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Peer-reviewedCC BYJournal of the American Chemical Society

Intermolecular Reductive Coupling of Ketones and Alkenes under Ferrioxalate Photocatalysis

  • Dalila Arnaldi1,2
  • Niccolò Intini1,2
  • Partha Pratim Sen1,2
  • Sergio Adalid1,2
  • Kristýna Kellovská1,2
  • Michael G. Guerzoni3
  • Thomas D. Svejstrup3
  • Fabio Juliá1,2
  1. 1Facultad de Química, Centro de Investigación Multidisciplinar Pleiades-Vitalis
  2. 2Universidad de Murcia; Campus de Espinardo
  3. 3Early Chemical Development, Pharmaceutical Sciences, R&D, AstraZeneca Pharmaceuticals
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Abstract

High Resolution Image Download MS PowerPoint Slide Ketones and alkenes are among the most frequent functional groups found in natural products, feedstock, and bioactive compounds. Hence, the use of both functionalities as cross-coupling handles retains a marked synthetic potential for Csp 3 –Csp 3 bond formation. However, the reaction between ketones and alkenes has traditionally relied on intramolecular systems or the use of activated coupling partners, while intermolecular reactions involving unbiased substrates have found limited success. Here we report a strategy for the direct coupling of unactivated ketones with unactivated alkenes enabled by ferrioxalate photocatalysis. This catalytic platform allows the inner-sphere reduction of ketones to access ketyl radicals that effectively react with alkenes despite the adverse polarity mismatch. This method gives access to a wide range of tertiary alcohols, which are generally assembled through Grignard reagent additions, using alkenes in place of organometallic nucleophiles, allowing this transformation to proceed with broad tolerance to diverse polar and protic functional groups. Overall, this reactivity blueprint constitutes a platform for the fast exploration of Csp 3 -rich chemical space, capitalizing on the diversity of readily available alkene and ketone building blocks. The utility of the method is demonstrated in several applications, showcasing the enabling potential of this platform for synthetic and medicinal chemistry.

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Cite

BibTeXRIS
BibTeX
@article{arnaldi2026intermolecular,
  title = {{Intermolecular Reductive Coupling of Ketones and Alkenes under Ferrioxalate Photocatalysis}},
  author = {Dalila Arnaldi and Niccolò Intini and Partha Pratim Sen and Sergio Adalid and Kristýna Kellovská and Michael G. Guerzoni and Thomas D. Svejstrup and Fabio Juliá},
  journal = {Journal of the American Chemical Society},
  year = {2026},
  month = jul,
  doi = {10.1021/jacs.6c10799},
  url = {https://doi.org/10.1021/jacs.6c10799},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Intermolecular Reductive Coupling of Ketones and Alkenes under Ferrioxalate Photocatalysis
AU  - Dalila Arnaldi
AU  - Niccolò Intini
AU  - Partha Pratim Sen
AU  - Sergio Adalid
AU  - Kristýna Kellovská
AU  - Michael G. Guerzoni
AU  - Thomas D. Svejstrup
AU  - Fabio Juliá
PY  - 2026
DA  - 2026/07/13
JO  - Journal of the American Chemical Society
DO  - 10.1021/jacs.6c10799
UR  - https://doi.org/10.1021/jacs.6c10799
AB  - High Resolution Image Download MS PowerPoint Slide Ketones and alkenes are among the most frequent functional groups found in natural products, feedstock, and bioactive compounds. Hence, the use of both functionalities as cross-coupling handles retains a marked synthetic potential for Csp 3 –Csp 3 bond formation. However, the reaction between ketones and alkenes has traditionally relied on intramolecular systems or the use of activated coupling partners, while intermolecular reactions involving unbiased substrates have found limited success. Here we report a strategy for the direct coupling of unactivated ketones with unactivated alkenes enabled by ferrioxalate photocatalysis. This catalytic platform allows the inner-sphere reduction of ketones to access ketyl radicals that effectively react with alkenes despite the adverse polarity mismatch. This method gives access to a wide range of tertiary alcohols, which are generally assembled through Grignard reagent additions, using alkenes in place of organometallic nucleophiles, allowing this transformation to proceed with broad tolerance to diverse polar and protic functional groups. Overall, this reactivity blueprint constitutes a platform for the fast exploration of Csp 3 -rich chemical space, capitalizing on the diversity of readily available alkene and ketone building blocks. The utility of the method is demonstrated in several applications, showcasing the enabling potential of this platform for synthetic and medicinal chemistry.
SN  - 0002-7863
SN  - 1520-5126
SN  - 1943-2984
ER  -