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Chemoselective Cleavage of Si–C(sp3) Bonds in Unactivated Tetraalkylsilanes Using Iodine Tris(trifluoroacetate)

  • Keitaro Matsuoka
    Keitaro Matsuoka
    Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
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  • , 
  • Narumi Komami
    Narumi Komami
    Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
    More by Narumi Komami
  • , 
  • Masahiro Kojima
    Masahiro Kojima
    Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
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    Orcidhttp://orcid.org/0000-0002-4619-2621
  • , 
  • Tsuyoshi Mita
    Tsuyoshi Mita
    Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Japan
    JST, ERATO Maeda Artificial Intelligence for Chemical Reaction Design and Discovery Project, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
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    Orcidhttp://orcid.org/0000-0002-6655-3439
  • , 
  • Kimichi Suzuki
    Kimichi Suzuki
    Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Japan
    JST, ERATO Maeda Artificial Intelligence for Chemical Reaction Design and Discovery Project, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
    Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan
    More by Kimichi Suzuki
    Orcidhttp://orcid.org/0000-0002-4080-5036
  • , 
  • Satoshi Maeda
    Satoshi Maeda
    Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Japan
    JST, ERATO Maeda Artificial Intelligence for Chemical Reaction Design and Discovery Project, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
    Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan
    More by Satoshi Maeda
    Orcidhttp://orcid.org/0000-0001-8822-1147
  • , 
  • Tatsuhiko Yoshino*
    Tatsuhiko Yoshino
    Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
    *[email protected]
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    Orcidhttp://orcid.org/0000-0001-9441-9272
  • , and 
  • Shigeki Matsunaga*
    Shigeki Matsunaga
    Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
    Global Station for Biosurfaces and Drug Discovery, Hokkaido University, Sapporo 060-0812, Japan
    *[email protected]
    More by Shigeki Matsunaga
    Orcidhttp://orcid.org/0000-0003-4136-3548
Cite this: J. Am. Chem. Soc. 2021, 143, 1, 103–108
Publication Date (Web):December 24, 2020
https://doi.org/10.1021/jacs.0c11645
Copyright © 2020 American Chemical Society
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    Abstract

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    Organosilanes are synthetically useful reagents and precursors in organic chemistry. However, the typical inertness of unactivated Si–C(sp3) bonds under conventional reaction conditions has hampered the application of simple tetraalkylsilanes in organic synthesis. Herein we report the chemoselective cleavage of Si–C(sp3) bonds of unactivated tetraalkylsilanes using iodine tris(trifluoroacetate). The reaction proceeds smoothly under mild conditions (−50 °C to room temperature) and tolerates various polar functional groups, thus enabling subsequent Tamao–Fleming oxidation to provide the corresponding alcohols. NMR experiments and density functional theory calculations on the reaction indicate that the transfer of alkyl groups from Si to the I(III) center and the formation of the Si–O bond proceed concertedly to afford an alkyl-λ3-iodane and silyl trifluoroacetate. The developed method enables the use of unactivated tetraalkylsilanes as highly stable synthetic precursors.

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