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2015 | 2 | 1 |

Article title

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.







Physical description


11 - 2 - 2015
15 - 6 - 2015
27 - 11 - 2014


  • 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.
  • [33] Mashima K., Kusano K.-h., Sato N., Matsumura Y.-i., NozakiK., Kumobayashi H., Sayo N., Hori Y., Ishizaki T., AkutagawaS., Takaya H., Cationic BINAP-Ru(II) Halide Complexes:Highly Efficient Catalysts for Stereoselective AsymmetricHydrogenation of alpha- and beta-Functionalized Ketones, J.Org. Chem., 1994, 59, 3064-3076.
  • [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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