Is Carbon Dioxide Able to Activate Halogen/Lithium Exchange?
作者： Krzysztof Durka , Sergiusz Luliński , Marek Dąbrowski , Janusz Serwatowski
关键词: Solvent 、 Aqueous solution 、 Electrophile 、 Solvent effects 、 Carboxylation 、 Chemistry 、 Reaction mechanism 、 Pentane 、 Tetrahydrofuran 、 Photochemistry
摘要: The unexpected effect of carbon dioxide on halogen–lithium exchange (HLE) reactions selected haloarenes with tBuLi was investigated. In an aliphatic hydrocarbon solvent (pentane), the HLE does not occur at ca. –70 °C but, surprisingly, pouring mixture reactants onto dry ice and subsequent aqueous acidic hydrolysis gave carboxylic acids resulting from quench first-formed aryllithiums dioxide. This suggests that CO2 acts as a promoter and, subsequently, serves electrophile to trap aryllithium intermediates are generated in situ. Theoretical DFT calculations were used develop plausible mechanism for reaction, which indicates is much weaker donor than tetrahydrofuran (THF) so cleavage inert cubic tetramers into more reactive solvated dimeric species (tBuLi)2(CO2)4 disfavored by 42.8 kJ per mol (tBuLi)4. It possible this deaggregation process occurs some extent when large excess used.
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