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Title: Comparative profiling of well-defined copper reagents and precursors for the trifluoromethylation of aryl iodides

Abstract

A number of copper reagents were compared for their effectiveness in trifluoromethylating 4-iodobiphenyl, 4-iodotoluene, and 2-iodotoluene. Yields over time were plotted in order to refine our understanding of each reagent performance, identify any bottlenecks, and provide more insight into the rates of the reactions. Interestingly, differences in reactivity were observed when a well-defined [LCuCF 3] complex was employed directly or generated in situ from precursors by published reports. Relative reactivities were also found to highly dependent on the nature of the iodoarenes.

Authors:
 [1];  [1];  [1];  [1]
  1. Lehigh Univ., Bethlehem, PA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lehigh Univ., Bethlehem, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1502977
Grant/Contract Number:  
[SC0009363]
Resource Type:
Accepted Manuscript
Journal Name:
Beilstein Journal of Organic Chemistry
Additional Journal Information:
[ Journal Volume: 13]; Journal ID: ISSN 1860-5397
Publisher:
Beilstein-Institut
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; benchmarking; copper; fluorine; fluoroalkylation; trifluoromethylation

Citation Formats

Kaplan, Peter T., Lloyd, Jessica A., Chin, Mason T., and Vicic, David A. Comparative profiling of well-defined copper reagents and precursors for the trifluoromethylation of aryl iodides. United States: N. p., 2017. Web. doi:10.3762/bjoc.13.225.
Kaplan, Peter T., Lloyd, Jessica A., Chin, Mason T., & Vicic, David A. Comparative profiling of well-defined copper reagents and precursors for the trifluoromethylation of aryl iodides. United States. doi:10.3762/bjoc.13.225.
Kaplan, Peter T., Lloyd, Jessica A., Chin, Mason T., and Vicic, David A. Mon . "Comparative profiling of well-defined copper reagents and precursors for the trifluoromethylation of aryl iodides". United States. doi:10.3762/bjoc.13.225. https://www.osti.gov/servlets/purl/1502977.
@article{osti_1502977,
title = {Comparative profiling of well-defined copper reagents and precursors for the trifluoromethylation of aryl iodides},
author = {Kaplan, Peter T. and Lloyd, Jessica A. and Chin, Mason T. and Vicic, David A.},
abstractNote = {A number of copper reagents were compared for their effectiveness in trifluoromethylating 4-iodobiphenyl, 4-iodotoluene, and 2-iodotoluene. Yields over time were plotted in order to refine our understanding of each reagent performance, identify any bottlenecks, and provide more insight into the rates of the reactions. Interestingly, differences in reactivity were observed when a well-defined [LCuCF3] complex was employed directly or generated in situ from precursors by published reports. Relative reactivities were also found to highly dependent on the nature of the iodoarenes.},
doi = {10.3762/bjoc.13.225},
journal = {Beilstein Journal of Organic Chemistry},
number = ,
volume = [13],
place = {United States},
year = {2017},
month = {10}
}

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Figures / Tables:

Scheme 1 Scheme 1: Reagents and precursors used for trifluoromethylation reactions.

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Works referenced in this record:

Aromatic Trifluoromethylation with Metal Complexes
journal, August 2011

  • Tomashenko, Olesya A.; Grushin, Vladimir V.
  • Chemical Reviews, Vol. 111, Issue 8
  • DOI: 10.1021/cr1004293

Organometallic Aspects of Fluoroalkylation Reactions with Copper and Nickel
journal, August 2013


Trifluoromethylation of aryl and heteroaryl halides
journal, March 2011


Towards a Practical and Efficient Copper-Catalyzed Trifluoromethylation of Aryl Halides
journal, July 2012


Aromatic trifluoromethylation catalytic in copper
journal, January 2009

  • Oishi, Masahiro; Kondo, Hideaki; Amii, Hideki
  • Chemical Communications, Issue 14
  • DOI: 10.1039/b823249k

Cooperative Effect of Silver in Copper-Catalyzed Trifluoromethylation of Aryl Iodides Using Me 3 SiCF 3
journal, June 2011

  • Weng, Zhiqiang; Lee, Richmond; Jia, Weiguo
  • Organometallics, Vol. 30, Issue 11
  • DOI: 10.1021/om200204y

Cu-catalyzed trifluoromethylation of aryl iodides with trifluoromethylzinc reagent prepared in situ from trifluoromethyl iodide
journal, January 2013

  • Nakamura, Yuzo; Fujiu, Motohiro; Murase, Tatsuya
  • Beilstein Journal of Organic Chemistry, Vol. 9
  • DOI: 10.3762/bjoc.9.277

Copper-Catalyzed Trifluoromethylation of Aryl Iodides with Potassium (Trifluoromethyl)trimethoxyborate
journal, January 2011

  • Knauber, Thomas; Arikan, Fatih; Röschenthaler, Gerd-Volker
  • Chemistry - A European Journal, Vol. 17, Issue 9
  • DOI: 10.1002/chem.201002749

Methyl fluorosulphonyldifluoroacetate; a new trifluoromethylating agent
journal, January 1989

  • Chen, Qing-Yun; Wu, Sheng-Wen
  • Journal of the Chemical Society, Chemical Communications, Issue 11
  • DOI: 10.1039/c39890000705

Structure of Bis(trifluoromethyl)cuprate and Its Role in Trifluoromethylation Reactions
journal, December 2008

  • Dubinina, Galyna G.; Ogikubo, Junichi; Vicic, David A.
  • Organometallics, Vol. 27, Issue 23
  • DOI: 10.1021/om800794m

Active Trifluoromethylating Agents from Well-Defined Copper(I)−CF 3 Complexes
journal, July 2008

  • Dubinina, Galyna G.; Furutachi, Hideki; Vicic, David A.
  • Journal of the American Chemical Society, Vol. 130, Issue 27
  • DOI: 10.1021/ja802946s

A Broadly Applicable Copper Reagent for Trifluoromethylations and Perfluoroalkylations of Aryl Iodides and Bromides
journal, March 2011

  • Morimoto, Hiroyuki; Tsubogo, Tetsu; Litvinas, Nichole D.
  • Angewandte Chemie International Edition, Vol. 50, Issue 16
  • DOI: 10.1002/anie.201100633

CSi bond cleavage of trihalomethyltrimethylsilane by alkoxo- and aryloxogold or -copper complexes
journal, November 2000


Simple, Stable, and Easily Accessible Well-Defined CuCF3 Aromatic Trifluoromethylating Agents
journal, June 2011

  • Tomashenko, Olesya A.; Escudero-Adán, Eduardo C.; Martínez Belmonte, Marta
  • Angewandte Chemie International Edition, Vol. 50, Issue 33
  • DOI: 10.1002/anie.201101577

A novel and convenient method for trifluoromethylation of organic halides using CF3SiR'3/KF/Cu(I) system
journal, January 1991


Mechanism of Trifluoromethylation of Aryl Halides with CuCF 3 and the Ortho Effect
journal, September 2014

  • Konovalov, Andrey I.; Lishchynskyi, Anton; Grushin, Vladimir V.
  • Journal of the American Chemical Society, Vol. 136, Issue 38
  • DOI: 10.1021/ja507564p

Toward Benchmarking in Catalysis Science: Best Practices, Challenges, and Opportunities
journal, March 2016

  • Bligaard, Thomas; Bullock, R. Morris; Campbell, Charles T.
  • ACS Catalysis, Vol. 6, Issue 4
  • DOI: 10.1021/acscatal.6b00183

    Works referencing / citing this record:

    Exploring the Role of Coinage Metalates in Trifluoromethylation: A Combined Experimental and Theoretical Study
    journal, March 2019

    • Martínez de Salinas, Sara; Mudarra, Ángel L.; Odena, Carlota
    • Chemistry – A European Journal, Vol. 25, Issue 40
    • DOI: 10.1002/chem.201900496

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