Selective functionalization of methane, ethane, and higher alkanes by cerium photocatalysis

With the recent soaring production of natural gas, the use of methane and other light hydrocarbon feedstocks as starting materials in synthetic transformations is becoming increasingly economically attractive, although it remains chemically challenging. We report the development of photocatalytic C-...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2018-08, Vol.361 (6403), p.668-672
Main Authors: Hu, Anhua, Guo, Jing-Jing, Pan, Hui, Zuo, Zhiwei
Format: Article
Language:English
Subjects:
Alcohol
Alcohols
Alkanes
Alkenes
Alkylation
Ambient temperature
Amination
Aromatic compounds
Azo compounds
Catalysis
Catalysts
Cerium
Charge transfer
Continuous flow
Ethane
Hydrocarbons
Irradiation
Light irradiation
Methane
Natural gas
Organic chemistry
Photocatalysis
Radiation
Radicals
Raw materials
Salts
Transformations
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Summary:With the recent soaring production of natural gas, the use of methane and other light hydrocarbon feedstocks as starting materials in synthetic transformations is becoming increasingly economically attractive, although it remains chemically challenging. We report the development of photocatalytic C-H amination, alkylation, and arylation of methane, ethane, and higher alkanes under visible light irradiation at ambient temperature. High catalytic efficiency (turnover numbers up to 2900 for methane and 9700 for ethane) and selectivity were achieved using abundant, inexpensive cerium salts as photocatalysts. Ligand-to-metal charge transfer excitation generated alkoxy radicals from simple alcohols that in turn acted as hydrogen atom transfer catalysts. The mixed-phase gas/liquid reaction was adapted to continuous flow, enabling the efficient use of gaseous feedstocks in scalable photocatalytic transformations.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.aat9750