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Synthesis
DOI: 10.1055/s-0043-1774943
DOI: 10.1055/s-0043-1774943
feature
Isocyanoalkene Addition–Cyclization–Decarboxylation Cascades
Financial support from the Division of Chemistry, National Science Foundation (NSF) (#1953128) is gratefully acknowledged.
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Abstract
A rare conjugate addition to isocyanoalkenes with ethyl cyanoacetate triggers an efficient addition–cyclization–decarboxylation cascade. Using finely dispersed NaOH in THF as a base and nucleophile, is critical in facilitating the proton transfers, the ester hydrolysis, and the subsequent decarboxylation. The strategy provides an efficient route to valuable nitrile-substituted 2,3-dihydro-1H-pyrroles while providing fundamental insight into conjugate additions to isocyanoalkenes.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0043-1774943.
- Supporting Information
Publikationsverlauf
Eingereicht: 16. Mai 2024
Angenommen nach Revision: 13. Juni 2024
Artikel online veröffentlicht:
15. Juli 2024
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References
- 1 Giustiniano M, Basso A, Mercalli V, Massarotti A, Novellino E, Tron GC, Zhu J. Chem. Soc. Rev. 2017; 46: 1295
- 2 See the Supporting Information for search details.
- 3a Spallarossa M, Wang Q, Riva R, Zhu J. Org. Lett. 2016; 18: 1622
- 3b van Berkel SS, Boegels BG. M, Wijdeven MA, Westermann B, Rutjes FP. J. T. Eur. J. Org. Chem. 2012; 3543
- 4 Pirrung MC, Ghorai S, Ibarra-Rivera TR. J. Org. Chem. 2009; 74: 4110
- 5 King RB, Efraty A. J. Chem. Soc., Perkin Trans. 1 1974; 1371
- 6 Chepyshev SV, Montelongo JA. L, Chao A, Fleming FF. Angew. Chem. Int. Ed. 2017; 56: 4310 ; and references contained therein
- 7 Marrazzo J.-PR, Chao A, Li Y, Fleming FF. J. Org. Chem. 2022; 87: 488
- 8 Saegusa T, Murase I, Ito Y. J. Org. Chem. 1971; 36: 2876
- 9a Zhang X, Wang X, Gao Y, Xu X. Chem. Commun. 2017; 53: 2427
- 9b Xin X, Liu X, Zhang D, Zhang R, Liang Y, Han F, Dong D. Org. Biomol. Chem. 2014; 12: 5477
- 10 Terkeltaub R, Lee J, Min J, Shin S, Saag KG. Arthritis Rheumatol. 2023; 75: 1275
- 11 https://www.centerwatch.com/clinical-trials/listings/NCT05586958/tigulixostat-phase-3-study-placebo-controlled-in-gout-patients (accessed April 29, 2024)
- 12 Li Y, Fleming FF. Angew. Chem. Int. Ed. 2016; 55: 14770
- 13 Yang X, Fleming FF. Acc. Chem. Res. 2017; 50: 2556
- 14a Hsieh C.-E, Tsao C.-Y, Chuang C.-H, Chen L.-W, Chou C.-M. J. Org. Chem. 2021; 86: 12168
- 14b Brandt K, Haas A, Hardt T, Mayer-Figge H, Merz K, Wallmichrath T. J. Fluorine Chem. 1999; 97: 115
- 15 Lewis acids evaluated to promote cascade on 1a with malononitrile that were not successful include: ZnI2, MgBr2, GaCl3, BF3·OEt2, Yt(OTf)3, AgOTf, and Ag2CO3.
- 16 Neplyuev VM. Zh. Org. Khim. 1981; 17: 2232
- 17 Satoh T. Chem. Soc. Rev. 2007; 36: 1561
- 18 Chao A, Alwedi E, Fleming FF. Synthesis 2019; 51: 2122
- 19 Alwedi E, Lujan-Montelongo JA, Pitta BR, Chao A, Cortés-Mejía R, del Campo JM, Fleming FF. Org. Lett. 2018; 20: 5910