Direct Acetoxylation of Arenes

Abstract

Acetoxylation of arenes is an important reaction and an unmet need in chemistry. We report a metal-free, direct acetoxylation reaction using sodium nitrate under an anhydrous environment of trifluoroacetic acid, acetic acid, and acetic anhydride. Arenes (31 examples), with oxidation potentials (E ox , in V vs SCE) lower than benzene (2.48 V), were acetoxylated with good yields and regioselectivity. A stepwise, single electron-transfer mechanism is proposed.

Antiviral Profiling of C-18- or C-19-Functionalized Semisynthetic Abietane Diterpenoids

“…We attempted the direct acetoxylation of 27 as reported recently for similar aromatic systems, giving nitration products instead. 29 …”

“…Under these new conditions, the reaction was completed in about 3 h, giving 90–93% yield of pure phenol after chromatography with n -hexane–EtOAc (7:3). We attempted the direct acetoxylation of 27 as reported recently for similar aromatic systems, giving nitration products instead …”

“…We attempted the direct acetoxylation of 27 as reported recently for similar aromatic systems, giving nitration products instead. 29 Antiviral Evaluation. The synthesized compounds 5, 6, and 12−26 (Scheme 1) were evaluated for antiviral activity against the viruses HHV-1 (human Alpha herpesvirus type 1), CHIKV (Chikungunya virus), ZIKV (Zika virus), and DENV-2 (Dengue virus type 2) (Table 1).…”

A fruitful century for the scalable synthesis and reactions of biphenyl derivatives: applications and biological aspects

“…Oxygenated arenes, for example aryl acetates, are valuable synthetic precursors for pharmaceuticals, natural products, and functional materials. 146 dimethylphosphonoacetic acid (125) and phosphoric acid (H 3 PO 4 ). Under puried nitrogen condition, a mixture of sodium nitrate (NaNO 3 ) in triuoroacetic acid (TFA), ACOH, and Ac 2 O was mixed with a solution of biphenyl ( 2) afforded [1,1′-biphenyl]acetate (127).…”

C–H Acyloxylation of Polycyclic Aromatic Hydrocarbons

“…After this report, several methods for direct oxygenation of PAHs through an arene radical cation intermediate were reported; however, applicable oxygen nucleophiles were limited to triflate, trifluoroacetate, or other halogenated acetates . The development of a general method for C–H acyloxylation of PAHs, therefore, remains an important task …”