Cyclizing Radical Carboiodination, Carbotelluration, and Carboaminoxylation of Aryl Amines

Abstract

Radical carboiodination of various aryl amines is reported. Aryl diazonium salts, generated in situ from the corresponding aryl amines, are reacted with Bu4NI to provide the corresponding aryl radicals which undergo 5-exo or 6-exo cyclization. Iodine abstraction eventually affords the carboiodinated products in good to excellent yields. If TEMPO is added, the cascade provides the cyclized carboaminoxylation products. Running the reaction in the presence of PhTeTePh affords the phenyltellurated cyclized products.

Boron‐Promoted Ether Interchange Reaction: Synthesis of Alkyl Nitroaromatic Ethers from Methoxynitroarenes

“…1‐(Allyloxy)‐2‐nitrobenzene (3i) Light yellow oil (conditions A: 46 mg, yield 51 % ) or (conditions B: 47 mg, yield 52 % ), (46 mg, yield 51 %), flash chromatography eluting with petroleum ether/ethyl acetate (30:1). 1 H NMR (CDC1 3 , 400 MHz) 7.84 (dd, J = 8.1 Hz, 1.6 Hz, 1H), 7.53–749 (m, 1H), 7.08 (d, J = 8.4 Hz, 1H), 7.05–7.01 (m, 1H), 6.09–5.99 (m, 1H), 5.51–5.47 (m, 1H), 5.35–5.32 (m, 1H), 4.70–4.68 (m, 2H).…”

“…The products were characterized by 1 H NMR, 13 C NMR, MS or HRMS. [15] [16] [16] [17] [18] [18] Light green oil (con-…”

Metal‐Free C(sp3)‐O Bond Formation through Radical Translocation: A Mild, Efficient, and Practical Approach to α‐Alkoxybenzamides

“…For example, Carrillo and co‐workers reported that ascorbic acid can act as an appropriate initiator in intermolecular C−H arylation of arenes with anilines . In addition, iodide, benzoyl peroxide (BPO), and porphyrin have been identified as efficient initiators to generate aryl radicals from aryl diazonium salts. Inspired by these precedents, we initially studied the radical translocation of readily prepared o ‐aminobenzamide 1 a with methanol ( 2 a ) in the presence of n Bu 4 NI as an initiator and t BuONO as a nitrosating agent at room temperature under N 2 for 3 h. Interestingly, the desired product 3 aa was isolated in 6 % yield (Table , entry 1).…”

Photo‐induced Carboiodination: A Simple Way to Synthesize Functionalized Dihydrobenzofurans and Indolines

“…Nonetheless, there are still some restrictions including 1) relatively high reaction temperatures, 2) special and expensive ligands, and 3) the required absence of a β‐H next to the iodine. In 2014, Studer and coworkers reported another elegant Sandmeyer‐type protocol to synthesize intermediate IV . In their report, they employed an in situ generated diazonium salt as the key reactant species, which could be reduced by the iodide to form the phenyl radical.…”

“…In 2014, Studer andc oworkers reported another elegantS andmeyer-type protocol to synthesize intermediate IV. [9] In their report, they employed an in situ generated diazonium salt as the key reactants pecies, which could be reduced by the iodide to form the phenyl radical. Due to the favorable intramolecular ring closure, the phenyl radical can be trapped by the double bonds to form the desired rings.…”