TMEDA-Assisted Effective Direct Ortho Arylation of Electron-Deficient<i>N</i>-Heteroarenes with Aromatic Grignard Reagents

Zhuo, Fang‐Fang; Xie, Wen-Wen; Yang, Yu‐Rong; Zhang, Lei; Wang, Pei; Yuan, Rui; Da, Chao‐Shan

doi:10.1021/jo400152f

Cited by 44 publications

(35 citation statements)

References 58 publications

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“…Zhuo et al [18] reported the synthesis of herteobiaryls by the reactions of ArMgX 21 and hetero aryls 22-25 in the presence of TMEDA and toluene. In conclusion, they have demonstrated that TMEDA could efficiently enhance the direct o-arylation of electron-deficient hetero N-arenes with ArMgX under mild conditions.…”

Section: Arylation Via Grignard Reagent-mediated Reactionmentioning

confidence: 99%

Synthetic journey towards transition metal-free arylations

Roopan

Palaniraja

2014

Res Chem Intermed

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In general, aryl-aryl transformations were investigated via transition metal-catalysed reactions. However, transition metal-mediated organic synthesis provided higher yields but has some flaws such as high cost, and the need for careful exclusion of air and moisture during the reactions. Possibly, there may be contamination of the product from traces of heavy metals present. To overcome these kinds of disadvantages, continuous efforts have been focused on the recent development of aryl-aryl formation through transition metal-free (TMF) reactions. However, most of these cross-couplings reaction were limited to hetero and electron-rich arenes which require strong inorganic bases. Our critical review includes a synthetic pathway to prepared X-aryl (X = C, N, O and S) motif by a transition metal-free scenario. Formerly, TMF reactions were carried out by various sources like strong bases, diazodium salt, aryliodonium salt, organo-catalysts and versatile energy sources like microwave heating, visible light and photochemical reactor. In this review, we have focused on the transition metal-free arylations.

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Section: Arylation Via Grignard Reagent-mediated Reactionmentioning

confidence: 99%

Synthetic journey towards transition metal-free arylations

Roopan

Palaniraja

2014

Res Chem Intermed

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“…[31][32][33][34][35][36][37][38] The synthesis of the latter quinoline was achieved therough Sonogashira coupling by using the typical [PdCl 2 (PPh 3 ) 2 ]/ CuI system, [31] Suzuki cross-coupling, [32] iron-catalyzed Fe(acac) 3 cross-coupling of aromatic Grignard reagent (2-thienylmagnesium bromide) with 2-chloroquinoline, [33] and through reaction of quinoline with 2-thienylmagnesium bromide in the presence of TMEDA. [34] Furthermore, 2-thiophenyl-4-aryl-disubstituted quinolines obtained by Sonogashira coupling from acyl chlorides, alkynes, and 2-aminothiophenols using the [PdCl 2 (PPh 3 ) 2 ]/CuI system [35] have also been reported. Moreover, quinoline derivatives with the thienyl motif in other positions of the quinoline moiety are known; their synthesis has been mainly performed by modified Suzuki coupling.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Electrochemistry, Crystal Structures, and Optical Properties of Quinoline Derivatives with a 2,2′‐Bithiophene Motif

et al. 2014

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New quinolines bearing a 2,2Ј-bithiophene motif have been prepared through Ru-and In-catalyzed reactions as well as by Suzuki cross-coupling reactions. The novel quinolines have been characterized by using EI-HRMS and NMR spectroscopy. Additionally, the molecular structures of the novel quinolines were confirmed by X-ray crystallography. The photophysical and electrochemical properties of all quinoline derivatives were investigated by using absorption and luminescence spectroscopy and cyclic voltammetry. The main intense absorption bands associated with the quinoline derivatives were located between 350 and 450 nm. Intense blue-

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“…These results are in line with the observation of TMEDA-catalyzed arylation of azines with arylmagnesium bromides reported by Da. 8 No functionalization of the distal positions 9 was observed for quinolines and isoquinoline. This direct alkylation reaction is complimentary to the deoxygenative ortho -alkylation of heterocyclic N -oxides.…”

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confidence: 99%

Organocatalytic Synthesis of Methylene-Bridged N-Heterobiaryls

et al. 2016

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A one-step synthesis of 1,1′- and 2,2′-methylene-bridged N-heterobiaryls directly from the corresponding N-heterocycles in a reaction with methylmagnesium chloride in the presence of catalytic amounts of N,N,N′N′-tetramethylethylenediamine (TMEDA) under thermal and microwave conditions is reported. The split-and-merge methylenation of 2,2′-N-heterobiaryls and the direct ortho-alkylation of quinoline and isoquinoline with Grignard reagents have also been developed. Mechanistic studies identified several intermediates and provided insights into the formation and roles of magnesium hydride species in the process.

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TMEDA-Assisted Effective Direct Ortho Arylation of Electron-DeficientN-Heteroarenes with Aromatic Grignard Reagents

Cited by 44 publications

References 58 publications

Synthetic journey towards transition metal-free arylations

Synthetic journey towards transition metal-free arylations

Synthesis, Electrochemistry, Crystal Structures, and Optical Properties of Quinoline Derivatives with a 2,2′‐Bithiophene Motif

Organocatalytic Synthesis of Methylene-Bridged N-Heterobiaryls

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