Subscribe to RSS
DOI: 10.1055/a-2288-6944
A Photochemical Strategy for the Synthesis of Caprolactams via Dearomative Ring Expansion of Nitroarenes
R.S.-B. thanks the European Union Horizon 2020 innovation programme for a Marie Skłodowska-Curie grant, agreement no. 956324 (PhotoReAct).
![](https://www.thieme-connect.de/media/synthesis/202415/lookinside/thumbnails/ss-2024-f0054-op_10-1055_a-2288-6944-1.jpg)
Abstract
This paper outlines a novel strategy for the preparation of seven-membered-ring lactams from simple nitroarenes. The approach is based on a photochemical dearomative ring expansion starting with the conversion of the nitro group into a singlet nitrene. This process is mediated by blue light, occurs at room temperature and overall enables the insertion of the nitro N-atom into the benzenoid framework. This step transforms the aromatic starting material into a seven-membered ring azepine that, following hydrogenation and hydrolysis, is converted into the desired caprolactams in just three steps.
Key words
singlet nitrene - photoexcited nitroarenes - ring expansion - azepines - hydrogenation - caprolactams - N-insertionSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2288-6944.
- Supporting Information
Publication History
Received: 15 February 2024
Accepted after revision: 15 March 2024
Accepted Manuscript online:
15 March 2024
Article published online:
02 April 2024
© 2024. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References
- 1 Llarrull LI, Testero SA, Fisher JF, Mobashery S. Curr. Opin. Microbiol. 2010; 13: 551
- 2 Caruano J, Muccioli GG, Robiette R. Org. Biomol. Chem. 2016; 14: 10134
- 3 Saldívar-González FI, Lenci E, Trabocchi A, Medina-Franco JL. RSC Adv. 2019; 9: 27105
- 4 Perry CM. Am. J. Cardiovasc. Drugs 2012; 12: 415
- 5 Kumar R, Shah S, Paramita Das P, Bhagavanbhai GG. K, Al Fatesh A, Chowdhury B. Catal. Rev.: Sci. Eng. 2019; 61: 516
- 6 Chandrasekhar S. Compr. Org. Synth. 2014; 7: 770
- 7 Chenault HK. Synthesis of Pyrrolidones and Caprolactams by Ring Modification or Multi-component Ring-Forming Reaction. In Handbook of Pyrrolidone and Caprolactam Based Materials, Vol. 1, Chap. 3. Musa OM. John Wiley & Sons Ltd; Weinheim: 2021
- 8 Komatsu N, Simizu S, Sugita T. Synth. Commun. 1992; 22: 277
- 9 Rasouli MA, Mahdavi M, Rashidi Ranjbar P, Saeedi M, Shafiee A, Foroumadi A. Tetrahedron Lett. 2012; 53: 7088
- 10 Alonso DA, Falvello LR, Mancheño B, Nájera C, Tomás M. J. Org. Chem. 1996; 61: 5004
- 11 Chen Y, Du J, Zuo Z. Chem 2020; 6: 266
- 12 Peixoto D, Malta G, Cruz H, Barroso S, Carvalho AL, Ferreira LM, Branco PS. J. Org. Chem. 2019; 84: 3793
- 13 Babu GV. S, Bhaskaran A, Sridhar B, Rao TV, Parvathaneni SP. ChemistrySelect 2021; 6: 5
- 14 Mykura R, Sánchez-Bento R, Matador E, Duong VK, Varela A, Angelini L, Carbajo RJ, Llaveria J, Ruffoni A, Leonori D. Nat. Chem. 2024; in press DOI: 10.1038/s41557-023-01429-1.
- 15 Testa AC. J. Phys. Chem. 1975; 79: 644
- 16 Gritsan NP, Platz MS. Chem. Rev. 2006; 106: 3844
- 17a DeGraff BA, Gillespie DW, Sundberg RJ. J. Am. Chem. Soc. 1974; 96: 7491
- 17b Huisgen R, Vossius D, Appl M. Chem. Ber. 1958; 91: 1
- 18 Chapman O, Roux J.-P. J. Am. Chem. Soc. 1978; 100: 282
- 19 Satake K, Okuda R, Hashimoto M, Fujiwara Y, Watadani I, Okamoto H, Kimura M, Morosawa S. J. Chem. Soc., Chem. Commun. 1991; 1154
- 20 Negele S, Wieser K, Severin T. J. Org. Chem. 1998; 63: 1138
- 21 Lavinda O, Witt CH. Angew. Chem. Int. Ed. 2022; 61: e202114183
- 22 Overberger CG, Kozlowski JH, Radlmann E. J. Polym. Sci., Part A-1: Polym. Chem. 1972; 10: 2265
- 23 Chen M, Dong G. J. Am. Chem. Soc. 2017; 139: 7757
- 24 Reimschuessel HK, Sibilia JP. J. Org. Chem. 1969; 34: 959
- 25 Denmark SE, Xie M. J. Org. Chem. 2007; 72: 7050
- 26 Kitagawa O, Velde DV, Dutta D, Morton M, Takusagawa F, Aubé J. J. Am. Chem. Soc. 1995; 117: 5169