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Absolute Configuration and Conformation of (−)-R-t-Butylphenylphosphinoamidate: Chiroptical Spectroscopy and X-ray Analysis

[Image: see text] The absolute configuration and conformations of (−)-tert-butylphenylphosphinoamidate were determined using three different chiroptical spectroscopic methods, namely vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotatory dispersion (ORD). In...

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Detalles Bibliográficos
Autores principales: Petrovic, Ana G., Polavarapu, Prasad L., Łopusiński, Andrzej, Krasowska, Dorota, Wieczorek, Wanda, Szyrej, Małgorzata, Błaszczyk, Jarosław, Drabowicz, Józef
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7684576/
https://www.ncbi.nlm.nih.gov/pubmed/32786637
http://dx.doi.org/10.1021/acs.joc.0c00756
Descripción
Sumario:[Image: see text] The absolute configuration and conformations of (−)-tert-butylphenylphosphinoamidate were determined using three different chiroptical spectroscopic methods, namely vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotatory dispersion (ORD). In each of the spectroscopic methods used, experimental data for the (−)-enantiomer of tert-butylphenylphosphinoamidate were measured in the solution phase. Using the concentration-dependent experimental infrared spectra, the existence of dimers in the solution was investigated, and the monomer–dimer equilibrium constant was determined. Concomitant quantum mechanical predictions of the VCD, ECD, and ORD for monomeric tert-butylphenylphosphinoamidate were carried out using density functional theory (DFT) calculations using the B3LYP functional and the 6-31G(d), 6-311G(2d,2p) and aug-cc-pVDZ basis sets. Similar predictions for dimeric tert-butylphenylphosphinoamidate were also obtained using the B3LYP/6-31G(d) method. A comparison of theoretically predicted data with the corresponding experimental data led to the elucidation of the absolute configuration as (−)-(R)-tert-butylphenylphosphinoamidate with one predominant conformation in the solution. This conclusion was independently supported by X-ray analysis of the complex with (+)-R-2,2′-dihydroxy-1,1′-binaphthol ((+)-R- BINOL).