Metal-Free C-Arylation of Nitro Compounds with Diaryliodonium Salts

Abstract

An efficient, mild, and metal-free arylation of nitroalkanes with diaryliodonium salts has been developed, giving easy access to tertiary nitro compounds. The reaction proceeds in high yields without the need for excess reagents and can be extended to αarylation of nitroesters. Nitroalkanes were selectively C-arylated in the presence of other easily arylated functional groups, such as phenols and aliphatic alcohols.

Synthesis, Characterization and Unusual Reactivity of Vinylbenziodoxolones—Novel Hypervalent Iodine Reagents

“…The reaction conditions were briefly screened, to conclude that increased amount of VBX 6 a (entry 3) or prolonged reaction time (entry 4) did not improve the conversion to 9 . On the other hand, conditions similar to those used in our previously reported arylation of nitrocyclohexane further increased the product ratio 9 : 8 and delivered 9 in a satisfactory yield of 57 % (entry 5). The addition of two equivalents of the radical scavenger 1,1‐diphenylethylene (DPE) did not affect the yield, indicating that radicals are not involved in product or by‐product formation…”

Diaryliodonium Salts in Organic Syntheses: A Useful Compound Class for Novel Arylation Strategies

“…A few months ago, the metal-free C-arylation of nitro compounds 54 was published by Olofsson's group using diaryliodonium salts. The reaction proceeds in high yields without the need for excess reagents and can be extended to α-arylation of Template for SYNLETT © Thieme Stuttgart · New YorkSynlett Letter / Cluster / New Tools nitrocycloalkanes (66) and nitroesters (67) (Scheme 27).…”

“…[54][55][56][57][58][59][60][61][62][63][64][65][66][67] Utilizing this concept, several syntheses of diverse heterocyclic skeletons were developed in the last few years in our and other laboratories. The copper catalyzed synthesis of new oxazoline derivatives (89) from propargyl amides (88) and diaryliodonium salts was recently developed by our research group.…”

Straightforward and Sustainable Synthesis of Sulfonamides in Water under Mild Conditions

“…The nitro function appears as a promising alternative to amines. Indeed, nitro‐containing molecules are easily available by simple nitration with nitric acid, Henry reaction, palladium‐catalysed coupling of nitromethane or by functionalizing a nitro‐containing molecule using a hypervalent iodine reagent . The nitro function is mainly used as a precursor for the preparation of amines by reduction.…”

“…Indeed, nitro-containing molecules are easily available by simple nitration with nitric acid, [32] Henry reaction, [33] palladium-catalysed coupling of nitromethane [34] or by functionalizing a nitro-containing molecule using a hypervalent iodine reagent. [35] The nitro function is mainly used as a precursor for the preparation of amines by reduction. Due to their good stability and large availability, nitro groups constitute good nitrogen donors.…”