Angewandte Chemie International Edition
10.1002/anie.201803967
COMMUNICATION
In conclusion, a new domino process has been developed
towards the elusive coupling of tri- and tetrasubstituted epoxides
and CO by an organocatalytic strategy. This novel reactivity
2
[6]
a) L.-C. Yang, Z.-Q. Rong, Y.-N. Wang, Z. Y. Tan, M. Wang, Y. Zhao,
Angew. Chem. Int. Ed. 2017, 56, 2927-2931; b) Z.-Q. Rong, L.-C. Yang,
S. Liu, Z. Yu, Y.-N. Wang, Z. Y. Tan, R.-Z. Huang, Y. Lan, Y. Zhao, J.
Am. Chem. Soc. 2017, 139, 15304-15307.
allows for the synthesis of otherwise elusive cyclic carbonates
under mild reaction conditions, is operationally friendly and allows
for regio-selective formation of mono-carbonates using bis- or tris-
epoxy-based substrates. This substrate-controlled conversion of
carbon dioxide offers access to new, functional heterocyclic
scaffolds with amplified potential in synthetic chemistry.
[
7]
a) Q. Lu, F. J. R. Klauck, F. Glorius, Chem. Sci. 2017, 8, 3379-3383; b)
A. Khan, L. Yang, J. Xu, L. Y. Jin, Y. J. Zhang, Angew. Chem. Int. Ed.
2014, 53, 11257-11260; c) A. Khan, R. Zheng, Y. Kan, J. Ye, J. Xing, Y.
J. Zhang, Angew. Chem. Int. Ed. 2014, 53, 6439–6442; d) V. Laserna,
G. Fiorani, C. J. Whiteoak, E. Martin, E. Escudero-Adán, A. W. Kleij,
Angew. Chem. Int. Ed. 2014, 53, 10416-10419; e) W. Guo, J. González-
Fabra, N. A. G. Bandeira, C. Bo, A. W. Kleij, Angew. Chem. Int. Ed. 2015,
54, 11686-11690; f) Y. Liu, W.-M. Ren, K.-K. He, W.-Z. Zhang, W.-B. Li,
M. Wang, X.-B. Lu, J. Org. Chem. 2016, 81, 8959-8966.
Acknowledgements
[
[
8]
9]
For general reviews concerning their synthesis using different Lewis
acids: a) A. Decortes, A. M. Castilla, A. W. Kleij, Angew. Chem. Int. Ed.
2010, 49, 9822-9837; b) P. P. Pescarmona, M. Taherimehr, Catal. Sci.
Technol. 2012, 2, 2169-2187; c) M. North, R. Pasquale, C. Young, Green
Chem. 2010, 12, 1514-1539.
We thank the CERCA Program/Generalitat de Catalunya, ICREA,
the Spanish MINECO (CTQ2017-88920-P and SEV-2013-0319),
and AGAUR (2017-SGR-232). S. S. thanks Covestro for support.
Dr. Marta Giménez and Cristina Rivero are thanked for help with
the high-pressure reactions and Dr. Noemí Cabello for the MS
measurements.
For recent contributions based on metal approaches towards tri-
substituted cyclic carbonates though mostly with important limitations in
scope and yields: a) G. Fiorani, M. Stuck, C. M. Martín, M. Martínez-
Belmonte, E. Martin, E. C. Escudero-Ada
016, 9, 1304-1311; b) J. Martínez, J. Fernández-Baeza, L. F. Sánchez-
Barba, J. A. Castro-Osma, A. Lara-Sánchez A. Otero, ChemSusChem
017, 10, 2886-2890; c) C. Maeda, J. Shimonishi, R. Miyazaki, J.-Y.
́
n, A. W. Kleij, ChemSusChem
2
Keywords: carbon dioxide • domino process • epoxy alcohols •
organocatalysis • Payne rearrangement
2
Hasegawa, T. Ema, Chem. Eur. J. 2016, 22, 6556−6563; d) V. Laserna,
E. Martin, E. C. Escudero-Adán, A. W. Kleij, ACS Catal. 2017, 7, 5478-
[
1]
For general reviews: a) C. Martín, G. Fiorani, A. W. Kleij, ACS Catal.
015, 5, 1353-1370; b) J. W. Comerford, I. D. V. Ingram, M. North, X. Wu,
5482; e) L. Longwitz, J. Steinbauer, A. Spannenberg, T. Werner, ACS
2
Catal. 2018, 8, 665-672.
Green Chem. 2015, 17, 1966-1987; c) G. Fiorani, W. Guo, A. W. Kleij,
Green Chem. 2015, 17, 1375-1389; d) M. Alves, B. Grignard, R. Mereau,
C. Jerome, T. Tassaing, C. Detrembleur, Catal. Sci. Technol. 2017, 7,
[
[
10] For a compelling review on naturally occurring organic carbonates: H.
Zhang, H.-B. Liu, J.-M. Yue, Chem. Rev. 2014, 114, 883-898.
11] a) C. J. Whiteoak, E. Martin, E. C. Escudero-Adán, A. W. Kleij, Adv.
Synth. Catal. 2013, 355, 2233-2239; b) C. J. Whiteoak, N. Kielland, V.
Laserna, E. C. Escudero-Adán, E. Martin, A. W. Kleij, J. Am. Chem. Soc.
2651-2684; e) M. Cokoja, M. E. Wilhelm, M. H. Anthofer, W. A. Herrmann,
F. E. Kühn, ChemSusChem 2015, 8, 2436-2454; f) R. Rajjak Shaikh, S.
Pornpraprom, V. D’Elia, ACS Catal. 2018, 8, 419-450.
2013, 135, 1228-1231.
[
2]
For reviews see: a) T. Sakakura, J.-C. Choi, H. Yasuda, Chem. Rev.
[
[
12] G. B. Payne, J. Org. Chem. 1962, 27, 3819-3822.
2007, 107, 2365-2387; b) B. Schäffner, F. Schäffner, S. P. Verevkin, A.
13] J. Rintjema, R. Epping, G. Fiorani, E. Martín, E. C. Escudero-Adán, A.
W. Kleij, Angew. Chem. Int. Ed. 2016, 55, 3972-3976.
Börner, Chem. Rev. 2010, 110, 4554-4581. For polymers derived from
cyclic carbonates: c) D. J. Darensbourg, A. I. Moncada, W. Choi, J. H.
Reibenspies, J. Am. Chem. Soc. 2008, 130, 6523-6533; d) A. K. Diallo,
E. Kirillov, M. Slawinski, J.-M. Brusson, S. M. Guillaume, J.-F. Carpentier,
Polym. Chem. 2015, 6, 1961-1971; e) H. Matsukizono, T. Endo, J. Polym.
Sci., A: Polym. Chem. 2016, 54, 487-497.
[14] Note that the known, nucleophilic bromide-based catalyst TBAB showed
a combined yield of only 7% for 2a/2b (2a:2b = 55:45), see the
Supporting Information for details. This demonstrates that the in situ
formation of a nucleophilic species derived from the epoxy alcohol
substrate is far more effective than the use of an external nucleophile.
[15] Primary alcohols can be easily protected using AcIm, see: a) H.
Hagiwara, K. Morohashi, T. Suzuki, M. Ando, I. Yamamoto, M. Kato,
Synth. Commun. 1998, 28, 2001-2006; b) R. C. Pratt, B. G. G. Lohmeijer,
D. A. Long, R. M. Waymouth, J. L. Hedrick, J. Am. Chem. Soc. 2006,
[
[
[
[
3]
4]
5]
a) N. Kielland, C. J. Whiteoak, A. W. Kleij, Adv. Synth. Catal. 2013, 355,
2115-2138; b) J. Vaitla, Y. Guttormsen, J. K. Mannisto, A. Nova, T. Repo,
A. Bayer, K. H. Hopmann, ACS Catal. 2017, 7, 7231-7244; c) Y. Li, X.
Cui, K. Dong, K. Junge, M. Beller, ACS Catal. 2017, 7, 1077-1086; d) M.
Börjesson, T. Moragas, D. Gallego, R. Martin, ACS Catal. 2016, 6, 6739-
128, 4556-4557.
6749; e) Q. Liu, L. Wu, R. Jackstell, M. Beller, Nat. Commun. 2015, 6,
16] For the one-pot reactions towards 913 typically we found 8:2 ratios
between the desired tetra-substituted carbonate and a disubstituted one
contrary to the syntheses of trisubstituted carbonate products 48. This
observation indicates that the acetyl-protection (third step in the one-pot
synthesis) is more competitive because of a slower base-induced
equilibration of both carbonates. For this reason most of the unprotected
tetrasubstituted carbonates were directly isolated.
5933.
a) W. Guo, A. Cai, J. Xie, A. W. Kleij, Angew. Chem. Int. Ed. 2017, 56,
1797-11801; b) A. Cai, W. Guo, L. Martínez-Rodríguez, A. W. Kleij, J.
1
Am. Chem. Soc. 2016, 138, 14194-14197; c) W. Guo, L. Martínez-
Rodríguez, R. Kuniyil, E. Martin, E. C. Escudero-Adán, F. Maseras, A.
W. Kleij, J. Am. Chem. Soc. 2016, 138, 11970-11978; d) W. Guo, L.
Martínez-Rodríguez, E. Martín, E. C. Escudero-Adán, A. W. Kleij, Angew.
Chem. Int. Ed. 2016, 55, 11037-11040.
[
[
17] For details, see CCDC 1832243 and 1832244.
18] Pure trisubstituted carbonate 21 was isolated (30%) as
a single
a) H. Wang, M. M. Lorion, L. Ackermann, ACS Catal. 2017, 7, 3430-
diastereoisomer (dr >99:1) by chromatographic separation; note,
however, that initially quantitative formation of a mixture of both the tri-
and monosubstituted carbonate occurred (ratio tri/mono = 83:17, dr =
3433; b) H. Wang, M. M. Lorion, L. Ackermann, Angew. Chem. Int. Ed.
2017, 56, 6339-6342; c) Q. Lu, F. J. R. Klauck, F. Glorius, Chem. Sci.
2017, 8, 3379.
57:43 for the trisubstituted product).
This article is protected by copyright. All rights reserved.