The Electrochemical trans-Chloroformyloxylation of Unactivated Alkenes

Abstract

An attempted aryl selenium-catalyzed formation of cis-chlorohydrins from alkenes was unsuccessful but led to an electrochemical investigation for the trans-selective chloroformyloxylation of cyclic and acyclic alkenes in moderate to good yields. Interestingly, when 1,1-disubstituted alkenes were used, the corresponding vinyl chloride derivatives were obtained, and the application of 1-phenylcyclohex-1-ene led to the formation of an allyl chloride derivative.

Key words

addition reaction - alkenes - chloroformyloxylation - electrochemistry - trans-selectivity - vinyl chlorides

Publication History

Received: 08 February 2024

Accepted after revision: 10 March 2024

Article published online:
20 March 2024

• References and Notes

• 1a Bellucci G, Bianchini R, Ambrosetti R. J. Am. Chem. Soc. 1985; 107: 2464
• 1b Bellucci G, Chiappe C, Bianchini R, Lenoir D, Herges R. J. Am. Chem. Soc. 1995; 117: 12001
• 1c Bianchini R, Lenoir D, Herges R, Grunenberg J, Chiappe C, Lemmen P. Angew. Chem. Int. Ed. 1997; 36: 1284
• 1d Bock J, Guria S, Wedek V, Hennecke U. Chem. Eur. J. 2021; 27: 4517
• 1e Landry ML, Burns NZ. Acc. Chem. Res. 2018; 51: 1260
• 1f Ortgies S, Breder A. ACS Catal. 2017; 7: 5828
• 2a Cresswell AJ, Eey ST.-C, Denmark SE. Angew. Chem. Int. Ed. 2015; 54: 15642
• 2b Cresswell AJ, Eey ST.-C, Denmark SE. Nat. Chem. 2015; 7: 146
• 2c Fu L, Mu X, Li B. J. Mol. Model. 2018; 24: 91
• 3 Strehl J, Fastie C, Hilt G. Chem. Eur. J. 2021; 27: 17341
• 4a Hilt G. Synthesis 2023; 55: 565
• 4b Göttlich R. In Science of Synthesis, Vol. 35, Chap. 35.1.5.1. Wirth T. Thieme; Stuttgart: 2007: 189
• 5a Cornforth JW, Green DT. J. Chem. Soc. C 1970; 846
• 5b Dowle MD, Davies DI. Chem. Soc. Rev. 1979; 8: 171
• 6a Santi C, Santoro S. Organoselenium Chemistry: Synthesis and Reactions, Chap. 1. Wirth T. Wiley-VCH; Weinheim: 2011. 1
• 6b Lin HM, Tang Y, Li ZH, Liu KD, Yang J, Zhang YM. ARKIVOC 2012; (viii): 146
• 7 Ruiz J, Araúz R, Ceroni M, Vivanco M, Van der Maelen JF, García-Granda S. Organometallics 2010; 29: 3058
• 8a Liu L, Zhang-Negrerie D, Du Y, Zhao K. Org. Lett. 2014; 16: 436
• 8b de Souza AV. A, Mendonça GF, Bernini RB, de Mattos MC. S. J. Braz. Chem. Soc. 2007; 18: 1575
• 8c Kim RH, Kim JN, Park HJ, Ryu EK. Bull. Korean Chem. Soc. 1997; 18: 110
• 8d Kim RH, Kim JN, Ryu EK. Synth. Commun. 1992; 22: 2521

The formation of a cis- chloroformyloxylation product was not observed. For an electrochemical chlorohydrin synthesis, see:
• 9a Ashurova ND, Agaev AA, Muradov MM. Russ. J. Appl. Chem. 2012; 85: 839

For an electrochemical iodohydrin synthesis, see:
• 9b Luan S, Castanheiro T, Poisson T. Adv. Synth. Catal. 2022; 364: 2741

For other selected electrochemical alkene functionalization reactions, see:
• 9c Thadathil DA, Varghese A, Radhakrishnan KV. Asian J. Org. Chem. 2021; 10: 2820
• 9d Siu JC, Fu N, Lin S. Acc. Chem. Res. 2020; 53: 547
• 9e Mei H, Yin Z, Liu J, Sun H, Han J. Chin. J. Chem. 2019; 37: 292
• 9f Martins GM, Shirinfar B, Hardwick T, Ahmed N. ChemElectroChem 2019; 6: 1300
• 9g Sun X, Ma H.-X, Mei T.-S, Fang P, Hu Y. Org. Lett. 2019; 21: 3167
• 9h Kundu G, Lambert TH. J. Am. Chem. Soc. 2024; 146: 1794
• 10 A similar significant change in reactivity was also observed for the electrochemical bromination of alkenes, see: Strehl J, Abraham ML, Hilt G. Angew. Chem. Int. Ed. 2021; 60: 9996
• 11 Zhang G, Bai R.-X, Li C.-H, Feng C.-G, Lin G.-Q. Tetrahedron 2019; 75: 1658