Advances and Adventures in Amination Reactions of Olefins and Alkynes

Beller, Matthias; Breindl, Claudia; Eichberger, Martin; Hartung, Christian G.; Seayad, Jayasree; Thiel, Oliver R.; Tillack, Annegret; Trauthwein, Harald

doi:10.1055/s-2002-34240

Cited by 192 publications

(36 citation statements)

References 8 publications

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“…[8][9][10][11] However, these methods have some drawbacks, such as the need for activation of aryl/ alkyl halides, the toxicities of the alkylating agents, and the use of strong reducing reagents, which are undesirable from an environmental point of view. Alternatively, in recent years a number of reports on the hydroamination [12][13][14][15][16] or hydroamino-methylation of olefins or alkynes [17][18][19][20] for the synthesis of amines have appeared.…”

Section: Introductionmentioning

confidence: 99%

Amination of Alcohols Catalyzed by Copper‐Aluminium Hydrotalcite: A Green Synthesis of Amines

et al. 2009

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Copper‐aluminium hydrotalcite (CuAl‐HT)/K2CO3 has been employed in the activation of various benzyl alcohols with benzylamines to afford the corresponding amines in good to high yields. Experimentation showed that the reaction takes place through sequential transformations: the oxidation of alcohols into carbonyl compounds, imine formation between amines and carbonyl compounds, and then reduction ofimines to amines, heterogeneously catalyzed by non‐noble Cu‐Al HT catalyst in a one‐pot and straightforward fashion. The process was further extended to amination of alcohols with anilines, which are often resistant to alkylation reactions when substituted with strong electron‐withdrawing groups. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Introductionmentioning

confidence: 99%

Amination of Alcohols Catalyzed by Copper‐Aluminium Hydrotalcite: A Green Synthesis of Amines

et al. 2009

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“…This method, pioneered by our group several years ago, [5] is currently an area of active research. [6,7] On the other hand, in the recent years, the palladium-catalyzed cross-coupling reaction of aryl halides with amines, known as the Buchwald±Hartwig reaction, [8] has emerged as a very powerful procedure for the creation of CÀN bonds (Scheme 2 A). Over the last few years, the work of the Buchwald and Hartwig groups, and others, has led to the development of very efficient catalytic systems for this transformation.…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Cross‐Coupling Reactions of Amines with Alkenyl Bromides: A New Method for the Synthesis of Enamines and Imines

Barluenga

Fernández

Aznar

et al. 2004

Chemistry A European J

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The palladium-catalyzed cross-coupling reaction of alkenyl bromides with secondary and primary amines gives rise to enamines and imines, respectively. This new transformation expands the applicability of palladium-catalyzed C-N bond forming reactions (the Buchwald-Hartwig amination), which have mostly been applied to aryl halides. After screening of different ligands, bases, and solvents, the catalytic combination [Pd(2)(dba)(3)]/BINAP in the presence of NaOtBu in toluene gave the best results in the cross-coupling of secondary amines with 1-bromostyrene (dba=dibenzylideneacetone, BINAP=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl). The corresponding enamines are obtained cleanly and in nearly quantitative yields. However, steric hindrance seems to be a limitation of the reaction, as amines carrying large substituents are not well converted. The same methodology can be applied to the coupling of secondary amines with 2-bromostyrene. Moreover, the reaction with substituted 2-bromopropenes allows regioselective synthesis of isomerizable terminal enamines without isomerization of the double bond. The best catalytic conditions for the cross-coupling of 1-bromostyrene with primary amines include again the use of the Pd(0)/BINAP/NaOtBu system. The reaction gives rise to the expected imines in very short times and with low catalyst loadings. A set of structurally diverse imines can be prepared by this methodology through variations in the structure of both coupling partners. However, 2-bromostyrene failed to give good results in this coupling reaction, probably due to product inhibition of the catalytic cycle. Competition experiments of vinyl versus aryl amination reveal that the reaction occurs preferentially on vinyl bromides.

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“…Earlier mechanistic studies by Milstein on a achiral Ir-catalyst system indicated that the iridium-catalyzed norbornene hydroamination involves amine activation as a key step in the catalytic cycle [27] rather than alkene activation, which is observed for most other late transition metal-catalyzed hydroamination reactions [28]. Thus, the iridium-catalyzed hydroamination of norbornene with aniline is initiated by an oxidative addition of aniline to the metal center, followed by insertion of the strained olefin into the iridiumÀamido bond (Scheme 11.4).…”

Section: ð11:6þmentioning

confidence: 99%

Asymmetric Hydroamination

Reznichenko

Hultzsch

2010

Chiral Amine Synthesis

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Advances and Adventures in Amination Reactions of Olefins and Alkynes

Abstract: Recent developments in the area of transition metalcatalyzed amination of olefins and alkynes are reviewed. Special emphasis is given to rhodium-catalyzed oxidative aminations of aromatic olefins.M. Beller et al.

Cited by 192 publications

References 8 publications

Amination of Alcohols Catalyzed by Copper‐Aluminium Hydrotalcite: A Green Synthesis of Amines

Amination of Alcohols Catalyzed by Copper‐Aluminium Hydrotalcite: A Green Synthesis of Amines

Palladium‐Catalyzed Cross‐Coupling Reactions of Amines with Alkenyl Bromides: A New Method for the Synthesis of Enamines and Imines

Asymmetric Hydroamination

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