Vinylene Carbonate: A Versatile Synthon in Organic Synthetic Chemistry

doi:10.6023/cjoc202401036

Abstract

In recent years, vinylene carbonate has become a new and ideal multifunctional synthon, which is widely used in a variety of organic transformations. Especially in the field of transition metal-catalyzed C—H functionalization, it can be used to construct target molecules containing carbon and heterocyclic skeletons. Since Nishii and Miura first reported that vinylene carbonate participates in coupling reactions as an “ethynol surrogate” in 2009, it has been successively reported as an “acetylene surrogate”, “C1 synthon”, “acylmethylation reagent”, and others. These developments not only highlight the multifunctional transformation of vinylene carbonate, but also provide new ideas for the synthesis of complex compounds. The latest research progress of vinylene carbonate in recent years is summarized and the prospects for its future development based on the different reaction roles of vinylene carbonate in synthetic chemistry are proposed.

Key words: vinyl carbonate, C—H functionalization, cyclization, N-heterocycles

Cite this article

Yu Lin, Haifeng Fu, Hua Cao, Xiang Liu. Vinylene Carbonate: A Versatile Synthon in Organic Synthetic Chemistry[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2147-2173.

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Fig. & Tab. 39

Scheme 1. Application of vinylene carbonate as multifunctional synthon in organic synthesis

Scheme 2. First report on ethylene carbonate as a "ethynol surrogate"

Scheme 3. Rh-catalyzed [4+1]/[4+2] cyclization of azobenzenes and vinylene carbonate

Scheme 4. Rh-catalyzed cyclization reaction of sulfonylbenzamide with vinyl carbonate

Scheme 5. Ru-catalyzed cyclization of 2-arylquinazolinone and ethylene carbonate

Scheme 6. Annulation reaction of N-arylphthalazinones/N-arylindazolones with vinylene carbonate

Scheme 7. Reaction mechanism of annulation reaction of N-arylphthalazinones with vinylene carbonate

Scheme 8. Rhodium-catalyzed C—H activation/annulation of sulfoxonium ylides with vinylene carbonate

Scheme 9. Cyclization reaction of azinium-N-imines with vinyl carbonate

Scheme 10. Substrate scope

Scheme 11. Reaction mechanism and products derivations

Scheme 12. Rhodium-catalyzed C—H/N—H annulation using vinylene carbonate as an oxidizing acetylene surrogate

Scheme 13. Mechanism of rhodium-catalyzed C—H/N—H annulation

Scheme 14. Synthesis of isocoumarins via Rh-catalysis

Scheme 15. Rhodium-catalyzed oxidative C—H/C—H annulation of imidazopyridines and pyrazole

Scheme 16. Rhodium-catalyzed [4+2] annulation between N-arylmethanimines with vinylene carbonate

Scheme 17. Possible reaction mechanism

Scheme 18. Synthesis of isoquinolino[1,2-b] quinazolinones

Scheme 19. Rh-catalyzed annulation of benzamidines with vinylene carbonate

Scheme 20. Rhodium-catalyzed C—H bond activation and vinylene transfer of enaminones with vinylene carbonate

Scheme 21. Cyclization of azobenzenes and vinylene carbonate

Scheme 22. Rh(III)-catalyzed annulation of 1-phenylpyrazolidinones with vinylene carbonate

Scheme 23. Rhodium-catalyzed direct vinylene annulation of sulfoxonium ylides and N-carbamoylindoles with vinylene carbonate

Scheme 24. Co(III)-catalyzed annulation of benzamides and acrylamides with vinylene carbonate

Scheme 25. Cyclization of N-phenylpivalamides with vinylene carbonate

Scheme 26. Mn(II)-catalyzed [4+2] annulation of N-arylbenzamidines with vinylene carbonate

Scheme 27. Synthesis of benzo-fused indolizines via the 1,3-dipolar cycloadditions of N-isoquinoline salts with vinylene carbonate

Scheme 28. [4+1] annulation of amidine with vinylene carbonate

Scheme 29. Rh-catalyzed annulation of aniline with vinylene carbonate

Scheme 30. Rh-catalyzed [4+1] cyclization reaction of aryl azobenzene and vinylene carbonate

Scheme 31. RhIII-catalyzed formal [5+1] cyclization of 2-pyrrolyl/indolylanilines with vinylene carbonate

Scheme 32. Rh-catalyzed formylmethylation

Scheme 33. Rh-catalyzed C2/C7 alkylation of indole derivatives with vinyl carbonate

Scheme 34. C—H acetylation of N-(2-pyrimidyl)indoles

Scheme 35. Formylmethylation of isoxazoles with vinylene carbonates

Scheme 36. Ruthenium-catalyzed C—H formylmethylation of indolines

Scheme 37. Iridium-catalyzed arylation of vinylene carbonate with arylboronic acids

Scheme 38. Annulation of 2-indolylanilines/2-pyrrolylanilines with vinylene carbonate

Scheme 39. Possible reaction mechanism of 2-pyrrolylanilines with vinylene carbonate

References 37

[1]	(a) Newman, M. S.; Addor, R. W. J. Am. Chem. Soc. 1955, 77, 3789. pmid: 15704944
	(b) Arjona, O.; Medel, R.; Plumet, J.; Herrera, R.; JiménezVázquez, H. A.; Tamariz, J. J. Org. Chem. 2004, 69, 2348. pmid: 15704944
	(c) Afarinkia, K. Bearpark, M. J.; Ndibwami, A. J. Org. Chem. 2005, 70, 1122. pmid: 15704944
	(d) Tabanelli, T.; Giliberti, C.; Mazzoni, R.; Cucciniello, R.; Cavani, F. Green Chem. 2019, 21, 329. doi: 10.1039/c8gc02811g pmid: 15704944
[2]	(a) Ding, L.; Li, Y.; Li, Y.; Liang, Y.; Huang, J. Eur. Polym. J. 2001, 37, 2453.
	(b) Rzhekhina, E. K. Polym. Sci., Ser. D 2012, 5, 86.
	(c) Chauveau, C.; Fouquay, S.; Michaud, G.; Simon, F.; Carpentier, J.-F.; Guillaume, S. M. Eur. Polym. J. 2019, 116, 144. doi: 10.1016/j.eurpolymj.2019.03.052
	(d) Dobi, Z.; Reddy, B. N.; Renders, E.; Van Raemdonck, L.; Mensch, C.; De Smet, G.; Chen, C.; Bheeter, C.; Sergeyev, S.; Herrebout, W. A.; Maes, B. U. W. ChemSusChem 2019, 12, 3103.
[3]	(a) Cui, X.; Chauvin, R.; Pi, C.; Wu, Y.; Cui, X. Adv. Synth. Catal. 2023, 365, 3400.
	(b) Ge, Y.; Yan, Q.; Nan, J. Org. Chem. Front. 2023, 10, 5717.
[4]	Hara, H.; Hirano, M.; Tanaka, K. Org. Lett. 2009, 11, 1337.
[5]	(a) Muraoka, T.; Kinbara, K.; Aida, T. Nature 2006, 440, 512. pmid: 11720562
	(b) Banghart, M. R.; Mourot, A.; Fortin, D. L.; Yao, J. Z.; Kramer, R. H.; Trauner, D. Angew. Chem., Int. Ed. 2009, 48, 9097. doi: 10.1002/anie.200904504 pmid: 11720562
	(c) Puntoriero, F.; Ceroni, P.; Balzani, V.; Bergamini, G.; Voegtle, F. J. Am. Chem. Soc. 2007, 129, 10714. pmid: 11720562
	(d) DiCesare, N.; Lakowicz, J. R. Org. Lett. 2001, 3, 3891. pmid: 11720562
	(e) Hunger, K. Industrial Dyes Chemistry, Properties, Applications, Wiley-VCH, Weinheim, 2003. pmid: 11720562
	(f) Burland, D. M.; Miller, R. D.; Walsh, C. A. Chem. Rev. 1994, 94, 31. pmid: 11720562
	(g) Nguyen, T. H. L.; Gigant, N.; Joseph, D. ACS Catal. 2018, 8, 1546. pmid: 11720562
[6]	Park, M. S.; Moon, K.; Oh, H.; Lee, J. Y.; Ghosh, P.; Kang, J. Y.; Park, J. S.; Mishra, N. K.; Kim, I. S. Org. Lett. 2021, 23, 5518. doi: 10.1021/acs.orglett.1c01866 pmid: 34228466
[7]	Wang, L.; Shao, Y.; Chen, F.; Qian, P.-C.; Cheng, J. Chin. J. Org. Chem. 2022, 42, 242. (in Chinese)
	(王璐, 邵莺, 陈帆, 钱鹏程, 成江, 有机化学, 2022, 42, 242.) doi: 10.6023/cjoc202106023
[8]	Wang, Z.-H.; Wang, H.; Wang, H.; Li, L.; Zhou, M.-D. Org. Lett. 2021, 23, 995.
[9]	Kim, S.; Park, H. K.; Kang, J. Y.; Mishra, N. K.; Kim, I. S. Synthesis 2022, 54, A.
[10]	Song, J.-L.; Xiao, L.; Chen, S.-Y.; Zheng, Y.-C.; Liu, Y.-Z.; Zhang, S.-S.; Shu, B. Adv. Synth. Catal. 2023, 365, 1457.
[11]	(a) Liu, X.; Li, W.; Jiang, W.; Lu, H.; Liu, J.; Lin, Y.; Cao, H. Org. Lett. 2022, 22, 613.
	(b) Zhu, B.; Li, W.; Chen, H.; Wu, M.; Hu, J.; Cao, H.; Liu, X. Adv. Synth. Catal. 2022, 364, 2911.
	(c) Shi, X.; Lin, Y.; Wei, J.; Zhao, L.; Guo, P.; Cao, H.; Liu, X. Org. Chem. Front. 2023, 10, 2892.
[12]	Li, W.; Zhang, M.; Yan, J.; Ni, L.; Cao, H.; Liu, X. Org. Chem. Front. 2022, 9, 2529.
[13]	Ghosh, K.; Nishii, Y.; Miura, M. ACS Catal. 2019, 9, 11455.
[14]	Mihara, G.; Ghosh, K.; Nishii, Y.; Miura, M. Org. Lett. 2020, 22, 5706. doi: 10.1021/acs.orglett.0c02112 pmid: 32638595
[15]	Ghosh, K.; Nishii, Y.; Miura, M. Org. Lett. 2020, 22, 3547.
[16]	Hu, Y.; Nan, J.; Yin, J.; Huang, G.; Ren, X.; Ma, Y. Org. Lett. 2021, 23, 8527.
[17]	Wang, L.; Jiang, K.; Zhang, N.; Zhang, Z. Asian J. Org. Chem. 2021, 10, 1671.
[18]	Huang, X.; Xu, Y.; Li, J.; Lai, R.; Luo, Y.; Wang, Q.; Yang, Z.; Wu, Y. Chin. Chem. Lett. 2021, 32, 3518.
[19]	Liu, M.; Yan, K.; Wen, J.; Liu, W.; Wang, M.; Wang, L.; Wang, X. Adv. Synth. Catal. 2022, 364, 512.
[20]	Hu, W.; Pi, C.; Hu, D.; Han, X.; Wu, Y.; Cui, X. Org. Lett. 2022, 24, 2613.
[21]	Li, N.; Zhang, X.; Fan, X. Tetrahedron Lett. 2022, 103, 153984.
[22]	Li, X.; Huang, T.; Song, Y.; Qi, Y.; Li, L.; Li, Y.; Xiao, Q.; Zhang, Y. Org. Lett. 2020, 22, 5925.
[23]	Yu, Y.; Wang, Y.; Li, B.; Tan, Y.; Zhao, H.; Li, Z.; Zhang, C.; Ma, W. Adv. Synth. Catal. 2022, 364, 838.
[24]	Li, Y.; Wang, H.; Li, Y.; Li, Y.; Sun, Y.; Xia, C.; Li, Y. J. Org. Chem. 2021, 86, 18204.
[25]	Zhao, L.; Li, W.; Liu, J.; Ni, L.; Liu, Z.; Shen, H.; Cao, H.; Liu, X. Org. Biomol. Chem. 2022, 20, 9604.
[26]	Wang, C.; Fan, X.; Chen, F.; Qian, P.-C.; Cheng, J. Chem. Commun. 2021, 57, 3929.
[27]	Nan, J.; Yin, J.; Gong, X.; Hu, Y.; Ma, Y. Org. Lett. 2021, 23, 8910.
[28]	Zhang, W.; Li, C.; Wang, B.; Gao, H.; Li, H. Chin. J. Org. Chem. 2022, 42, 172. (in Chinese)
	(张文杰, 李超, 王博超, 高慧, 李洪基, 有机化学, 2022, 42, 172.) doi: 10.6023/cjoc202107038
[29]	Nan, J.; Ma, Q.; Yin, J.; Liang, C.; Tian, L.; Ma, Y. Org. Chem. Front. 2021, 8, 1764.
[30]	Kato, M.; Ghosh, K.; Nishii, Y.; Miura, M. Chem. Commun. 2021, 57, 8280.
[31]	Hu, W.; Wang, X.; Yu, X.; Zhu, X.; Hao, X.-Q.; Song, M.-P. Asian J. Org. Chem. 2021, 10, 2557.
[32]	Li, B.-S.; Guo, H.-X.; Sun, W.; Sun, M. Tetrahedron Lett. 2022, 99, 153854.
[33]	Kumara, P.; Kapur, M. Chem. Commun. 2022, 58, 4476.
[34]	Liu, M.; Yan, K.; Wen, Ji.; Shang, W.; Sui, X.; Wang, X. Adv. Synth. Catal. 2022, 364, 1580.
[35]	Wang, Z.; Xue, F.; Hayashi, T. Angew. Chem., Int. Ed. 2019, 58, 11054. doi: 10.1002/anie.201906148 pmid: 31192491
[36]	Hu, F.-P.; Zhang, X.-G.; Wang, M.; Wang, H.-S.; Huang, G.-S. Chem. Commun. 2021, 57, 11980.
[37]	(a) Cai, X.; Song, X.; Yang, X.; Zhang, X.; Fan, X. Org. Chem. Front. 2023, 10, 1015.
	(b) Li, X.; Cheng, H.; Shao, J.; Zhang, G.; Zhang, S. Org. Lett. 2024, 26, 1304.

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