (intramolecular cross-cycloaddition) of dienylcyclopropane 1,1-diesters has been successfully developed. In this reaction, three new rings and four new stereocenters were generated in one-pot. This supplies a strategy for rapid construction of 6,6- and 6,7-fused carbocyclic skeletons which are common cores in many biologically important natural products.
Key words
annulation - cyclopropane - cycloaddition - Diels–Alder reaction - domino reaction - natural productsSupporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
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References and Notes
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- 8 When dienylcyclopropane 1,1-diesters (1a or 1e) as a mixture of Z/E-isomers reacted with dienophiles, the ratio of Z/E-isomers increased as the reaction proceeded, which indicated that the E-isomers showed better reactivity than the Z-isomers.
- 9 Typical Procedure A; Two-Stage Process: In a 25-mL tube were added dienylcyclopropane 1,1-diester 1a (88 mg, 0.39 mmol), MVK (2b; 0.5 mL, 7.86 mmol), p-hydroquinone (10 mg, 0.091 mmol) and toluene (3 mL) under N2. The tube was sealed and the reaction was carried out in an oil bath (120 °C). After complete consumption of 1a (monitored by TLC), the mixture was concentrated. Sc(OTf)3 (19 mg, 0.0384 mmol, 20 mol%) and DCE (4 mL) were then added, and the mixture was stirred at r.t. under an atmosphere of nitrogen until the reaction was complete (monitored by TLC). The solvent was evaporated under vacuum and the residue was purified by silica gel column chromatography to afford 4b (35% yield based on 1a, dr = 5:1). 1H NMR (400 MHz, CDCl3): δ = 5.66 (dd, J = 7.5, 2.1 Hz, 1 H), 5.45–5.54 (m, 1 H), 4.47 (d, J = 7.4 Hz, 1 H), 3.78 (s, 3 H), 3.75 (s, 3 H), 2.79 (dd, J = 13.5, 7.9 Hz, 1 H), 2.45 (d, J = 13.5 Hz, 1 H), 2.12–2.21 (m, 1 H), 2.11–2.01 (m, 3 H), 1.77 (d, J = 1.5 Hz, 1 H), 1.57–1.68 (m, 2 H), 1.41–1.50 (m, 1 H), 1.34 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 172.51, 170.49, 130.05, 126.77, 86.68, 74.79, 68.14, 52.73, 52.61, 39.48, 38.09, 34.56, 29.06, 25.90, 20.10, 19.15. HRMS (ESI): m/z [M + Na]+ calcd for C16H22O5: 317.1359; found: 317.1360.
- 10 Typical Procedure B; Domino Process: In a 25-mL tube were added dienylcyclopropane 1,1-diester 1f (102 mg, 0.39 mmol), MVK (2b; 0.5 mL, 7.86 mmol), p-hydroquinone (10 mg, 0.091 mmol) and toluene (3 mL) in N2. The tube was sealed and the reaction was carried out in an oil bath (120 °C). After completion of the reaction (monitored by TLC), the solvent was evaporated under vacuum and the residue was purified by silica gel column chromatography to afford 4i (51% based on 1f, dr = 20:1). 1H NMR (400 MHz, CDCl3): δ = 7.28–7.35 (m, 4 H), 7.23 (dd, J = 5.2, 3.3 Hz, 1 H), 6.01 (d, J = 3.4 Hz, 1 H), 4.34–4.39 (m, 1 H), 3.80 (s, 3 H), 3.74 (s, 3 H), 2.39–2.56 (m, 4 H), 2.16–2.25 (m, 2 H), 1.65–1.79 (m, 2 H), 1.60 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 170.90, 140.27, 128.22, 126.78, 125.09, 124.93, 90.08, 81.41, 66.27, 52.64, 44.60, 41.70, 41.03, 25.13, 24.13, 14.72. HRMS (ESI): m/z [M + H]+ calcd for C21H24O5: 357.1697; found: 357.1702.
Platensymecin:
Icetexane:
Cyathane:
Eudesmane:
Clerodane:
For reviews on donor-acceptor cyclopropanes, see: