Iron‐Catalyzed Reductive Cross‐Coupling of Alkyl Electrophiles with Olefins
Abstract
In terms of its abundance and its minimal toxicity, iron has advantages relative to other transition metals. Although alkyl–alkyl bond construction is central to organic synthesis, examples of iron-catalyzed alkyl–alkyl couplings of alkyl electrophiles are relatively sparse. Herein we report an iron catalyst that achieves cross-coupling reactions of alkyl electrophiles wherein olefins, in the presence of a hydrosilane, are used in place of alkylmetal reagents. Carbon–carbon bond formation proceeds at room temperature, and the method employs commercially available components (Fe(OAc)₂, Xantphos, and Mg(OEt)₂); interestingly, this set of reagents can be applied directly to a distinct hydrofunctionalization of olefins, hydroboration. Mechanistic studies are consistent with the generation of an alkyl radical from the alkyl electrophile, as well as with reversibility for elementary steps that precede carbon–carbon bond formation (olefin binding to iron and β-migratory insertion).
Additional Information
© 2023 Wiley-VCH GmbH. We thank Robert L. Anderson, Dr. Caiyou Chen, Hyungdo Cho, Dr. Dylan J. Freas, Dr. Asik Hossain, and Christian Johansen for assistance and helpful discussions. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences; grant R35-GM145315), the Resnick Sustainability Institute, the John Stauffer Fund (support for C. E. D. A.), the Beckman Institute (support of the EPR facility and the Center for Catalysis and Chemical Synthesis), the Gordon and Betty Moore Foundation (support of the Center for Catalysis and Chemical Synthesis), the Dow Next-Generation Educator Fund (grant to the California Institute of Technology), and the Peters laboratory (Mössbauer spectrometer). Data Availability Statement: The data that support the findings of this study are available in the Supporting Information of this article. The authors declare no conflict of interest.Attached Files
Supplemental Material - anie202306663-sup-0001-misc_information.pdf
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Additional details
- Eprint ID
- 122407
- Resolver ID
- CaltechAUTHORS:20230725-746869000.33
- PMCID
- PMC10528270
- NIH
- R35-GM145315
- Resnick Sustainability Institute
- John Stauffer Fund
- Caltech Beckman Institute
- Gordon and Betty Moore Foundation
- Dow Next Generation Education Fund
- Created
-
2023-08-16Created from EPrint's datestamp field
- Updated
-
2023-08-16Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute