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Abstract <p>The reaction of tetralone azine with methyllithium in tetrahydrofuran releases 1 mol of CH<sub>4</sub> and yields the lithium salt of enamine <b>I</b>, which crystallizes as a dimer in which lithium atoms bridge the <i>sp</i><sup>3</sup>- and <i>sp</i><sup>2</sup>-hybridized nitrogen atoms of two ligands, forming a six-membered LiNNLiNN metallacycle (CCDC no.&#xa0;2426300). Analysis of the electron density topology using the noncovalent interaction index and source function revealed that each lithium atom in complex <b>I</b> interacts with the NNCC fragment of the ligand. Charge distribution analysis in the ligand anion showed that position C(2) is the most favorable site for electrophilic attack. DFT calculations demonstrated that phosphorylation of deprotonated tetralone azine with PCl<sub>3</sub> is thermodynamically more favorable by 12.6 kcal/mol than phosphorylation at the nitrogen atom.</p>

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Metallation of Ketazines: Reaction of Tetralone Azine with Methyllithium

  • 期刊论文

  • 发表日期：

    2025年6月1日

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  • V. V. Sushev,
  • N. V. Zolotareva,
  • M. D. Grishin,
  • R. V. Rumyantcev,
  • G. K. Fukin,
  • A. N. Kornev

摘要

Abstract

The reaction of tetralone azine with methyllithium in tetrahydrofuran releases 1 mol of CH4 and yields the lithium salt of enamine I, which crystallizes as a dimer in which lithium atoms bridge the sp3- and sp2-hybridized nitrogen atoms of two ligands, forming a six-membered LiNNLiNN metallacycle (CCDC no. 2426300). Analysis of the electron density topology using the noncovalent interaction index and source function revealed that each lithium atom in complex I interacts with the NNCC fragment of the ligand. Charge distribution analysis in the ligand anion showed that position C(2) is the most favorable site for electrophilic attack. DFT calculations demonstrated that phosphorylation of deprotonated tetralone azine with PCl3 is thermodynamically more favorable by 12.6 kcal/mol than phosphorylation at the nitrogen atom.