Adding a structural context to the deprotometalation and trans-metal trapping chemistry of phenyl-substituted benzotriazole

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Fuentes, M. Ángeles and Kennedy, Alan R. and Mulvey, Robert E. and Parkinson, John A. and Rantanen, Toni and Robertson, Stuart D. and Snieckus, Victor (2015) Adding a structural context to the deprotometalation and trans-metal trapping chemistry of phenyl-substituted benzotriazole. Chemistry - A European Journal, 21 (42). pp. 14812-14822. ISSN 1521-3765 (https://doi.org/10.1002/chem.201502534)

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Abstract

Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single-component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1-phenyl-1H-benzotriazole, which was previously deprotonated by an in situ ZnCl2• TMEDA/LiTMP (TMEDA=N,N,N′,N′-tetramethylethylenediamine; TMP=2,2,6,6-tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single-component base as the crystalline product obtained was [{4-R-1-(2-lithiophenyl)-1H-benzotriazole• 3THF}2], [R=2-C6H4(Ph)NLi], in which ring opening of benzotriazole and N2 extrusion had occurred. Supporting lithiation by adding iBu2Al(TMP) induces trans-metal trapping, in which C-Li bonds transform into C-Al bonds to stabilise the metalated intermediate. X-ray diffraction studies revealed homodimeric [(4-R′-1-phenyl-1H-benzotriazole)2], [R′=(iBu)2Al(μ-TMP)Li], and its heterodimeric isomer [(4-R′-1-phenyl-1H-benzotriazole){2-R′-1-phenyl-1H-benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy.

ORCID iDs

Fuentes, M. Ángeles, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564, Parkinson, John A. ORCID logoORCID: https://orcid.org/0000-0003-4270-6135, Rantanen, Toni, Robertson, Stuart D. ORCID logoORCID: https://orcid.org/0000-0002-9330-8770 and Snieckus, Victor;
  • Item type:Article
    ID code:55447
    Dates:
    Date
    Event
    12 October 2015
    Published
    21 September 2015
    Published Online
    7 August 2015
    Accepted
    Notes:This is the peer reviewed version of the following article: Fuentes, M. Á., Kennedy, A. R., Mulvey, R. E., Parkinson, J. A., Rantanen, T., Robertson, S. D., & Snieckus, V. (2015). Adding a structural context to the deprotometalation and trans-metal trapping chemistry of phenyl-substituted benzotriazole. Chemistry - A European Journal , 21(42), 14812-14822, which has been published in final form at http://dx.doi.org/10.1002/chem.201502534. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:03 Feb 2016 15:24
    Last modified:11 Nov 2024 11:18
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/55447
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