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Title: Aromatic C–H bond cleavage by using a Cu( i ) ate-complex

Abstract

In situ X-ray absorption spectroscopy (XAS), infrared (IR) and nuclear magnetic resonance (NMR) techniques were used to identify the structures and reactivity of copper-containing active intermediates in the sp 2 C–H bond cleavage reaction of electron-deficient aromatics. An ate-complex [Cu(OtBu)2]Na was found to be able to cleave the C–H bond of benzothiazole (ArH) producing [ArCuI(OtBu)]Na with a rate constant of 3.2 × 10 -2 mol -1 L s -1 at -50 °C and with an activation enthalpy of 0.73 kcal mol-1 at room temperature.

Authors:
; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSFC); Ministry of Education of the People's Republic of China
OSTI Identifier:
1392425
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Organic Chemistry Frontiers (Online)
Additional Journal Information:
Journal Volume: 3; Journal Issue: 8; Journal ID: ISSN 2052-4129
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Guanghui, Yi, Hong, Xin, Jie, Deng, Yi, Bai, Ruopeng, Huang, Zhiliang, Miller, Jeffrey T., Kropf, A. Jeremy, Bunel, Emilio E., Qi, Xiaotian, Lan, Yu, and Lei, Aiwen. Aromatic C–H bond cleavage by using a Cu( i ) ate-complex. United States: N. p., 2016. Web. doi:10.1039/C6QO00201C.
Zhang, Guanghui, Yi, Hong, Xin, Jie, Deng, Yi, Bai, Ruopeng, Huang, Zhiliang, Miller, Jeffrey T., Kropf, A. Jeremy, Bunel, Emilio E., Qi, Xiaotian, Lan, Yu, & Lei, Aiwen. Aromatic C–H bond cleavage by using a Cu( i ) ate-complex. United States. doi:10.1039/C6QO00201C.
Zhang, Guanghui, Yi, Hong, Xin, Jie, Deng, Yi, Bai, Ruopeng, Huang, Zhiliang, Miller, Jeffrey T., Kropf, A. Jeremy, Bunel, Emilio E., Qi, Xiaotian, Lan, Yu, and Lei, Aiwen. Fri . "Aromatic C–H bond cleavage by using a Cu( i ) ate-complex". United States. doi:10.1039/C6QO00201C.
@article{osti_1392425,
title = {Aromatic C–H bond cleavage by using a Cu( i ) ate-complex},
author = {Zhang, Guanghui and Yi, Hong and Xin, Jie and Deng, Yi and Bai, Ruopeng and Huang, Zhiliang and Miller, Jeffrey T. and Kropf, A. Jeremy and Bunel, Emilio E. and Qi, Xiaotian and Lan, Yu and Lei, Aiwen},
abstractNote = {In situ X-ray absorption spectroscopy (XAS), infrared (IR) and nuclear magnetic resonance (NMR) techniques were used to identify the structures and reactivity of copper-containing active intermediates in the sp2 C–H bond cleavage reaction of electron-deficient aromatics. An ate-complex [Cu(OtBu)2]Na was found to be able to cleave the C–H bond of benzothiazole (ArH) producing [ArCuI(OtBu)]Na with a rate constant of 3.2 × 10-2 mol-1 L s-1 at -50 °C and with an activation enthalpy of 0.73 kcal mol-1 at room temperature.},
doi = {10.1039/C6QO00201C},
journal = {Organic Chemistry Frontiers (Online)},
issn = {2052-4129},
number = 8,
volume = 3,
place = {United States},
year = {2016},
month = {1}
}

Works referenced in this record:

Overcoming the “Oxidant Problem”: Strategies to Use O 2 as the Oxidant in Organometallic C–H Oxidation Reactions Catalyzed by Pd (and Cu)
journal, January 2012

  • Campbell, Alison N.; Stahl, Shannon S.
  • Accounts of Chemical Research, Vol. 45, Issue 6
  • DOI: 10.1021/ar2002045

CHEMISTRY: Palladium-Catalyzed Oxidation of Organic Chemicals with O2
journal, September 2005


Room-Temperature Copper-Catalyzed Oxidation of Electron-Deficient Arenes and Heteroarenes Using Air
journal, April 2012

  • Liu, Qiang; Wu, Pan; Yang, Yuhong
  • Angewandte Chemie International Edition, Vol. 51, Issue 19
  • DOI: 10.1002/anie.201200750

Palladium Oxidase Catalysis: Selective Oxidation of Organic Chemicals by Direct Dioxygen-Coupled Turnover
journal, June 2004


Copper-Catalyzed Direct Alkynylation of Electron-Deficient Polyfluoroarenes with Terminal Alkynes Using O 2 as an Oxidant
journal, March 2010

  • Wei, Ye; Zhao, Huaiqing; Kan, Jian
  • Journal of the American Chemical Society, Vol. 132, Issue 8
  • DOI: 10.1021/ja910461e

Reactivity of Dioxygen−Copper Systems
journal, February 2004

  • Lewis, Elizabeth A.; Tolman, William B.
  • Chemical Reviews, Vol. 104, Issue 2
  • DOI: 10.1021/cr020633r

An Aromatic Glaser−Hay Reaction
journal, December 2009

  • Do, Hien-Quang; Daugulis, Olafs
  • Journal of the American Chemical Society, Vol. 131, Issue 47
  • DOI: 10.1021/ja907479j

X-ray absorption edge determination of the oxidation state and coordination number of copper. Application to the type 3 site in Rhus vernicifera laccase and its reaction with oxygen
journal, October 1987

  • Kau, Lung Shan; Spira-Solomon, Darlene J.; Penner-Hahn, James E.
  • Journal of the American Chemical Society, Vol. 109, Issue 21
  • DOI: 10.1021/ja00255a032

Revealing the halide effect on the kinetics of the aerobic oxidation of Cu( i ) to Cu( ii )
journal, January 2015

  • Deng, Yi; Zhang, Guanghui; Qi, Xiaotian
  • Chemical Communications, Vol. 51, Issue 2
  • DOI: 10.1039/C4CC05720A

Transition metal catalyzed oxidative functionalization of carbon–hydrogen bonds
journal, March 2006


Copper-Catalyzed Aerobic Oxidative CH Functionalizations: Trends and Mechanistic Insights
journal, October 2011

  • Wendlandt, Alison E.; Suess, Alison M.; Stahl, Shannon S.
  • Angewandte Chemie International Edition, Vol. 50, Issue 47
  • DOI: 10.1002/anie.201103945

Copper-Catalyzed Direct C–H Oxidative Trifluoromethylation of Heteroarenes
journal, December 2011

  • Chu, Lingling; Qing, Feng-Ling
  • Journal of the American Chemical Society, Vol. 134, Issue 2
  • DOI: 10.1021/ja209992w

Cu(II)-Catalyzed Functionalizations of Aryl C−H Bonds Using O 2 as an Oxidant
journal, May 2006

  • Chen, Xiao; Hao, Xue-Shi; Goodhue, Charles E.
  • Journal of the American Chemical Society, Vol. 128, Issue 21
  • DOI: 10.1021/ja061715q

Direct Observation of Reduction of Cu(II) to Cu(I) by Terminal Alkynes
journal, January 2014

  • Zhang, Guanghui; Yi, Hong; Zhang, Guoting
  • Journal of the American Chemical Society, Vol. 136, Issue 3
  • DOI: 10.1021/ja410756b