Resolving P-stereogenic enantiomers at nonambient-conditions

The phosphorus (P)-stereogenic enantiomers are used in many fields of chemistry, for example in chiral catalysis, stereoselective transformation and optical resolution. They are in the forefront of interest in the last decade. Several dialkyl-arylphosphine oxide compounds have been prepared by Péter Bagi and his co-workers [1]. The newly synthetized phosphorous derivatives are sensitive racemic compounds. Trying several resolving agents, resolution was performed and the enantiomers were separated with (R,R)- or (S,S) -spiro-TADDOL (-1,4-dioxaspiro[4.5]decane-2,3-diylbis(diphenylmethanol)) in gram scale. Some diastereomers of the series (i.e. methylphenylpropylphosphine oxide and ethylphenylpropylphosphine oxide) were crystallized in nitrogen atmosphere, and investigated by single crystal X-ray diffraction (Figure 1). The absolute configurations of the dialkyl-arylphosphine oxides were successfully determined [2]. We present the structures of a few diastereomers formed using TADDOL, where the SXRD results revealed the main interactions which contribute to the enantiomeric recognition. Hirshfeld surface analysis and DFT calculation were performed using the software Crystal Explorer in order to understand the secondary interaction network.

Holczbauer, T., Varga, B., Herbay, R., Székely, G., Madarász, J., Mátravölgyi, B., Fogassy, E., Keglevich, G., & Bagi, P. (2021). Resolving P-stereogenic enantiomers at nonambient conditions. Acta Crystallographica Section A Foundations and Advances, 77(a2), C1020–C1020.

Tamas Holczbauer is grateful for the support of the National Research, Development and Innovation Office-NKFIH (Grant No. OTKA PD 128504 and OTKA K 124544).

Conference/Event Name
XXV IUCr Congress


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