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Base-catalyzed Anti-markovnikov Hydroamination Of Vinylarenes : Scope, Limitations And Computational Studies

Patricia Horrillo-Martínez, Kai C Hultzsch, A. Gil, V. Branchadell
Published 2007 · Chemistry

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The hydroamination of vinylarenes with primary and secondary amines was studied with catalytic amounts as low as 2 mol-% of LiN(SiMe3)2/TMEDA. Reactions proceeded readily at 120 °C in the absence of solvent to give selective anti-Markovnikov addition. Slow addition was observed at 25 °C with either electron-deficient p-chlorostyrene or secondary cyclic amines such as pyrrolidine, piperidine, or morpholine. Primary amines were prone to a second hydroamination reaction to form tertiary amine byproducts. The selectivity for the mono(hydroamination) products could be improved with a two-fold excess of the amine. KN(SiMe3)2 showed higher catalytic activity but lower selectivity in comparison to that of LiN(SiMe3)2, resulting in undesired C–H-activation byproducts. The mechanism of the lithium-catalyzed hydroamination and the influence of TMEDA was studied with density functional theory. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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