Abstract
We have carried out a detailed computational study on the neutral-neutral direct hydroamination reactions between various substituted ethylene derivatives with ammonia, using the density functional theory based B3LYP/6-31++G(2df,2p) level of theory. Analysis of the potential energy surfaces for all these reactions shows that in all these cases thermodynamically the Markovnikov product is more stable than the anti-Markovnikov product. Analysis of the transition states for all these reactions shows that kinetically in some cases the Markovnikov product is preferable whereas other cases the anti-Markovnikov product is preferable. This gives a clear indication on how to control the selectivity in these reactions by mere alteration of the substituent. We observed that, in the case of ethylene with an electron withdrawing substituent (i.e. CH2=CH–NO2) reacting with ammonia, the barrier height is reduced by approximately 70 kJ/mol and at the same time the anti-Markovnikov product is preferred kinetically. This situation clearly mimics the general catalytic hydroamination reaction where the ethylene is being activated by the catalyst. Also, this suggests that a stronger electron withdrawing group than −NO2 will possibly be able to reduce the barrier height further and ultimately a non-catalytic neutral-neutral direct hydroamination reaction will be physically attainable.
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Acknowledgements
SS thanks Claude-Leon foundation of South Africa for the postdoctoral fellowship. This material is based on work supported by the National Research Foundation, South Africa. This publication was made possible (in part) by a grant from the Carnegie Corporation of New York. The statements made and views expressed are, however, solely the responsibility of the author
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Sitha, S., Jewell, L.L. (2012). Neutral-Neutral Direct Hydroamination Reactions of Substituted Alkenes: A Computational Study on the Markovnikov Selection Rule. In: Gupta Bhowon, M., Jhaumeer-Laulloo, S., Li Kam Wah, H., Ramasami, P. (eds) Chemistry for Sustainable Development. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-8650-1_23
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