Toward ideal carbon dioxide functionalization

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This Perspective recapitulates recent developments of carbon dioxide utilization in carbon-carbon bond formation reactions, with an intention of paving a way toward sustainable CO 2 -functionalization and its tangible applications in synthetic chemistry. CO 2 functionalization reactions possess intrinsic drawbacks: the high kinetic inertness and thermodynamic stability of CO 2 . Numerous procedures for CO 2 utilization depend on energy-intensive processes (i.e. high pressure and/or temperature), often solely relying on reactive substrates, hampering its general applications. Recent efforts thus have been dedicated to catalytic CO 2 -utilization under ambient reaction conditions, however, it is still limited to a few activation modes and the use of reactive substrates. Herein, ideal CO 2 -functionalization with particular emphasis on sustainability will be discussed based on the following sub-categories; (1) metal-catalyzed ‘reductive' carboxylation reaction of halides, olefins and allyl alcohols, (2) photochemical CO 2 -utilization, (3) redox-neutral CO 2 -functionalization, and (4) enantioselective catalysis incorporating CO 2 to form C-CO 2 bonds (excluding strain mediated reactions with epoxide- and aziridine-based substrates). Recent progress in these fields will be discussed with the proposed reaction mechanisms and selected examples, highlighting redox-neutral, umpolung, and asymmetric carboxylation to postulate ideal CO 2 functionalization reactions to be developed in the near future.

Original languageEnglish
JournalChemical Science
Issue number14
Pages (from-to)3905-3926
Number of pages22
Publication statusPublished - 2019

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