Synlett 2017; 28(09): 1116-1120
DOI: 10.1055/s-0036-1588704
letter
© Georg Thieme Verlag Stuttgart · New York

Visible-Light-Mediated Dealkylative Coupling of Trialkylamines with Dialkyl Acetylenedicarboxylates

Fangnan Liu
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. of China   Email: zhiguo.zhang@zju.edu.cn
,
Zhiguo Zhang*
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. of China   Email: zhiguo.zhang@zju.edu.cn
,
Zongbi Bao
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. of China   Email: zhiguo.zhang@zju.edu.cn
,
Baogen Su
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. of China   Email: zhiguo.zhang@zju.edu.cn
,
Huabin Xing
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. of China   Email: zhiguo.zhang@zju.edu.cn
,
Qiwei Yang
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. of China   Email: zhiguo.zhang@zju.edu.cn
,
Yiwen Yang
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. of China   Email: zhiguo.zhang@zju.edu.cn
,
Qilong Ren
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. of China   Email: zhiguo.zhang@zju.edu.cn
› Author Affiliations
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.

Supporting Information

 
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  • 13 A control experiment with a dialkylamine and an acetylenedicarboxylate gave the corresponding product in 95% yield within three hours.
  • 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.