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A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

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Uncovering the hidden reactivity of benzyne/aryne precursors utilized under milder condition: Bonding and stability

Sai Manoj N V T Gorantla¹, Kartik Chandra Mondal¹

¹Department of Chemistry, Indian Institute of Technology Madras, Chennai, India.

Journal of Computational Chemistry

|July 21, 2022

Abstract:

Arenes [C₆ H₃ R(TMS)(OTf); also called benzyne/aryne precursors] containing inter-related leaving groups Me₃ Si (TMS) and CF₃ SO₃ (OTf) on the adjacent positions (1,2-position) are generally converted to their corresponding aryne-intermediates via the addition of fluoride anion (F^- ) and subsequent elimination of TMS and OTf groups. This reaction is believed to proceed via the formation of an anionic intermediate [C₆ H₄ (TMS-F)(OTf)]^- . The EDA-NOCV analysis (EDA-NOCV = energy decomposition analysis-natural orbital for chemical valence) of over 35 such precursors of varied types have been reported to reveal bonding and stability of C_Ar Si and COTf bonds. EDA-NOCV showed that the nature of the C_Ar Si bond of C₆ H₃ R(TMS)(OTf) can be expressed as both dative and electron sharing [C_Ar Si, C_Ar →Si]. The C_Ar OTf bond, on the other hand, can be described explicitly as dative [C_Ar ←OTf]. The nature of C_Ar Si bond of [C₆ H₄ (TMS-F)(OTf)]^- exclusively changes to covalent dative σ-bond C_Ar →S(Me)3F on the attachment of F^- to the TMS group of C₆ H₄ (TMS)(OTf). Introduction of σ-electron withdrawing group (like OMe, NMe₂ , and NO₂ ) to the ortho-position of the TMS group of functionalized arynes C₆ H₃ R(TMS)(OTf) prefer to have a covalent dative σ-bond (C_Ar →Si) over an electron-sharing covalent σ-bond (C_Ar Si). If this σ-electron withdrawing group is shifted from ortho-position to meta- and para-positions, then the preference for a dative bond decreases significantly, implying that the electronic effect on the nature of chemical bonds affects through bond paths. This effect dies with distance, similar to the well-known inductive effect.

Keywords:

DFT calculation EDA-NOCV QTAIM benzyne/aryne precursor electron-sharing versus dative bond

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