Transition-Metal-Mediated Nucleophilic Aromatic Substitution with Acids

O’Reilly, Matthew E. and Johnson, Samantha I. and Nielsen, Robert J. and Goddard, William A., III and Gunnoe, T. Brent (2016) Transition-Metal-Mediated Nucleophilic Aromatic Substitution with Acids. Organometallics, 35 (12). pp. 2053-2056. ISSN 0276-7333. doi:10.1021/acs.organomet.6b00285. https://resolver.caltech.edu/CaltechAUTHORS:20160722-083932887

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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.

Item Type:

Article

Related URLs:

URL	URL Type	Description
http://dx.doi.org/10.1021/acs.organomet.6b00285	DOI	Article
http://pubs.acs.org/doi/abs/10.1021/acs.organomet.6b00285	Publisher	Article
http://pubs.acs.org/doi/suppl/10.1021/acs.organomet.6b00285	Publisher	Supporting Information

ORCID:

Author	ORCID
Nielsen, Robert J.	0000-0002-7962-0186
Goddard, William A., III	0000-0003-0097-5716
Gunnoe, T. Brent	0000-0001-5714-3887

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.

Group:

Resnick Sustainability Institute

Funders:

Funding Agency	Grant Number
Department of Energy (DOE)	DE-SC0001298
NSF	CHE-1465145
NSF	DMR-1436985
NSF	CBET-1512759
Resnick Sustainability Institute	UNSPECIFIED

Issue or Number:

DOI:

10.1021/acs.organomet.6b00285

Record Number:

CaltechAUTHORS:20160722-083932887

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20160722-083932887

Official Citation:

Transition-Metal-Mediated Nucleophilic Aromatic Substitution with Acids Matthew E. O’Reilly, Samantha I. Johnson, Robert J. Nielsen, William A. Goddard, III, and T. Brent Gunnoe Organometallics 2016 35 (12), 2053-2056 DOI: 10.1021/acs.organomet.6b00285

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No commercial reproduction, distribution, display or performance rights in this work are provided.

ID Code:

69159

Collection:

CaltechAUTHORS

Deposited By:

Tony Diaz

Deposited On:

25 Jul 2016 22:14

Last Modified:

11 Nov 2021 04:10

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