Subscribe to RSS
DOI: 10.1055/a-1484-1028
Radical Carbosulfonylation of Propellane: Synthesis of Sulfonyl β-Keto-bicyclo[1,1,1]pentanes
C.Z. is grateful for the financial support from the National Natural Science Foundation of China (21971173), the Project of Scientific and Technologic Infrastructure of Suzhou (SZS201905), the Undergraduate Training Program for Innovation and Entrepreneurship, Soochow University (202010285003), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).
![](https://www.thieme-connect.de/media/synthesis/202118/lookinside/thumbnails/ss-2021-f0143-st_10-1055_a-1484-1028-1.jpg)
Abstract
The construction of multiply functionalized bicyclo[1.1.1]pentanes (BCPs) is of high synthetic value, as they are frequently harnessed as bioisosteres of 1,3-disubstituted benzene rings, alkynes, and tert-butyl groups in medicinal chemistry. Herein, we disclose a practical radical-mediated carbosulfonylation of propellane for the synthesis of sulfonyl β-keto-substituted BCPs by using vinyl sulfonates as dual-function reagent. This protocol features broad functional group tolerance and excellent atom-economy, leading to a variety of valuable difunctionalized BCP derivatives under mild photochemical conditions.
Key words
bicyclo[1.1.1]pentanes - propellane - sulfonylation - photochemical - C–C cleavage - radical reactionsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1484-1028.
- Supporting Information
Publication History
Received: 15 March 2021
Accepted after revision: 16 April 2021
Accepted Manuscript online:
16 April 2021
Article published online:
19 May 2021
© 2021. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References
- 1a Burkhard JA, Guérot C, Knust H, Carreira EM. Org. Lett. 2012; 14: 66
- 1b Carreira EM, Fessard TC. Chem. Rev. 2014; 114: 8257
- 1c Gianatassio R, Lopchuk JM, Wang J, Pan C.-M, Malins LR, Prieto L, Brandt TA, Collins MR, Gallego GM, Sach NW, Spangler JE, Zhu H, Zhu J, Baran PS. Science 2016; 351: 241
- 2a Stepan AF, Subramanyam C, Efremov IV, Dutra JK, O’Sullivan TJ, DiRico KJ, McDonald WS, Won A, Dorff PH, Nolan CE, Becker SL, Pustilnik LR, Riddell DR, Kauffman GW, Kormos BL, Zhang L, Lu Y, Capetta SH, Green ME, Karki K, Sibley E, Atchison KP, Hallgren AJ, Oborski CE, Robshaw AE, Sneed B, O’Donnell CJ. J. Med. Chem. 2012; 55: 3414
- 2b Measom ND, Down KD, Hirst DJ, Jamieson C, Manas ES, Patel VK, Somers DO. ACS Med. Chem. Lett. 2017; 8: 43
- 2c Goh YL, Cui YT, Pendharkar V, Adsool VA. ACS Med. Chem. Lett. 2017; 8: 516
- 2d Nicolaou KC, Vourloumis D, Totokotsopoulos S, Papakyriakou A, Karsunky H, Fernando H, Gavrilyuk J, Webb D, Stepan AF. ChemMedChem 2016; 11: 31
- 3 Pellicciari R, Raimondo M, Marinozzi M, Natalini B, Costantino G, Thomsen C. J. Med. Chem. 1996; 39: 2874
- 4 Filosa R, Marinozzi M, Costantino G, Hermit MB, Thomsen C, Pellicciari R. Bioorg. Med. Chem. Lett. 2006; 14: 3811
- 5 Goh YL, Cui YT, Pendharkar V, Adsool VA. ACS Med. Chem. Lett. 2017; 8: 516
- 6 Pu Q, Zhang H, Guo L, Cheng M, Doty AC, Ferguson H, Fradera X, Lesburg CA, McGowan MA, Miller JR, Geda P, Song X, Otte K, Sciammetta N, Solban N, Yu W, Sloman DL, Zhou H, Lammens A, Neumann L, Bennett DJ, Pasternak A, Han Y. ACS Med. Chem. Lett. 2020; 11: 1548
- 7 Barbachyn MR, Hutchinson DK, Toops DS, Reid RJ, Zurenko GE, Yagi BH, Schaadt RD, Allison JW. Bioorg. Med. Chem. Lett. 1993; 3: 671
- 8a Dilmaç AM, Spuling E, de Meijere A, Bräse S. Angew. Chem. Int. Ed. 2017; 56: 5684
- 8b Kanazawa J, Uchiyama M. Synlett 2019; 30: 1
- 8c Makarov IS, Brocklehurst CE, Karaghiosoff K, Koch G, Knochel P. Angew. Chem. Int. Ed. 2017; 56: 12774
- 8d Yu S, Jing C, Noble A, Aggarwal VK. Angew. Chem. Int. Ed. 2020; 59: 3917
- 8e Bär RM, Kirschner S, Nieger M, Bräse S. Chem. Eur. J. 2018; 24: 1373
- 8f Bär RM, Heinrich G, Nieger M, Fuhr O, Bräse S. Beilstein J. Org. Chem. 2019; 15: 1172
- 8g Schwärzer K, Zipse H, Karaghiosoff K, Knochel P. Angew. Chem. Int. Ed. 2020; 59: 20235
- 8h Makarov IS, Brocklehurst CE, Karaghiosoff K, Koch G, Knochel P. Angew. Chem. Int. Ed. 2017; 56: 12774
- 8i Trongsiriwat N, Pu Y, Nieves-Quinones Y, Shelp RA, Kozlowski MC, Walsh PJ. Angew. Chem. Int. Ed. 2019; 58: 13416
- 8j Caputo DF. J, Arroniz C, Dürr AB, Mousseau JJ, Stepan AF, Mansfield SJ, Anderson EA. Chem. Sci. 2018; 9: 5295
- 8k Gianatassio R, Lopchuk JM, Wang J, Pan C.-M, Malins LR, Prieto L, Brandt TA, Collins MR, Gallego GM, Sach NW, Spangler JE, Zhu H, Zhu J, Baran PS. Science 2016; 351: 241
- 8l Kanazawa J, Maeda K, Uchiyama M. J. Am. Chem. Soc. 2017; 139: 17791
- 8m Shin S, Lee S, Choi W, Kim N, Hong S. Angew. Chem. Int. Ed. 2021; 60: 7873
- 8n Kondo M, Kanazawa J, Ichikawa T, Shimokawa T, Nagashima Y, Miyamoto K, Uchiyama M. Angew. Chem. Int. Ed. 2020; 59: 1970
- 8o Dockery KP, Bentrude WG. J. Am. Chem. Soc. 1994; 116: 10332
- 8p Dockery KP, Bentrude WG. J. Am. Chem. Soc. 1997; 119: 1388
- 8q Marinozzi M, Fulco MC, Rizzo R, Pellicciari R. Synlett 2004; 1027
- 8r Nugent J, Arroniz C, Shire BR, Sterling AJ, Pickford HD, Wong ML. J, Mansfield SJ, Caputo DF. J, Owen B, Mousseau JJ, Duarte F, Anderson EA. ACS Catal. 2019; 9: 9568
- 9a Whitham GH. Organosulfur Chemistry . Oxford University Press; Oxford/New York: 1995
- 9b Alba A.-NR, Companyó X, Rios R. Chem. Soc. Rev. 2010; 39: 2018
-
9c
Ahmad I.
Shagufta,
Int. J. Pharm. Pharm. Sci. 2015; 7: 19
- 9d Trost BM, Kalnmals CA. Chem. Eur. J. 2019; 25: 11193
- 9e Patai S, Rappoport Z, Stirling CJ. M. The Chemistry of Sulphones and Sulphoxides . Wiley; New York: 1988
- 10a Wu Z, Xu Y, Wu X, Zhu C. Tetrahedron 2020; 76: 131692
- 10b Wu Z, Xu Y, Liu J, Wu X, Zhu C. Sci. China Chem. 2020; 63: 1025
- 11 Xie L, Zhen X, Huang S, Su X, Lin M, Li Y. Green Chem. 2017; 19: 3530
For selected reviews:
For selected examples: