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2015 | 2 | 1 |
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Synthesis of novel chiral bithiophenebased phosphine oxides as Lewis bases in organocatalytic stereoselective reactions

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Novel enantiomerically pure tetramethylbithiophene diphosphine oxides (tetraMe-BITIOPO) featuring differently substituted aromatic rings at the phosphorous atoms were synthesized, fully characterized and isolated in enantiomerically pure form. The new Lewis bases were tested as organocatalysts in two different reactions involving trichlorosilyl compounds. The introduction of electron donating substituents on the aromatic rings connected to the phosphine oxide groups positively affected the chemical and stereochemical catalytic efficiency of these ligands. The new catalysts were able to promote the allylation of aldehydes with allyltrichlorosilane in up to 76% yield and up to 86% enantiomeric excess (ee), and the direct aldol reaction to afford β-hydroxy ketones in high diastereoselectivity (up to 88:12 anti:syn ratio) and up to 72% ee.

Opis fizyczny
  • Dipartimento di Chimica, Universita’ degli Studi di
    Milano, via Golgi 19, 20133 Milano, Italy
  • Dipartimento di Chimica, Universita’ degli Studi di
    Milano, via Golgi 19, 20133 Milano, Italy
  • Dipartimento del Farmaco, Istituto Superiore di Sanità,
    viale Regina Elena 299, 00161 Roma, Italy
  • Dipartimento di Scienza ed Alta Tecnologia
    dell’Università dell’Insubria, via Valleggio, 11, 22100 Como, Italy
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  • [32] In this case, an inseparable mixture of mono- bis- andtriphosphoric chloride products were obtained.
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  • [34] Yields were not optimized.
  • [35] For full characterization and spectroscopic data see: Rossi S.,Chiral Lewis bases activation of trichlorosilyl derivatives, PhDThesis, Università degli Studi di Milano, Milano, Italy, 2010.
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