10.1002/adsc.201801194
Advanced Synthesis & Catalysis
166.70, 164.75, 52.99, 52.28, 46.17, 41.42, 39.69, 25.23,
18.80. IR vC=O: 1604 cm-1 (vs). HRMS (ESI): [M-
CO2+H]+ calcd for C8H15N2: 139.1230; Found: 139.1226.
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1
3b. White solid (0.38 g, 85% yield). H NMR (400 MHz,
d6-DMSO): δ 3.64-3.73 (m, 2H), 3.49-3.56 (m, 2H), 3.31-
3.36 (m, 5H), 2.13-2.18 (m, 2H), 1.88-1.96 (m 2H), 1.52-
1.61 (m, 2H), 1.21-1.29 (m, 2H), 0.89 (t, J = 7.2 Hz, 3H).
13C NMR (100 MHz, d6-DMSO): δ 167.48, 164.83, 53.58,
52.84, 52.51, 44.26, 42.23, 29.29, 25.92, 19.69, 19.32,
14.11. IR vC=O: 1608 cm-1 (vs). HRMS (ESI): [M-
CO2+H]+ calcd for C11H21N2: 181.1699; Found: 181.1700.
3c White solid (0.44 g, 86% yield). 1H NMR (400 MHz,
d6-DMSO): δ 7.33-7.39 (m, 5H), 4.93 (d, J = 15.4 Hz, 1H),
4.69 (d, J = 15.4 Hz, 1H), 3.75 (q, J = 9.2 Hz, 1H), 3.68 (d,
J = 8.4 Hz, 1H), 3.57 (dt, J = 2.1, 9.2 Hz, 1H), 3.34-3.42
(m. 2H), 3.13-3.18 (m, 1H), 2.16-2.28 (m, 2H), 1.83-1.96
(m, 2H). 13C NMR (100 MHz, d6-DMSO): δ 167.06,
164.83, 134.90, 128.64, 128.12, 127.92, 55.29, 53.46,
52.83, 43.69, 41.84, 25.39, 18.76. IR vC=O: 1611 cm-1 (vs).
HRMS (ESI): [M-CO2+H]+ calcd for C14H19N2: 215.1543 .
Found: 215.1541.
3d White solid (0.34 g, 87% yield). 1H NMR (400 MHz,
d6-DMSO): δ 3.57 (t, J = 7.2 Hz, 2H), 3.34 (t, J = 5.4 Hz,
2H), 3.05 (s, 3H), 2.34 (dt, J = 7.7, 12.2 Hz, 1H), 1.94-1.95
(m, 2H), 1.76-1.82 (m, 1H), 1.29 (s, 3H). 13C NMR (100
MHz, d6-DMSO): δ 170.35, 167.97, 56.24, 51.58, 47.17,
41.84, 34.62, 21.34, 18.71. IR vC=O: 1600 cm-1 (vs).
HRMS (ESI): [M-CO2+H]+ calcd for C9H17N2: 153.1386.
Found: 153.1387.
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Representative experimental procedure for the
carboxylative cyclization of CO2 with functionalized
propargylic alcohols to α-alkylidene cyclic carbonates
In a glove box, a 10 ml autoclave containing a stir bar was
charged with propargylic alcohol 4a (0.80 g, 5 mmol), and
catalyst THPE-CO2 3a (45.5 mg, 0.25 mmol, 5 mol%).
After purging the autoclave with CO2 three times, the
sealed autoclave was pressurized to the appropriate
pressure with CO2. The reaction was carried out at 60 °C
for 2 h with continuous stirring. Then, the autoclave was
cooled, and the excess CO2 was vented. The residue was
purified by column chromatography (eluent: petroleum
ether/EtOAc=10:1) to give the corresponding α-alkylidene
1
cyclic carbonate 5a (0.94 g, 92 %) as a white solid. H
NMR (400 MHz, CDCl3): δ = 7.51-7.53 (m, 2H), 7.23-
7.35 (m, 3H), 5.47 (s, 1H), 1.66 (s, 6H). 13C NMR (100
MHz, CDCl3): δ = 151.2, 150.5, 132.4, 128.7, 128.8, 127.5,
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1
101.3, 85.5, 27.4. All the resonances in H and 13C NMR
spectra were in good agreement with literature values.[8]
X-Ray structure: Supplementary crystallographic data
was deposited at the Cambridge Crystallographic Data
Centre (CCDC) under the numbers CCDC 1455223 (3a),
CCDC 1455222 (3c), CCDC 1401873 (3d), CCDC
1455756 (5s') and can be obtained free of charge from via
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Acknowledgements
[5] M. Devillard, R. Declercq, E. Nicolas, A. W. Ehlers, J.
Backs, N. Saffon-Merceron, G. Bouhadir, J. C.
Slootweg, W. Uhl, D. Bourissou, J Am Chem Soc 2016,
138, 4917-4926.
This work is supported by National Natural Science Foundation
of China (Grant No. 21402021), the Fundamental Research
Funds for the Central Universities (DUT18LK55) and the
Program for Changjiang Scholars and Innovative Research Team
in University (IRT-17R14). X.-B. Lu gratefully acknowledges the
Chang Jiang Scholars Program (No. T2011056) from Ministry of
Education, People’s Republic of China.
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