3 years ago

Nucleophilic Addition of Ketones To Acetylenes and Allenes: A Quantum-Chemical Insight

Nucleophilic Addition of Ketones To Acetylenes and Allenes: A Quantum-Chemical Insight
Vladimir B. Orel, Elena Yu. Schmidt, Boris A. Trofimov, Alexander S. Bobkov, Vladimir B. Kobychev, Nadezhda M. Vitkovskaya
A CBS-Q//B3 based study has been carried out to elucidate the mechanism of the KOH/DMSO superbase catalyzed ketones nucleophilic addition to alkyl propargyl and alkyl allenyl ethers yielding, along with (Z)-monoadducts, up to 26% of unexpected (E)-diadducts. The impact of different substrates (alkynes versus allenes) on the reaction mechanism has been discussed in detail. Along with the model reaction of acetone addition to propyne and allene, the addition of acetone and acetophenone to methyl propargyl and methyl allenyl ethers is considered. The limiting reaction stage of the starting ketone carbanion addition to propargyl and allenyl systems occurs with activation energies typical for vinylation of ketones. In contrast, the addition of intermediate α-carbanions to the terminal position of methyl allenyl ether is associated with unusually low activation barriers. The results obtained explain the composition of the reaction products and indicate the participation of mainly the allene form in the reaction.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b02263

DOI: 10.1021/acs.joc.7b02263

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