Elemental F2 with Transannular Dienes: Regioselectivities and Mechanisms |
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| Authors: | Dr Maxim V Ponomarenko Prof?Dr Yuriy A Serguchev Dr Markus E Hirschberg Prof?Dr Gerd‐Volker Röschenthaler Prof?Dr Andrey A Fokin |
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| Institution: | 1. Organic Reactions Mechanism Department, Institute of Organic Chemistry, NAS of Ukraine, 5 Murmanskaya Str., 02094 Kiev (Ukraine);2. School of Engineering and Science, Jacobs University Bremen gGmbH, Campus Ring 1, 28759 Bremen (Germany);3. Inorganic Chemistry, Bergische Universit?t Wuppertal, Gau?strasse 20, 42097 Wuppertal (Germany);4. Department of Organic Chemistry, Kiev Polytechnic Institute, pr. Pobedy 37, 03056 Kiev (Ukraine) |
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| Abstract: | 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 F2 with the terminal dienes of bicyclo3.3.1]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 (CFCl3, CHCl3) solvents were found. The presence of KF in CFCl3 and CHCl3 facilitates the addition and substantially reduces the formation of tar products. |
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| Keywords: | density functional theory dienes electrophilic addition fluorine reaction mechanisms |
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