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Synlett 2015; 26(01): 101-107
DOI: 10.1055/s-0034-1378926
DOI: 10.1055/s-0034-1378926
letter
Diastereoselective One-Pot Synthesis of Succinimides Bearing a Chromone Unit
Further Information
Publication History
Received: 15 August 2014
Accepted after revision: 12 October 2014
Publication Date:
11 November 2014 (online)
Abstract
A diastereoselective synthesis of highly substituted succinimide derivatives with chromone and carboxylic ester functionalities from 3-formylchromones, Meldrum’s acid, and alkyl isocyanides in the presence of alcohols in moderate to good yields is described.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1378926.
- Supporting Information
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References and Notes
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- 15 General Procedure for the Synthesis of Alkyl-1-alkyl-4-(4-oxo-4H-chromen-3-yl)-2,5-dioxopyrrolidine-3-carboxylates 6A mixture of the appropriate 3-formylchromone 1 (1 mmol) and Meldrum’s acid (2, 1 mmol) was stirred in anhydrous CH2Cl2 (10 mL) for 3 h at r.t., and then alcohol 4 (1 mmol) followed by alkyl isocyanide 3 (1 mmol) was added at r.t. After complete conversion, as monitored by TLC using EtOAc–hexane (1:1) as eluent, the mixture was concentrated in vacuo, and the solid residue was washed with Et2O and crystallized from CH2Cl2–hexane (1:3) to afford pure product 6. rac-2-Adamantyl (3R,4S)-1-Benzyl-4-(6-methyl-4-oxo-4H-chromen-3-yl)-2,5-dioxopyrrolidine-3-carboxylate (6i)White powder; mp 195–196 °C (melt.). IR (KBr): νmax = 1783, 1709, 1646 (C=O), 1616 (C=C) cm–1.1H NMR (300.1 MHz, CDCl3): δ = 1.49–2.06 (14 H, m, adamantyl), 2.45 (3 H, s, CH3), 4.02 and 4.08 (2 H, AB-q system, 3 J HH = 6.1 Hz, CHCH), 4.75 and 4.86 (2 H, AB-q system, 2 J HH = 14.4 Hz, PhCH2 ), 5.00 (1 H, m, OCH), 7.26–7.94 (7 H, m, arom. H), 7.95 (1 H, d, 3 J HH = 5.9 Hz, arom. H.), 7.96 (1 H, s, C=CHO). 13C NMR (75.5 MHz, CDCl3): δ = 176.6, 174.9, 170.8, 166.8, 154.8, 154.6, 135.8, 135.6, 135.3, 128.6, 128.2, 127.8, 125.0, 123.4, 119.2, 118.0, 79.8, 52.0, 44.0, 43.2, 37.2, 36.3, 36.2, 31.8, 31.6, 31.5, 31.4, 27.0, 26.8, 21.0. Anal. Calcd (%) for C32H31NO6 (525.59): C, 73.13; H, 5.94; N, 2.66. Found: C, 72.81; H, 5.97; N, 2.70.X-ray Data for 6iC32H31N1O6, M = 525.58 g·mol–1, orthorhombic system, space group P212121, a =10.0889(19), b = 11.9344(19), c = 22.490(3) Å, V = 2707.9(8) Å3, Z = 4, D calcd= 1.289 g cm–3, μ(Mo Kα)= 0.089 mm–1, crystal dimension of 0.50 × 0.30 × 0.25 mm. The structure was solved by using SHELXS. The structure refinement and data reduction was carried out with SHELXL of the X-Step32 suite of programs.18 Crystallographic data for 6i have been deposited with the Cambridge Crystallographic Data Centre. Copies of the data can be obtained, free of charge, on application to The Director, CCDC 1019444, Union Road, Cambridge CB2 1EZ, UK. Fax: +44(1223)336033 or e-mail: deposit@ccdc.cam.ac.uk. rac-Dimethyl {1-(6-methyl-4-oxo-4H-chromen-3-yl)-2-oxo-2-[(1,1,3,3-tetramethylbutyl)amino]ethyl}malonate (5a)White powder; mp 198–201 °C (dec.). IR (KBr): νmax = 3330 (NH), 1730, 1681, 1649 (C=O), 1621 (C=C) cm–1. 1H NMR (300.1 MHz, CDCl3): δ = 0.83 (9 H, s, CMe3), 1.29 (6 H, br s, CMe2), 1.49 and 1.73 (2 H, AB-q system, 2 J HH = 14.8 Hz, CH2), 2.43 (3 H, s,CH3), 3.55 and 3.74 (6 H, 2 s, 2 OCH 3), 4.25 (1 H, d, 3 J HH = 12.4 Hz, CH) 4.58 (1 H, d, 3 J HH = 12.4 Hz, CH), 6.40 (1 H, s, NH), 7.34 (1 H, d, 3 J HH = 8.8 Hz, CH3C=CHCH), 7.48 (1 H, dd, 3 J HH = 8.8 Hz, 3 J HH = 1.6 Hz, CH3C=CHCH), 7.97 (1 H, s, C=CHO), 7.98 (1 H, s, CH3C=CHC). 13C NMR (75.5 MHz, CDCl3): δ = 177.0, 168.6, 167.9, 167.8, 154.3, 153.6, 135.5, 135.4, 125.2, 123.0, 119.6, 118.0, 55.2, 52.9, 52.9, 52.0, 51.4, 41.4, 31.4, 31.2, 29.1, 28.7, 20.9. Anal. Calcd (%) for C25H33NO7 (459.53): C, 65.34; H, 7.24; N, 3.05. Found: C, 65.50; H, 7.24; N, 3.08.
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- 18 X-STEP32 Version 1.07b, X-ray Structure Evaluation Package. Stoe & Cie; Darmstadt: 2000