Transition-Metal-Mediated Nucleophilic Aromatic Substitution with Acids
Abstract
Transition-metal-mediated nucleophilic aromatic substitution (S_NAr) reactions prefer that a suitably strong nucleophile be in an aprotic medium. Usually, using protic nucleophile/medium requires high reaction temperatures (>180 °C) to overcome the attenuated nucleophilicity for attack on the arene π system. Surprisingly, we demonstrate herein a Rh^(III)-mediated S_NAr reaction of a fluoroarene moiety with RCO_2H (R = CH_3, CF_3) in acid media that proceeds at moderate temperatures (<100 °C). We show both by experimental and with DFT calculations that the mechanism proceeds through an internal nucleophilic aromatic substitution (I-S_NAr), where the nucleophile coordinates to the metal ion prior to substitution, thereby mitigating the acid influence.
Additional Information
© 2016 American Chemical Society. Received: April 8, 2016; Published: June 9, 2016. The authors acknowledge support from the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0001298 for initial catalyst preparation and the National Science Foundation (CHE-1465145, DMR-1436985, and CBET 1512759) for support of mechanistic studies. S.I.J. was generously supported by the Resnick Sustainability Institute. The authors declare no competing financial interest.Attached Files
Supplemental Material - om6b00285_si_001.pdf
Supplemental Material - om6b00285_si_002.xyz
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Additional details
- Eprint ID
- 69159
- DOI
- 10.1021/acs.organomet.6b00285
- Resolver ID
- CaltechAUTHORS:20160722-083932887
- Department of Energy (DOE)
- DE-SC0001298
- NSF
- CHE-1465145
- NSF
- DMR-1436985
- NSF
- CBET-1512759
- Resnick Sustainability Institute
- Created
-
2016-07-25Created from EPrint's datestamp field
- Updated
-
2023-03-16Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute