Hydroamination reactions are chemical transformations in which a C-N bond is produced. The reaction entails the addition of a N-H group to an unsaturated carbon-carbon double bond. In the hydroamination reaction there are two possible regio-isomers that can be produced; the anti-Markovnikov and Markovnikov products. The hydroamination reaction is highly efficient and allows access to nitrogen-containing organic molecules, which can be synthesized from simple, and cheap starting materials.1 Traditionally, transition and rare earth metals were used to catalyze the hydroamination reactions.2 However, these metals are limited in supply and expensive. The use of alkaline earths as catalysts in catalytic transformations, particularly calcium, has recently gained a significant amount of interest. Calcium is abundant, cheap and biocompatible. These properties make calcium highly attractive for catalytic hydroamination reactions. In this study we computationally investigate, using DFT methods, the alkaline earth catalyzed intermolecular hydroamination of styrene and benzylamine. The alkene insertion transition state is determined to be the rate-determining step, followed by protonolysis to generate the N-benzyl-2-phenethylamineproduct. Our results offer substantial additional insight into the mechanistic pathway, and are in general agreement with synthetic experimental studies.3 We have been able rationalize why the anti-Markovnikov product is the only regio-isomer is observed synthetically,3 and to show why the barium catalyzed reaction is faster than the equivalent calcium catalysed reaction.4 1. K. C. Hultzsch, Org. Biomol. Chem., 2005, 3  , 1819. 2. M. Nobis and B. D. H�lscher, Angew. Chem. Int. Ed. Engl., 2001, 40 , 3983.3. C. Brinkmann, A. G. M. Barrett, M. S. Hill and P. A. Procopiou, J. Am. Chem. Soc., 2012, 134 , 2193.4. B. Liu, T. Roisnel, J. F. Carpentier and Y. Sarazin, Angew. Chem. Int. Ed., 2012, 51 , 4943.

Calcium catalyzed hydroamaination of styrene and benzylamine: A computational investigation

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.