Elemental F 2 with Transannular Dienes: Regioselectivities and Mechanisms

Three reaction paths, namely, molecule‐induced homolytic, free radical, and electrophilic, were modeled computationally at the MP2 level of ab initio theory and studied experimentally for the reaction of F 2 with the terminal dienes of bicyclo[3.3.1]nonane series. The addition of fluorine is accompa...

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Published in:Chemistry : a European journal 2014-08, Vol.20 (33), p.10383-10391
Main Authors: Ponomarenko, Maxim V., Serguchev, Yuriy A., Hirschberg, Markus E., Röschenthaler, Gerd‐Volker, Fokin, Andrey A.
Format: Article
Language:English
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Summary:Three reaction paths, namely, molecule‐induced homolytic, free radical, and electrophilic, were modeled computationally at the MP2 level of ab initio theory and studied experimentally for the reaction of F 2 with the terminal dienes of bicyclo[3.3.1]nonane series. The addition of fluorine is accompanied by transannular cyclization to the adamantane derivatives in which strong evidence for the electrophilic mechanism both in nucleophilic (acetonitrile) and non‐nucleophilic (CFCl 3 , CHCl 3 ) solvents were found. The presence of KF in CFCl 3 and CHCl 3 facilitates the addition and substantially reduces the formation of tar products.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201402640