Subscribe to RSS
DOI: 10.1055/s-0043-1775450
Nucleophilic Addition to N-Vinylpyridiniums by Using Ion-Pair Extraction with Tetracyanocyclopentadienides
This research was partially supported by Grant-in-Aids for Scientific Research (C) (22K06539) from the Japan Society for the Promotion of Science (JSPS), research fund from the Research Institute of Meijo University, and the Meijo University Research Promotion Organization for Carbon Neutrality.
Abstract
N-Vinylpyridinium is a useful electrophilic species in synthetic organic chemistry. In this study, we reinvestigated the addition reaction of N-vinylpyridinium, which has received limited attention in the past several decades. The reaction conditions were screened in detail with the aid of tetracyanocyclopentadienide (TCCP) ion-pair extraction and its extraction prediction equation, and the optimal reaction conditions were identified to entail the use of 2,2,2-trifluoroethanol (TFE) as an additive and dichloromethane as solvent. We successfully obtained 14 addition products with various substitution patterns, among which 3,5-dimethyl-N-vinylpyridinium provided the addition product in up to 85% yield. The reduction of the pyridinium core advanced smoothly, indicating that the TCCP anions did not significantly influence the reactivity of the platinum-catalyzed hydrogenation.
Key words
ion-pair extraction - addition - pyridinium - tetracyanocyclopentadienide - nitrogen heterocycleSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0043-1775450.
- Supporting Information
Publication History
Received: 14 December 2024
Accepted after revision: 27 January 2025
Article published online:
04 March 2025
© 2025. Thieme. All rights reserved
Georg Thieme Verlag KG
Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
-
References
- 1a Six-Membered Rings with One Heteroatom and Their Fused Carbocyclic Derivatives. In Comprehensive Heterocyclic Chemistry IV, Vol. 7. Maulide N. Elsevier; Amsterdam: 2022
- 1b For a recent review article, see: Sowmiah S, Esperança JM. S. S, Rebelo LP. N, Afonso CA. M. Org. Chem. Front. 2018; 5: 453
- 2a Raucher S, Bray BL, Lawrence RF. J. Am. Chem. Soc. 1987; 109: 442
- 2b O’Neill BT, Yohannes D, Bundesmann MW, Arnold EP. Org. Lett. 2000; 2: 4201
- 2c Carbonnel E, Alix F, Gembus V. Synthesis 2017; 49: 2057
-
3
Park T,
Torres E,
Fuchs PL.
Synthesis 2004; 1895
- 4a Buszek KR, Brown N. Org. Lett. 2007; 9: 707
- 4b Basch CH, Liao J, Xu J, Piane JJ. Watson M. P. J. Am. Chem. Soc. 2017; 139: 5313
- 5a He F.-S, Ye S, Wu J. ACS Catal. 2019; 9: 8943
- 5b Rössler SL, Jelier BJ, Magnier E, Dagousset G, Carreira EM, Togni A. Angew. Chem. Int. Ed. 2020; 59: 9254
- 5c Correa JT. M, Fernandes VA, Matsuo BT, Delgado JA, de Souza WC, Paixão MW. Chem. Commun. 2020; 56: 503
- 5d Kim M, Koo Y, Hong S. Acc. Chem. Res. 2022; 55: 3043
- 5e Wang Y, Bao Y, Tang M, Ye Z, Yuan Z, Zhu G. Chem. Commun. 2022; 58: 3847
- 5f Motsch BJ, Wengryniuk SE. Tetrahedron 2024; 162: 134119
- 6a Zhang Z, Han H, Wang L, Bu Z, Xie Y, Wang Q. Org. Biomol. Chem. 2021; 19: 3960
- 6b Rajman A, Kumbhar A. Chem. Pap. 2024; 78: 35
- 6c Zhang P, Hua L, Takahashi T, Jin S, Wang Q. Synthesis 2024; 56: 55
- 7 Egorova K, Gordeev EG, Ananikov VP. Chem. Rev. 2017; 117: 7132
- 8 Jennings MC, Minbiole KP. C, Wuest WM. ACS Infect. Dis. 2015; 1: 288
- 9 Sakai T, Noda N, Fujimoto C, Ito M, Takeuchi H, Nishiwaki M, Mori Y. Org. Lett. 2019; 21: 3081
- 10 Webster OW. J. Am. Chem. Soc. 1966; 88: 3046
- 11 Wang Z, Buser AM, Cousins IT, Demattio S, Drost W, Johansson O, Ohno K, Patlewicz G, Richard AM, Walker GW, White GS, Leinala E. Environ. Sci. Technol. 2021; 55: 15575
- 12 Sakai T, Seo S, Matsuoka J, Mori Y. J. Org. Chem. 2013; 78: 10978
- 13 Sakai T, Ota M, Ito M, Miura R, Fumimoto Y, Mori Y. Chem. Pharm. Bull. 2025; 73: 121
- 14 In the original paper by Motomizu, the term ‘A value’ was used to represent the magnitude of the lipophilicity of anions. However the term ‘A value’ is generally used for the magnitude of the steric bulk of substituents. In this paper, we will use ‘value of A’ instead of ‘A value’ to prevent confusion. See: Muller P. Pure Appl. Chem. 1994; 66: 1077
- 15a Motomizu S. Bunseki Kagaku 1984; 33: 31
- 15b Motomizu S. Bunseki Kagaku 1989; 38: 147
- 15c Yamamoto K, Motomizu S. Talanta 1991; 38: 477
- 16a Leo AJ. Chem. Rev. 1993; 93: 1281
-
16b The values for CLOGP were calculated using ChemBioDraw Professional 22.2
- 17 Kröhnke F. Angew. Chem. Int. Ed. 1963; 2: 225
- 18a Jung ME, Buszek KR. J. Am. Chem. Soc. 1988; 110: 3965
- 18b Lee S.-J, Tzeng C.-B, Lin S.-C, Chao I, Lu H.-F, Chou TS. J. Org. Chem. 1996; 61: 9293
- 19 Katritzky AR, Rubio O. J. Org. Chem. 1983; 48: 4017
- 20 Zhao reported the synthesis of a variety of vinylpyridiniums and demonstrated a nucleophilic addition reaction with piperidine; see: Liao L, Guo R, Zhao X. Angew. Chem. Int. Ed. 2017; 56: 3201
- 21 Katritzky AR, Mokrosz MJ. Heterocycles 1984; 22: 505
- 22 Hayes FN, Suzuki HK, Peterson DE. J. Am. Chem. Soc. 1950; 72: 4524
- 23 For further details, refer to Figure S2 in the Supporting Information. For 2,4-DM-BENAC-K, see: Sakai T, Takenaka R, Koike Y, Hira A, Mori Y. Chem. Pharm. Bull. 2022; 70: 650
For examples used in industry and natural product total synthesis, see:
For recent reviews, see: