Synlett, Table of Contents Synlett 2024; 35(16): 1906-1908DOI: 10.1055/s-0043-1763695 letter The Electrochemical trans-Chloroformyloxylation of Unactivated Alkenes Jona Queder , Gerhard Hilt Recommend Article Abstract Buy Article All articles of this category 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 Key wordsaddition reaction - alkenes - chloroformyloxylation - electrochemistry - trans-selectivity - vinyl chlorides Full Text References 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 Supplementary Material Supplementary Material Supporting Information
