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<p>The synthesis of the <i>cis</i>-chelates [Pd(DPA<b>)L</b>]BF<sub>4</sub>, [Rh(COD)<b>L</b>]BF<sub>4</sub> (DPA is diphenylallyl, COD is 1,5-cyclooctadiene), and Pt<b>L</b>Cl<sub>2</sub> with a <i>P</i>*,<i>P</i>-ligand (<b>L</b>) containing the rigid <i>P</i>-chiral bicyclophosphoramidite and phosphine donor centers was reported. The composition and structures of the complexes were confirmed by NMR spectroscopy and elemental analysis. The cationic compounds [Rh(COD)<b>L</b>]BF<sub>4</sub> and [Pd(DPA)<b>L</b>]BF<sub>4</sub> were additionally characterized by high-resolution mass spectrometry. The use of [Rh(COD)<b>L</b>]BF<sub>4</sub> (1 mol.%) in the Rh-catalyzed asymmetric hydrogenation of dimethyl itaconate provided up to 98% <i>ee</i> with the complete conversion of the starting substrate.</p>

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Chelate complexes of PdII, RhI, and PtII with P*,P-bidentate phosphine-bicyclophosphoramidite

  • 期刊论文

  • 发表日期：

    2025年8月1日

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  • I. V. Chuchelkin,
  • A. I. Lukankov,
  • V. K. Gavrilov,
  • I. D. Firsin,
  • E. S. Rud,
  • D. A. Fedorov,
  • A. N. Rodionov,
  • K. N. Gavrilov

摘要

The synthesis of the cis-chelates [Pd(DPA)L]BF4, [Rh(COD)L]BF4 (DPA is diphenylallyl, COD is 1,5-cyclooctadiene), and PtLCl2 with a P*,P-ligand (L) containing the rigid P-chiral bicyclophosphoramidite and phosphine donor centers was reported. The composition and structures of the complexes were confirmed by NMR spectroscopy and elemental analysis. The cationic compounds [Rh(COD)L]BF4 and [Pd(DPA)L]BF4 were additionally characterized by high-resolution mass spectrometry. The use of [Rh(COD)L]BF4 (1 mol.%) in the Rh-catalyzed asymmetric hydrogenation of dimethyl itaconate provided up to 98% ee with the complete conversion of the starting substrate.