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Synlett 2017; 28(09): 1116-1120
DOI: 10.1055/s-0036-1588704
DOI: 10.1055/s-0036-1588704
letter
Visible-Light-Mediated Dealkylative Coupling of Trialkylamines with Dialkyl Acetylenedicarboxylates
Authors
Further Information
Publication History
Received: 08 December 2016
Accepted after revision: 14 January 2017
Publication Date:
03 February 2017 (online)
Abstract
A dealkylative addition of trialkylamines to dialkyl acetylenedicarboxylates with eosin Y as a metal-free catalyst and molecular oxygen as the terminal oxidant was developed. This visible-light-mediated organocatalytic protocol is compatible with a wide variety of trialkylamines, giving the corresponding adducts in moderate to good yields.
Key words
dealkylation - addition - photoredox reaction - organocatalysis - trialkylamines - dialkyl acetylenedicarboxylatesSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588704.
- Supporting Information (PDF)
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References and Notes
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- 14 Dialkyl Aminomaleates 3; General Procedure A 10-mL Schlenk tube equipped with a magnetic stirrer bar and rubber septum was charged with the appropriate dialkyl acetylenedicarboxylate 2 (0.2 mmol) and eosin Y (0.006 mmol), and the tube was evacuated and backfilled with O2 three times. The appropriate trialkylamine 1 (0.4 mmol) and toluene (2.0 mL) were added from a syringe under O2. The mixture was then protected with an O2 balloon and irradiated at r.t. with a 3 W green LED placed at a distance of about 5.0 cm from the reaction vessel. When the reaction was complete (TLC), the solvent was removed under reduced pressure, and the crude product was purified by flash chromatography (silica gel). Dimethyl (2E)-2-(Diethylamino)but-2-enedioate (3a) Pale-yellow oil; yield: 26.3 mg (61%). IR (film): 3095, 2981, 2863, 1744, 1694, 1570, 1446, 1378, 1158 cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.59 (s, 1 H), 3.91 (s, 3 H), 3.61 (s, 3 H), 3.16 (q, J = 7.1 Hz, 4 H), 1.16 (t, J = 7.1 Hz, 6 H). 13C NMR (101 MHz, CDCl3): δ = 168.46, 166.25, 153.89, 82.96, 52.96, 50.79, 45.00, 12.79. HRMS (EI): m/z calcd for C10H17NO4: 215.1158; found: 215.1162. Dimethyl (2E)-2-(Dipropylamino)but-2-enedioate (3c) Pale-yellow oil; yield: 29.2 mg (60%). IR (film): 2969, 2880, 1745, 1695, 1574, 1157, 1131, 1050 cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.56 (s, 1 H), 3.91 (s, 3 H), 3.61 (s, 3 H), 3.03 (t, J = 7.8 Hz, 4 H), 1.60 (m, 4 H), 0.87 (t, J = 7.4 Hz, 6 H). 13C NMR (101 MHz, CDCl3): δ = 168.45, 166.25, 154.39, 83.17, 52.91, 50.80, 20.49, 11.28. HRMS (EI): m/z calcd for C12H21NO4: 243.1471; found: 243.1473. Diethyl (2E)-2-(Dipropylamino)but-2-enedioate (3d)Colorless oil; yield: 27.1 mg (50%). IR (film): 2970, 2900, 2879, 1741, 1694, 1574, 1439, 1209, 1155, 1130, 1052, 792 cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.54 (s, 1 H), 4.38 (q, J = 7.2 Hz, 2 H), 4.07 (q, J = 7.1 Hz, 2 H), 3.04 (t, J = 7.9 Hz, 4 H), 1.60 (m, 4 H), 1.36 (t, J = 7.2 Hz, 3 H), 1.22 (t, J = 7.2 Hz, 3 H), 0.87 (t, J = 7.4 Hz, 6 H). 13C NMR (101 MHz, CDCl3): δ = 167.91, 165.80, 154.41, 83.54, 62.09, 59.21, 52.68, 20.57, 14.65, 14.06, 11.28. HRMS (EI): m/z calcd for C14H25NO4: 271.1784; found: 271.1789. Dimethyl (2E)-2-(Dibutylamino)but-2-enedioate (3e) Pale-yellow oil; yield: 30.9 mg (57%). IR (film): 2958, 2918, 2849, 1745, 1696, 1574, 1462, 1373, 1155, 1133 cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.56 (s, 1 H), 3.91 (s, 3 H), 3.62 (s, 3 H), 3.07 (t, J = 7.8 Hz, 4 H), 1.55 (m, 4 H), 1.28 (m, 4 H), 0.91 (t, J = 7.3 Hz, 6 H). 13C NMR (101 MHz, CDCl3): δ = 168.48, 166.25, 154.34, 83.09, 52.90, 50.81, 29.34, 20.17, 13.87. HRMS (EI): m/z calcd for C14H25NO4: 271.1784; found: 271.1782. Diethyl (2E)-2-(Dibutylamino)but-2-enedioate (3f)Pale yellow oil ; yield: 29.3 mg (49%). IR (film): 2961, 2935, 2874, 1741, 1694, 1466, 1376, 1247, 1153, 1131, 1051, 1026, 791 cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.54 (s, 1 H), 4.37 (q, J = 7.2 Hz, 2 H), 4.07 (q, J = 7.1 Hz, 2 H), 3.07 (t, J = 7.8 Hz, 4 H), 1.56 (m, 4 H), 1.36 (t, J = 7.2 Hz, 3 H), 1.32–1.18 (m, 7 H), 0.91 (t, J = 7.3 Hz, 6 H). 13C NMR (101 MHz, CDCl3): δ = 167.93, 165.81, 154.37, 83.48, 62.10, 59.21, 50.79, 29.37, 20.20, 14.65, 14.05, 13.89. HRMS (EI): m/z calcd for C16H29NO4: 299.2097; found: 299.2096. Dimethyl (2E)-2-[Cyclohexyl(ethyl)amino]but-2-enedioate (3j) Pale-yellow oil; yield: 24.2 mg (45%). IR (film): 2921, 2854, 1745, 1695, 1567, 1446, 1379, 1257, 1191, 1157, 1139, 1048 cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.59 (s, 1 H), 3.93 (s, 3 H), 3.62 (s, 3 H), 3.17 (d, J = 7.1 Hz, 2 H), 3.09 (m, 1 H), 1.81 (m, 4 H), 1.63 (m, 2 H), 1.41 (m, 2 H), 1.23 (m, 2 H), 1.15 (t, J = 7.1 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 168.59, 166.49, 154.18, 82.65, 52.96, 50.80, 39.45, 31.41, 25.93, 25.40. HRMS (EI): m/z calcd for C14H23NO4: 269.1627; found: 269.1628. Dimethyl (2E)-2-[Methyl(octyl)amino]but-2-enedioate (3n) Pale-yellow oil; yield: 24.0 mg (42%). IR (film): 2957, 2925, 1747, 1698, 1576, 1436, 1410, 1242, 1153, 1074, 1045cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.56 (s, 1 H), 3.92 (s, 3 H), 3.63 (s, 3 H), 3.08 (t, J = 7.7 Hz, 2 H), 2.82 (s, 3 H), 1.57 (m, 2 H), 1.27 (m, 10 H), 0.87 (t, J = 6.7 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 168.36, 166.23, 154.93, 83.81, 53.49, 53.01, 50.88, 37.54, 31.89, 29.37, 29.29, 26.77, 22.76, 14.22. HRMS (EI): m/z calcd for C15H27NO4: 285.1940; found: 285.1944. Dimethyl (2E)-2-[Ethyl(2-methoxy-2-oxoethyl)amino]but-2-enedioate (3o)Yellow oil; yield: 15.0 mg (29%). IR (film): 2987, 2960, 2921, 1743, 1697, 1577, 1437, 1394, 1382, 1206, 1156, 1120, 1156, 1051 cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.62 (s, 1 H), 3.91 (s, 3 H), 3.85 (s, 2 H), 3.75 (s, 3 H), 3.62 (s, 3 H), 3.27 (q, J = 7.2 Hz, 2 H), 1.18 (t, J = 7.2 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 169.02, 167.92, 165.77, 153.98, 85.93, 53.14, 52.62, 51.04, 47.16, 12.72. HRMS (EI): m/z calcd for C11H17NO6: 259.1056; found: 259.1061.