Visible-Light-Driven Oxidative Chlorination of Alkyl sp³ C–H Bonds with HCl/Air at Room Temperature

Abstract

An aerobic chlorination of alkyl sp³ C–H bonds of functionalized alkanes and simple alkanes has been established successfully under visible light at room temperature. The reaction is performed in the presence of catalytic NaNO₂ using HCl or NaCl/acid as a chlorine source and air as a terminal oxidant under atmospheric pressure. It is suggested that NOCl from NaNO₂/HCl is a crucial species in the catalytic cycle involving an aerobic oxidation and a photochemical radical chlorination.

Key words

alkane - chlorination - air - oxidation - sodium nitrite

Publication History

Received: 16 December 2023

Accepted after revision: 05 February 2024

Accepted Manuscript online:
05 February 2024

Article published online:
26 February 2024

• References

• 1a Lin R, Amrute AP, Perezramirez J. Chem. Rev. 2017; 117: 4182
• 1b Kozlowski MC. Acc. Chem. Res. 2017; 50: 638
• 1c Oxidation of C‒H Bonds . Lu W, Zhou L. John Wiley & Sons; Hoboken: 2017
• 2 Manabe Y, Kitawaki Y, Nagasaki M, Fukase K, Matsubara H, Hino Y, Fukuyama T, Ryu I. Chem. Eur. J. 2014; 20: 12750
• 3 Zhao M, Lu W. Org. Lett. 2017; 19: 4560
• 4a Egloff G, Schaad RE, Lowry CD. Chem. Rev. 1931; 8: 1
• 4b Schmidt VA, Quinn RK, Brusoe AT, Alexanian EJ. J. Am. Chem. Soc. 2014; 136: 14389
• 5a Kennedy RJ, Stock AM. J. Org. Chem. 1960; 25: 1901
• 5b Hill CL, Smegal JA, Henly TJ. J. Org. Chem. 1983; 48: 3277
• 5c Takahiko K, Hidenobu M, Yoshihisa M. Chem. Lett. 1998; 27: 1085
• 5d Reis PM, Armando J, Silva L, da Silva JJ. R. F, Pombeiro AJ. L. Chem. Commun. 2000; 1845
• 5e Li Y, Ju J, Jia J, Sheng W, Han L, Gao J. Chin. J. Chem. 2010; 28: 2428
• 5f He Y, Goldsmith CR. Synlett 2010; 1377
• 6 Zhao M, Lu W. Org. Lett. 2018; 20: 5264
• 7 Dean JA. Lange’s Handbook of Chemistry, 15th ed. McGraw-Hill; New York: 1999
• 8a Mei C, Hu Y, Lu W. Synthesis 2018; 50: 2999
• 8b Xu L, Mei C, Zhao M, Lu W. ChemRxiv 2023; preprint DOI: 10.26434/chemrxiv-2023-hhfx1-v3.
• 9a Lynn EV. J. Am. Chem. Soc. 1919; 41: 368
• 9b Lynn EV, Hilton O. J. Am. Chem. Soc. 1922; 44: 645
• 9c Busch GE, Wilson KR. J. Chem. Phys. 1972; 56: 3655
• 9d Lebl R, Cantillo D, Kappe CO. React. Chem. Eng. 2019; 4: 738
• 9e Leifert D, Studer A. Angew. Chem. Int. Ed. 2020; 59: 74
• 10a Pass G, Sutcliffe H. Practical Inorganic Chemistry: Preparation, Reactions and Instrumental Methods. Chapman Hall; London: 1968
• 10b Williams DL. H. In Nitrosation Reactions and the Chemistry of Nitric Oxide . Elsevier Science; Amsterdam: 2004
• 11 Barham BP, Reid PJ. Chem. Phys. Lett. 2002; 361: 49
• 12a Radner F. J. Org. Chem. 1988; 53: 3548
• 12b Iskra J, Stavber S, Zupan M. Tetrahedron Lett. 2008; 49: 893
• 12c Ren Y.-L, Shang H, Wang J, Tian X, Zhao S, Wang Q, Li F. Adv. Synth. Catal. 2013; 355: 3437
• 13 Schrader AM, Schroll AL, Barany G. J. Org. Chem. 2011; 76: 7882
• 14 Sopeña S, Cozzolino M, Maquilón C, Escudero-Adán EC, Martínez Belmonte M, Kleij AW. Angew. Chem. Int. Ed. 2018; 57: 11203