American Chemical Society
cs2c01053_si_001.pdf (19.18 MB)

Catalytic Synthesis of a Methylmalonate Salt from Ethylene and Carbon Dioxide through Photoinduced Activation and Photoredox-Catalyzed Reduction of Nickelalactones

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journal contribution
posted on 2022-03-11, 13:03 authored by Kohei Takahashi, Yuji Sakurazawa, Asaki Iwai, Nobuharu Iwasawa
Catalytic 1,1-dicarboxylation of ethylene with CO2 to form a methylmalonate salt was achieved by a Ni/Ir dual-catalyst system under photoirradiation conditions. In this reaction, photoenergy was utilized not only for the reduction of the methylmalonate Ni­(II) complex but also for the transformation of the nickelalactone to the methylmalonate complex. By careful mechanistic investigations, it was revealed that photoirradiation promotes not only isomerization of five-membered to four-membered nickelalactones but also insertion of the second molecule of CO2 to form methylmalonate complexes via triplet excited states of the four-membered nickelalactones. This is an unprecedented example of catalytic methylmalonate synthesis from ethylene and CO2.