Iron‐Based Imidazolium Salts as Versatile Catalysts for the Synthesis of Quinolines and 2‐ and 4‐Allylanilines by Allylic Substitution of Alcohols

Abstract

Abstract. Readily available iron(III) based imidazolium salts have proven to be very versatile catalysts for the allylic substitution reaction of alcohols with anilines, allowing the synthesis of quinolines, 2-allylanilines and 4-allylanilines just by modulating the reaction conditions. Noteworthy, the formation of quinoline derivatives proceeds by orthoallylation of the corresponding aniline and subsequent oxidative cyclization mediated by atmospheric oxygen.The reaction using anilines as nucleophiles is selective to the C-alkylation versus the N-alkylation, under any reaction conditions studied.

Versatile Barium and Calcium Imidazolium‐Dicarboxylate Heterogeneous Catalysts in Quinoline Synthesis

“…We have employed functionalized imidazolium derivatives as precursors of N‐heterocyclic carbene (NHC) ligands for palladium . They can also be used in combination with metal salts, such as iron(III) chloride, to produce iron‐based Lewis acid ionic liquids (IBLAILs), which proved to be very versatile catalytic systems . Furthermore, we employed a metal‐organic framework based on imidazolium dicarboxylate as an efficient and robust catalyst for the oxidative coupling between carboxylic acids and formamides .…”

“…[19] They can also be used in combination with metal salts, such as iron(III) chloride, to produce iron-based Lewis acid ionic liquids (IBLAILs), which proved to be very versatile catalytic systems. [20] Furthermore, we employed a metal-organic framework based on imidazolium dicarboxylate as an efficient and robust catalyst for the oxidative coupling between carboxylic acids and formamides. [21] On the other hand, the use of heterogeneous catalysts based on alkaline earth metals is quite scarce.…”

Synthesis of C2-Symmetric Bisphosphines and Their Application in Enantioselective Transition Metal Catalysis

“…1 H, 13 C and 31 P NMR spectra were recorded on a Varian Mercury 400 MHz spectrometer as indicated, with chemical shifts reported in ppm relative to TMS (for 1 H and 13 C NMR), and relative to 85% aqueous phosphoric acid (for 31 P), using the residual solvent signal as a standard. 13…”

“…[1][2][3][4][5][6][7] In this context, there is a remarkable attention in this type of synthesis and over the past few years, extensive researches have been carried out in order to develop efficient chiral ligands. [8][9][10][11][12][13][14][15][16][17][18][19] The first known palladium-catalyzed enantioselective allylic alkylation was introduced by Trost and Strege with moderate enantioselectivities in the presence of chiral 2,3-Oisoproylidene-2,3dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP). [20] Since the initial report, it took many years to develop efficient enantioselective catalysts due to the complex enantiocontrol in allylic substitutions.…”

Alcohols in direct carbon-carbon and carbon-heteroatom bond-forming reactions: recent advances

“…110 Lee's group developed indium(III) chloride to gold(I) as a catalyst in dehydrative reactions with allylic alcohols. 111 Protocols for the direct catalytic dehydrative substitution of alcohols recently have been reviewed 112 and selected results are shown in (Table 16).…”