RT Journal Article
T1 Photolysis of CO₂ carbamate for hydrocarboxylation reactions
A1 Azzi, Emanuele
A1 Rodríguez Martínez, Manuel
A1 Kolusu, Sai Rohini Narayanan
A1 Scarfiello, Jacopo
A1 Varela Carrete, Jesús Ángel
A1 Nappi, Manuel
K1 Anions
K1 Hydrocarbons
K1 Inorganic carbon compounds
K1 Organic compounds
K1 Oxides
AB The conversion of carbon dioxide into value-added products has emerged as an alternative method to achieve net-zero emissions. While technologies that transform CO2 into fuels and chemical feedstocks have made great strides, the direct use of CO2 as a C1 synthon for the formation of new carbon–carbon bonds remains a critical challenge. Herein, we present a new catalytic CO2 activation mode for hydrocarboxylation reactions. Key to this methodology is the formation of a CO2 carbamate with a phenothiazine catalyst, which sets the required trigonal geometry for the release of CO2•– via photolysis upon absorption of visible light. The polarity-reversed CO2•– is employed in the hydrocarboxylation reactions of alkenes and heterocycles. This protocol is distinguished by its mild reaction conditions, wide substrate scope and broad applicability, even in the context of pharmaceutical cores. Our chemistry can also be utilized for the synthesis of carbon-13 labeled spirolactones using 13CO2. Mechanistic experiments support the photolysis of the CO2 carbamate as the main productive pathway under our optimized reaction conditions
PB American Chemical Society
YR 2026
FD 2026-01-12
LK https://hdl.handle.net/10347/46845
UL https://hdl.handle.net/10347/46845
LA eng
NO Azzi, E., Rodríguez-Martínez, M., Kolusu, S. R. N., Scarfiello, J., Varela, J. A., & Nappi, M. (2026). Photolysis of CO₂ Carbamate for Hydrocarboxylation Reactions. Journal of the American Chemical Society, 148(3), 3801–3810. https://doi.org/10.1021/jacs.5c21208
NO The authors thank CIQUS, AEI/MICIU (PID2020-113067GA-I00, TED2021-129833A-I00, RYC2022-035515-I, PID2023-151279NB-I00), the Xunta de Galicia (ED431F 2024/027, ED431C 2022/27, Centro de investigación do Sistema universitario de Galicia accreditation 2023-2027 - ED431G 2023/03) and the European Union (European Regional Development Fund - ERDF) for the financial support of this work. We are also thankful for the use of CIQUS/RIAIDT-USC analytical facilities, and CESGA (Xunta de Galicia) for computational time.
DS Minerva
RD 9 may 2026