Amination of Aromatic Olefins with Anilines: A New Domino Synthesis of Quinolines

Beller, Matthias; Thiel, Oliver R.; Trauthwein, Harald; Hartung, Christian G.

doi:10.1002/1521-3765(20000717)6:14<2513::aid-chem2513>3.0.co;2-v

Cited by 94 publications

(48 citation statements)

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“…Recently, more and more new simple and elegant syntheses of substituted quinolines have been described. [25][26][27][28][29][30][31][32][33][34][35][36][37][38] Among these methods, the procedure using a HCl-DMSO system seems to be a very practical method for substituted quinolines starting from imines and carbonyl compounds. 34 In view of the remarkable importance from the pharmacological, industrial and synthetic point, the development of new synthetic approaches using mild reaction conditions remains an active research field.…”

Section: Introductionmentioning

confidence: 99%

TMSCl-Catalyzed synthesis of substituted quinolines from arylimines and enolizable aldehydes

Geng¹,

Li²,

Bian³

et al. 2008

Arkivoc

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Some substituted quinolines were effectively synthesized utilizing chlorotrimethylsilane (TMSCl) as efficient promoter in the cyclization addition of enolizable aldehydes to arylimines under an air atmosphere in DMSO. The clean, mild and ecofriendly process with high yields and a simple workup of the desired compounds are attractive features of the reaction which enables a facile preparation of the quinoline ring.

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Section: Introductionmentioning

confidence: 99%

TMSCl-Catalyzed synthesis of substituted quinolines from arylimines and enolizable aldehydes

Geng¹,

Li²,

Bian³

et al. 2008

Arkivoc

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“…The constant presence of carbon monoxide was necessary to stabilize the Co 2 (CO) 8 under the reaction conditions, without this reduced yields of products were obtained due to the instability of the Co 2 (CO) 8 upon heating. Use of 4 -methoxyallylaniline led to the corresponding 6 -substituted quinoline in a 24% yield.…”

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confidence: 99%

“…The 2 -ethyl -3 -methyl substitution pattern is common to products derived from both mono -and di -allylanilines. The pathway initially suggested was that there was an initial cleavage of the allylic C -N bond by Co 2 (CO) 8 to generate a π -allyl intermediate. Palladium and ruthenium have been shown to cleave allylic C -N bonds in a similar fashion [25,26] .…”

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confidence: 99%

“…With the use of Co 2 (CO) 8 it has been shown that arylimines can undergo selective cross -coupling with diallylanilines to generate the corresponding quinolines [29] . The cross -coupling of phenyl benzaldimine with diallylaniline was studied in the presence of 10 mol% of Co 2 (CO) 8 .…”

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confidence: 99%

“…The cross -coupling of phenyl benzaldimine with diallylaniline was studied in the presence of 10 mol% of Co 2 (CO) 8 . The cross -coupling quinoline product was isolated in 47% yield (Equation (6.4) ).…”

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Cobalt and Nickel Catalyzed Reactions Involving CH and CN Activation Reactions

Becker

Jones

2010

Catalysis Without Precious Metals

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IntroductionHomogeneous transition metal catalyzed reactions have been very well studied over the past 50 years. The metal complexes used to accomplish these reactions have typically included noble transition metals or fi rst row metals. Due to the cost and pathogenicity of these noble metals, the development of new catalytic routes using non -precious metals is an active area of research. In this chapter, a review of the use of selected cobalt and nickel species towards catalytic reactions analogous to those seen with noble metals is presented. Catalysis with CobaltTransition metal catalyzed hetero -annulation provides a useful and convenient tool for the construction of N -heterocycles [1] . Quinolines are of special interest in that they display attractive applications in pharmaceuticals and are synthetic building blocks [2,3] . Catalytic processes employing palladium [4 -6] , rhodium [7 -9] , ruthenium [10 -14] , and iron [15] have been studied and developed to synthesize quinoline skeletons. There are fi ve common methods used to prepare substituted quinolines: the Skraup reaction [16] , the Doebner -Von Miller reaction [17] , the Conrad -Limpach reaction [18] , the Friedlaender reaction [19,20] , and the Pfi tzinger reaction [21,22] . All fi ve of the reactions require environmentally unfriendly acids or bases, high temperatures, or harsh conditions. Quinoline yields are usually low due to numerous side reactions. Even though much work has been done to fi nd catalytic routes to quinolines, the use of non -precious metals remains an active area of research.Recently, Jones et al. have published work on the conversion of diallylanilines and arylimines to quinolines [23,24] . It was found that N -allylaniline, when heated in the presence of 10 mol% Co 2 (CO) 8 and 1 atm of CO at 85 ° C, leads to the selective formation of 2 -ethyl -3 -methylquinoline (Equation (6.1) ). Aniline and propene 6 Catalysis Without Precious Metals. Edited by R. Morris Bullock

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Anti-Markovnikov Hydroamination of Terminal Alkynes

Tillack

Castro

Hartung

et al. 2002

Angew. Chem. Int. Ed.

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168

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Imines are of significant importance as intermediates for the synthesis of various amines and carbonyl compounds. In general, the synthesis of imines includes amination of a suitable aldehyde or ketone. A more atom-efficient route is the direct hydroamination of alkynes. [1] This method has the additional advantage that no water is produced as a by-product. Hence, various domino reactions (e.g. direct nucleophilic addition of organometallic reagents) are possible, which do not work in the presence of water.The homogeneously catalyzed intermolecular hydroamination of alkynes is known to proceed in the presence of Hg and Tl salts, [2] alkali metals (Cs), [3] Ti, [4] Zr, [5] Nd, [6] U, and Th [7] complexes. In addition, complexes of late-transition metals (such as Ru, Pd, [8] and Rh [9] ) have been used as catalysts for this transformation. Clearly, catalysts based on cheap and easily available titanium and zirconium complexes offer significant advantages compared to those based on toxic metals (Hg, Tl) or more expensive (U, Th, Ru, Pd, and Rh) complexes.Recently, important progress in the intermolecular hydroamination of alkynes with titanium complexes was made by Johnson and Bergman [10] and by Doye and co-workers. [4] While the former group developed the modified titanium complex [Cp(ArNH)(py)TiNAr] (Cp cyclopentadienyl, py pyridyl) and used it for the reaction of 2,6-dimethylaniline and diphenylacetylene, the latter group described an efficient and general method for the hydroamination of various internal alkynes using dimethyltitanocene as a catalyst. Bytschkov and Doye showed that the turnover frequency of this catalyst can be enhanced by using microwaves. [4c] Kinetic measurements by Bergman [10] and Doye [11] also established a general mechanism of the dimethyltitanocenecatalyzed intermolecular hydroamination of alkynes. Surprisingly little attention was paid to the hydroamination of terminal alkynes using titanium catalysts, [12] although the regioselective, sequential amination and hydroxylation of compounds that are unsaturated at the terminal position is one of the most challenging goals for industrial catalysis. Herein we report the first example of a titanocene-catalyzed anti-Markovnikov hydroamination of terminal aliphatic alkynes.Some time ago we started a program on catalytic amination reactions of olefins and alkynes. [13,9] Inspired by the work of Doye and Bergman, we also recently looked for easily available and stable titanocene complexes. Here, titanocene alkyne complexes of the type [Cp 2 Ti(h 2 -Me 3 SiCCR)] (Rosenthal×s catalyst) [14] appeared to be suited as amination catalysts. [15] These complexes ([Cp 2 Ti(h 2 -Me 3 SiCCSiMe 3 )] 1 [14a] and [Cp 2 Ti(h 2 -Me 3 SiCCPh] 2 [14b] ) are easily synthesized by reaction of titanocene dichloride with the corresponding silylated alkyne.Compared to previously used titanocene precatalysts, the titanacyclopropene complexes 1 and 2 are safe and stable under argon at room temperature for many months in German version. Indeed, hydroamination of...

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Amination of Aromatic Olefins with Anilines: A New Domino Synthesis of Quinolines

Cited by 94 publications

References 7 publications

TMSCl-Catalyzed synthesis of substituted quinolines from arylimines and enolizable aldehydes

TMSCl-Catalyzed synthesis of substituted quinolines from arylimines and enolizable aldehydes

Cobalt and Nickel Catalyzed Reactions Involving CH and CN Activation Reactions

Anti-Markovnikov Hydroamination of Terminal Alkynes

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