Long-range C-H bond activation by RhIII-carboxylates

Matthew E. O'Reilly; Ross Fu; Robert J. Nielsen; Michal Sabat; William A. Goddard; T. Brent Gunnoe

doi:10.1021/ja508367m

Long-range C-H bond activation by Rh^III-carboxylates

Matthew E. O'Reilly
, Ross Fu
, Robert J. Nielsen
, Michal Sabat
, William A. Goddard
, T. Brent Gunnoe

University of Virginia
California Institute of Technology
University of Virginia School of Engineering and Applied Science

Résultats de recherche: Contribution à un journal › Article › Revue par des pairs

26 Citations (Scopus)

Résumé

Traditional C-H bond activation by a concerted metalation-deprotonation (CMD) mechanism involves precoordination of the C-H bond followed by deprotonation from an internal base. Reported herein is a "through-arene" activation of an uncoordinated benzylic C-H bond that is 6 bonds away from a Rh^III ion. The mechanism, which was investigated by experimental and DFT studies, proceeds through a dearomatized xylene intermediate. This intermediate was observed spectroscopically upon addition of a pyridine base to provide a thermodynamic trap.

langue originale	Anglais
Pages (de - à)	14690-14693
Nombre de pages	4
journal	Journal of the American Chemical Society
Volume	136
Numéro de publication	42
Les DOIs	https://doi.org/10.1021/ja508367m
état	Publié - 1 nov. 2014
Modification externe	Oui

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10.1021/ja508367m

Contient cette citation

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title = "Long-range C-H bond activation by RhIII-carboxylates",

abstract = "Traditional C-H bond activation by a concerted metalation-deprotonation (CMD) mechanism involves precoordination of the C-H bond followed by deprotonation from an internal base. Reported herein is a {"}through-arene{"} activation of an uncoordinated benzylic C-H bond that is 6 bonds away from a RhIII ion. The mechanism, which was investigated by experimental and DFT studies, proceeds through a dearomatized xylene intermediate. This intermediate was observed spectroscopically upon addition of a pyridine base to provide a thermodynamic trap.",

author = "O'Reilly, \{Matthew E.\} and Ross Fu and Nielsen, \{Robert J.\} and Michal Sabat and Goddard, \{William A.\} and Gunnoe, \{T. Brent\}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2014",

month = nov,

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doi = "10.1021/ja508367m",

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TY - JOUR

T1 - Long-range C-H bond activation by RhIII-carboxylates

AU - O'Reilly, Matthew E.

AU - Fu, Ross

AU - Nielsen, Robert J.

AU - Sabat, Michal

AU - Goddard, William A.

AU - Gunnoe, T. Brent

PY - 2014/11/1

Y1 - 2014/11/1

N2 - Traditional C-H bond activation by a concerted metalation-deprotonation (CMD) mechanism involves precoordination of the C-H bond followed by deprotonation from an internal base. Reported herein is a "through-arene" activation of an uncoordinated benzylic C-H bond that is 6 bonds away from a RhIII ion. The mechanism, which was investigated by experimental and DFT studies, proceeds through a dearomatized xylene intermediate. This intermediate was observed spectroscopically upon addition of a pyridine base to provide a thermodynamic trap.

AB - Traditional C-H bond activation by a concerted metalation-deprotonation (CMD) mechanism involves precoordination of the C-H bond followed by deprotonation from an internal base. Reported herein is a "through-arene" activation of an uncoordinated benzylic C-H bond that is 6 bonds away from a RhIII ion. The mechanism, which was investigated by experimental and DFT studies, proceeds through a dearomatized xylene intermediate. This intermediate was observed spectroscopically upon addition of a pyridine base to provide a thermodynamic trap.

U2 - 10.1021/ja508367m

DO - 10.1021/ja508367m

M3 - Article

AN - SCOPUS:84908431040

SN - 0002-7863

VL - 136

SP - 14690

EP - 14693

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 42

ER -

Long-range C-H bond activation by RhIII-carboxylates

Résumé

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Contient cette citation

Long-range C-H bond activation by Rh^III-carboxylates