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. 2005 Jun 9;7(12):2505-8.
doi: 10.1021/ol050900q.

Superacid-catalyzed reactions of olefinic pyrazines: an example of anti-Markovnikov addition involving superelectrophiles

Yiliang Zhang  1 , Jason Briski, Yun Zhang, Rendy Rendy, Douglas A Klumpp
Affiliations

Superacid-catalyzed reactions of olefinic pyrazines: an example of anti-Markovnikov addition involving superelectrophiles

Yiliang Zhang et al. Org Lett. .

Abstract

[reaction: see text] Olefinic pyrazines are found to react with benzene in CF3SO3H and give anti-Markovnikov-type addition products. We propose that this is caused by two effects: destabilization of the carbocationic intermediates that would lead to Markovnikov-type products and the generation of a considerable amount of positive charge at the terminal carbon of the olefinic groups. This suggests that acid-catalyzed addition reactions can give anti-Markovnikov-type products when a multiply charged (i.e., superelectrophilic) group is adjacent to the olefinic site.

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Figures

Scheme 1
Scheme 1
Reactions of olefinic pyrazines.
Scheme 2
Scheme 2
Reactions of alcohols 6a-c.
Scheme 3
Scheme 3
Proposed mechanism of addition.
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