Transition-Metal-Mediated Nucleophilic Aromatic Substitution with Acids

Matthew E. O'Reilly; Samantha I. Johnson; Robert J. Nielsen; William A. Goddard; T. Brent Gunnoe

doi:10.1021/acs.organomet.6b00285

Transition-Metal-Mediated Nucleophilic Aromatic Substitution with Acids

Matthew E. O'Reilly
, Samantha I. Johnson
, Robert J. Nielsen
, William A. Goddard
, T. Brent Gunnoe

Research output: Contribution to journal › Article › peer-review

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 system. Surprisingly, we demonstrate herein a Rh^III-mediated S_NAr reaction of a fluoroarene moiety with RCO₂H (R = CH₃, CF₃) 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.

Original language	English
Pages (from-to)	2053-2056
Number of pages	4
Journal	Organometallics
Volume	35
Issue number	12
DOIs	https://doi.org/10.1021/acs.organomet.6b00285
Publication status	Published - 27 Jun 2016
Externally published	Yes

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title = "Transition-Metal-Mediated Nucleophilic Aromatic Substitution with Acids",

abstract = "Transition-metal-mediated nucleophilic aromatic substitution (SNAr) 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 system. Surprisingly, we demonstrate herein a RhIII-mediated SNAr reaction of a fluoroarene moiety with RCO2H (R = CH3, CF3) 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-SNAr), where the nucleophile coordinates to the metal ion prior to substitution, thereby mitigating the acid influence.",

author = "O'Reilly, \{Matthew E.\} and Johnson, \{Samantha I.\} and Nielsen, \{Robert J.\} and Goddard, \{William A.\} and \{Brent Gunnoe\}, T.",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

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day = "27",

doi = "10.1021/acs.organomet.6b00285",

language = "English",

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TY - JOUR

T1 - Transition-Metal-Mediated Nucleophilic Aromatic Substitution with Acids

AU - O'Reilly, Matthew E.

AU - Johnson, Samantha I.

AU - Nielsen, Robert J.

AU - Goddard, William A.

AU - Brent Gunnoe, T.

PY - 2016/6/27

Y1 - 2016/6/27

N2 - Transition-metal-mediated nucleophilic aromatic substitution (SNAr) 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 system. Surprisingly, we demonstrate herein a RhIII-mediated SNAr reaction of a fluoroarene moiety with RCO2H (R = CH3, CF3) 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-SNAr), where the nucleophile coordinates to the metal ion prior to substitution, thereby mitigating the acid influence.

AB - Transition-metal-mediated nucleophilic aromatic substitution (SNAr) 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 system. Surprisingly, we demonstrate herein a RhIII-mediated SNAr reaction of a fluoroarene moiety with RCO2H (R = CH3, CF3) 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-SNAr), where the nucleophile coordinates to the metal ion prior to substitution, thereby mitigating the acid influence.

UR - https://www.scopus.com/pages/publications/84976538786

U2 - 10.1021/acs.organomet.6b00285

DO - 10.1021/acs.organomet.6b00285

M3 - Article

AN - SCOPUS:84976538786

SN - 0276-7333

VL - 35

SP - 2053

EP - 2056

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Transition-Metal-Mediated Nucleophilic Aromatic Substitution with Acids

Abstract

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