Novel Prolinamide Organocatalysts Based on Calix[4]arene Scaffold for the Enantioselective Direct Aldol Reaction

Letters in Organic Chemistry

Volumn 7, Issue 6, 2010, Pages 461-466

  Li, Zheng Yi ^a,b   Lu, Cheng Xi ^a   Huang, Guoli ^a   Ma, Jie Jie ^a   Sun, Hongsheng ^a   Wang, Leyong ^a   Pan, Yi ^a  

^a NANJING UNIVERSITY   (China)

^b CHANGZHOU UNIVERSITY   (China)

Author keywords

Asymmetric aldol reaction; Calix 4 arene; Organocatalyst; Prolinamide

Indexed keywords

EID: 78650412828     PISSN: 15701786     EISSN: None     Source Type: Journal    
DOI: 10.2174/157017810791824919     Document Type: Article

References (52)

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39. Representative synthetic procedure of route A [5c]: To a solution of 5-amino-25,26,27,28-tetrabutoxycalix[4]arenes 14a (0.66 g, 1.0 mmol) in CH2Cl2 (50 mL) was added Boc-L-proline (0.24 g, 1.1 mmol), DCC (N,N'-dicyclohexyl carbodiimide) (0.31 g, 1.5 mmol) and DMAP (4-dimethylaminopyridine) (61 mg, 0.5 mmol). The mixture was stirred at room temperature for 10 h. After reaction, the insoluble DCU was removed by filtration. The filtrate was concentrated, and the residue was purified by column chromatography with petroleum ether / ethyl acetate (3:1, v/v) as an eluent to give 0.74 g Boc-protected product which was dissolved in CHCl3 (30 mL). After addition of TFA (1 mL), the reaction mixture was stirred at 50 °C for 3 h. The solvent was removed, CHCl3 (30 mL) and H2O (30 mL) were added. The pH of the mixture was adjusted to 8-9 by the addition of aqueous NaOH (2 M), and the water layer was extracted with additional CHCl3 (30 mL). The combined organic layer was washed with brine (30 mL) and dried over anhydrous Na2SO4. The solvent was removed to give pure target product 1 as a white solid. Yield: 86%. mp 65-67 °C. IR (KBr): 3448, 2959, 2930, 2869, 1683, 1601, 1525, 1459, 1382, 1291, 1245, 1087, 1028, 762 cm-1. 1H NMR (300 MHz, DMSO-d6): δ = 0.97 (t, J = 7.5 Hz, 12H, CH3), 1.37-1.53 (m, 8H, CH2), 1.57-1.76 (m, 4H, CH2), 1.80-1.95 (m, 8H, CH2), 2.84 (t, J = 6.5 Hz, 2H, NCH2), 3.08-3.18 (2d, J = 13.2 Hz, 4H, ArCH2Ar), 3.56-3.61 (m, 1H, NCHCO), 3.75-3.89 (m, 8H, ArOCH2), 4.29-4.36 (2d, J = 13.2 Hz, 4H, ArCH2Ar), 6.45-6.61 (m, 7H, ArH), 6.70 (d, J = 7.5 Hz, 2H, ArH), 6.95-7.01 (2d, J = 2.7 Hz, 2H, ArH), 9.52 (s, 1H, CONH); 13C NMR (75 MHz, CDCl3): δ = 14.1, 19.3, 19.4, 25.0, 25.8, 26.3, 26.9, 29.4, 30.7, 31.0, 32.1, 32.2, 32.4, 45.6, 47.3, 51.7, 61.0, 74.8, 74.9, 119.7, 121.6, 121.9, 122.0, 127.9, 128.2, 128.3, 131.6, 134.4, 134.6, 135.8, 136.0, 136.1, 153.5, 156.2, 157.0, 172.6. Anal. Calcd for C49H64N2O5: C, 77.33; H, 8.48; N, 3.68. Found: C, 77.61; H, 8.22; N, 3.96. ESI-MS: m/z = 761 ([M + 1]+, 100%), 783 ([M + Na]+, 32%), 799 ([M + K]+, 20%).
40. Representative synthetic procedure of route B [11]: To a solution of trans-4-hydroxy-L-N-Boc-proline (0.25 g, 1.1 mmol) in CH2Cl2 (30 mL) was added TEA (0.11 mL, 1.1 mmol) and ethyl chloroformate (0.14 mL, 1.1 mmol) at 0 °C under stirring. After 15 min, 5-amino-25,26,27,28-tetrabutoxycalix[4]arene 14a (0.66 g, 1.0 mmol) was added. The reaction was allowed to warm to ambient temperature and stirred for 7 h. After reaction, the mixture was washed with KHSO4 (1 M), saturated NaHCO3 and brine, and dried over anhydrous Na2SO4. The solvent was evaporated under vacuum, and the residue was purified by column chromatography with petroleum ether/ethyl acetate (2:1, v/v) as an eluent to give 0.65 g Boc-protected product which was dissolved in CHCl3 (30 mL). After addition of TFA (1 mL), the reaction mixture was stirred at 50 °C for 3 h. The solvent was removed, CHCl3 (30 mL) and H2O (30 mL) were added. The pH of the mixture was adjusted to 8-9 by the addition of aqueous NaOH (2 M), and the water layer was extracted with additional CHCl3 (30 mL). The combined organic layer was washed with brine (30 mL) and dried over anhydrous Na2SO4. The solvent was removed to give pure target product 6 as a yellow solid. Yield: 74%. mp 107-109 °C. IR (KBr): 3413, 2959, 2929, 2868, 1677, 1605, 1533, 1460, 1382, 1290, 1245, 1205, 1134, 1085, 1029, 962, 763 cm-1. 1H NMR (300 MHz, DMSO-d6): δ = 0.97 (t, J = 7.5 Hz, 12H, CH3), 1.37-1.52 (m, 8H, CH2), 1.67-2.03 (m, 10H, CH2), 2.72-2.91 (m, 2H, NCH2), 3.08-3.18 (2d, J = 13.2 Hz, 4H, ArCH2Ar), 3.75-3.89 (m, 9H, NCHCO + ArOCH2), 4.20 (m, 1H, HCOH), 4.29-4.36 (2d, J = 13.2 Hz, 4H, ArCH2Ar), 4.76 (br s, 1H, OH), 6.45-6.62 (m, 7H, ArH), 6.68 (d, J = 7.5 Hz, 2H, ArH), 6.94-6.98 (2d, J = 2.4 Hz, 2H, ArH), 9.55 (s, 1H, CONH); 13C NMR (75 MHz, CDCl3): δ = 14.0, 19.3, 19.4, 22.6, 29.6, 30.9, 31.3, 31.4, 31.9, 32.1, 32.2, 32.3, 39.6, 54.8, 59.7, 72.2, 74.8, 120.1, 121.6, 122.0, 128.0, 128.2, 131.3, 134.3, 134.5, 134.7, 135.5, 136.0, 153.9, 156.2, 156.9, 170.3. Anal. Calcd for C49H64N2O6: C, 75.74; H, 8.30; N, 3.61. Found: C, 75.47; H, 8.59; N, 3.87. ESI-MS: m/z = 778 ([M + 1]+, 9%), 800 ([M + Na]+, 100%), 816 ([M + K]+, 38%).
41. Synthesis of 11 from 17: The procedure was similar to the synthesis of 1 by route A [16]. Pale yellow solid, mp: 63-64 °C. Yield: 81%. IR (KBr): 3447, 3349, 2958, 2932, 2869, 1662, 1592, 1516, 1472, 1411, 1298, 1241, 1174, 1105, 1071, 1029, 973, 914, 830 cm-1. 1H NMR (300 MHz, CDCl3): δ = 0.97 (t, J = 7.5 Hz, 3H, CH3), 1.42-1.54 (m, 2H, CH2), 1.70-1.79 (m, 4H, CH2), 1.86 (br s, 1H, NH), 1.98-2.09 (m, 1H, CH2), 2.15-2.27 (m, 1H, CH2), 2.94-3.12 (m, 2H, NCH2), 3.82-3.87 (m, 1H, COCHN), 3.94 (t, J = 6.6 Hz, 2H, ArOCH2), 6.85 (d, J = 9.0 Hz, 2H, ArH), 7.49 (d, J = 9.0 Hz, 2H, ArH), 9.58 (s, 1H, CONH); 13C NMR (75 MHz, CDCl3): δ = 13.8, 19.1, 24.9, 26.2, 30.7, 31.2, 33.8, 47.2, 48.7, 60.8, 67.8, 114.6, 120.7, 130.9, 155.5, 172.9. Anal. Calcd for C15H22N2O2: C, 68.67; H, 8.45; N, 10.68. Found: C, 68.94; H, 8.24; N, 10.35. ESIMS: m/z = 263 ([M + 1]+, 100%), 285 ([M + Na]+, 22%), 525 ([2M + 1]+, 48%), 547 ([2M + Na]+, 17%).
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52. General procedure for the asymmetric aldol reaction: The catalyst 2 (2 mol%), benzoic acid (2 mol%) and aldehyde (0.5 mmol) was stirred in ketone (0.5 mL) for 48 h at -25 °C. After the reaction, the mixture was purified through flash column chromatography on silica gel with hexane/ethyl acetate mixture as eluents. The anti/syn ratio (diastereoselectivity) and enantiomeric excess (enantioselectivity) were determined by chiral HPLC analysis (Daicel Chiralpak AD-H, AS-H, or OD-H column).