Sustainable Methods in Hypervalent Iodine Chemistry

Structure–Activity Relationships for Hypervalent Iodine Electrocatalysis

“…TBAPF6 was recrystallized from minimum boiling ethanol and dried thoroughly before use. 1 4-Iodo-N,N-dimethylaniline (1), 2 4-iodo-4-phenoxybenzene (5), 3 4tert-butyliodobenzene (6), 4 tetrabutylammonium 4-iodobenzoate (13), 5 2-iodo-N,Ndimethylaniline (19), 6 tetrabutylammonium 2-iodobenzoate (28), 7 ethyl 2-iodobenzoate (29), 8 1-(tert-butylsulfonyl)-2-iodobenzene (31), 9 2-iodobenzenesulfonic acid (32), 10 1,1,1,3,3,3-hexafluoro-2-(2-iodophenyl)propan-2-ol (33), 11 2-iodo-5-methoxy-N,Ndimethylaniline (36), 12 3,4-diiodoanisole (39), 13 2-fluoro-1-iodo-4-methoxybenzene (40), 14 2-chloro-1-iodo-4-methoxybenzene (42), 15 ethyl-2-iodo-5-methoxybenzoate (44), 16 1-iodo-4-methoxy-2-(trifluoromethyl)benzene (46), 17 2,4,5-trimethoxyiodobenzene (49), 18 1,2diiodo-4,5-dimethoxybenzene (51), 13 1-bromo-2-iodo-4,5-dimethoxybenzene (53), 13 1iodo-4,5-dimethoxy-2-nitrobenzene (54), 19 ethyl 2-iodo-4,5-dimethoxybenzoate (56), 16 2iodo-4,5-dimethoxybenzoic acid (57), 13 1,4-diiodo-2,5-dimethoxybenzene (60), 13 5,6diiodobenzo[d] [1,3]dioxole (61), 20 5-iodo-2-methoxy-1,3-dimethylbenzene (62), 21 2,2'diiodo-4,4',6,6'-tetramethyl-1,1'-biphenyl (65) 22 , 1,5-diiodo-2,3,4-trimethoxybenzene (67), 23 and 1,2-diiodo-4,5-dimethylbenzene (68) 24 were synthesized according to literature methods.…”

“…Prepared from 2bromo-5-methoxybenzenethiol, S47 was obtained as a white solid (1.71 g, 43% yield). 1…”

“…1 H NMR (", 23 °C, 400 MHz, CDCl3): 8.00 (d, J = 8.7 Hz, 1H), 7.62 (d, J = 3.0 Hz, 1H), 6.81 (dd, J = 8.7, 3.0 Hz, 1H), 3.84, (s, 3H), 1.43 (s, 9H).13 C NMR (d, 23 ℃, 100 MHz, CDCl3): 159.8, 144.5, 138.5, 120.9, 120.0, 82.7, 62.8, 55.9, 24.4. Mp 159-161 °C.…”

“…1 H NMR (d, 23 ℃, 400 MHz, CDCl3): 7.33 (s, 2H), 6.75 (s, 2H), 3.94 (s, 6H), 3.89 (s, 6H).13 C NMR (d 23 ℃, 100 MHz, CDCl3): 14.97, 148.96, 141.4, 120.8, 113.1, 88.2, 56.18, 56.05. Mp 176-179 °C.…”

Recent Updates on Electrogenerated Hypervalent Iodine Derivatives and Their Applications as Mediators in Organic Electrosynthesis

“…HIRs are often considered as environmentally benign alternatives to various chemical oxidants, especially the highly toxic heavy-metal oxidizers, i.e., Pb(IV), Hg(II), and Tl(III) reagents ( Yoshimura and Zhdankin, 2016 ; Takenaga et al, 2020 ). Nevertheless, the current common preparation methods of HIRs pose environmental concerns to their widespread application and upscaling ( Liu et al, 2018 ; Elsherbini and Wirth, 2018 ; Frey et al, 2022 ). Typically, these preparation methods often require (over)stoichiometric amounts of hazardous or costly oxidants, such as m -chloroperbenzoic acid ( m -CPBA), CH 3 CO 3 H, NaBO 3 , NaIO 4 , oxone (2KHSO 5 ·KHSO 4 ·K 2 SO 4 ), H 2 O 2 , and Selectfluor, thus inevitably leading to an excess of waste products ( Francke et al, 2018 ; Francke, 2019 ; Elsherbini and Wirth, 2018 ).…”