Base-catalyzed anti-Markovnikov hydroamination of vinylarenes - Scope, limitations and computational studies

Patricia Horrillo-Martínez, Kai C. Hultzsch, Adrià Gil, Vicenç Branchadell

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72 Citations (Scopus)

Abstract

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(SiMe 3)2, resulting in undesired C-H-activation by-products. The mechanism of the lithium-catalyzed hydroamination and the influence of TMEDA was studied with density functional theory. © Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Original languageEnglish
Pages (from-to)3311-3325
JournalEuropean Journal of Organic Chemistry
Issue number20
DOIs
Publication statusPublished - 23 Jul 2007

Keywords

  • Density functional calculations
  • Homogeneous catalysis
  • Hydroamination
  • Lithium
  • Phenethylamines
  • Reaction mechanisms

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