A1 Vertaisarvioitu alkuperäisartikkeli tieteellisessä lehdessä
Thermal, Spectroscopic, and Crystallographic Analysis of Mannose-Derived Linear Polyols
Tekijät: Ida Mattsson, Manu Lahtinen, Anssi Peuronen, Abhijit Sau, Andreas Gunell, Tiina Saloranta-Simell, Reko Leino
Kustantaja: AMER CHEMICAL SOC
Julkaisuvuosi: 2018
Journal: Crystal Growth and Design
Tietokannassa oleva lehden nimi: CRYSTAL GROWTH & DESIGN
Lehden akronyymi: CRYST GROWTH DES
Vuosikerta: 18
Numero: 5
Aloitussivu: 3151
Lopetussivu: 3160
Sivujen määrä: 10
ISSN: 1528-7483
DOI: https://doi.org/10.1021/acs.cgd.8b00263
Tiivistelmä
The major diastereomer formed in the Barbier-type metal-mediated allylation of D-mannose has previously been shown to adopt a perfectly linear conformation, both in solid state and in solution, resulting in the formation of hydrogen-bonded networks and subsequent aggregation from aqueous solution upon stirring. Here, a comprehensive study of the solid state structure of both the allylated 0-mannose and its racemic form has been conducted. The binary melting point diagram of the system was determined by differential scanning calorimetry analysis, and the obtained results, along with structure determination by single crystal X-ray diffraction, confirmed that allylated mannose forms a true racemate. Further examination by powder X-ray diffraction and CP MAS C-13 NMR spectroscopy revealed polymorphism both in the pure enantiomer and in the racemate. In addition, the propargylated and hydrogenated analogues of allylated D-mannose were prepared and subjected to thermal and spectroscopic analyses. The crystal structure of the propargylated compound was successfully determined, showing a linear molecular conformation similar to that found for allylated D-mannose. Both new compounds likewise display aggregation behavior in water, further verifying that the low-energy linear conformation plays a significant role in this unusual behavior of these rodlike mannose derivatives.
The major diastereomer formed in the Barbier-type metal-mediated allylation of D-mannose has previously been shown to adopt a perfectly linear conformation, both in solid state and in solution, resulting in the formation of hydrogen-bonded networks and subsequent aggregation from aqueous solution upon stirring. Here, a comprehensive study of the solid state structure of both the allylated 0-mannose and its racemic form has been conducted. The binary melting point diagram of the system was determined by differential scanning calorimetry analysis, and the obtained results, along with structure determination by single crystal X-ray diffraction, confirmed that allylated mannose forms a true racemate. Further examination by powder X-ray diffraction and CP MAS C-13 NMR spectroscopy revealed polymorphism both in the pure enantiomer and in the racemate. In addition, the propargylated and hydrogenated analogues of allylated D-mannose were prepared and subjected to thermal and spectroscopic analyses. The crystal structure of the propargylated compound was successfully determined, showing a linear molecular conformation similar to that found for allylated D-mannose. Both new compounds likewise display aggregation behavior in water, further verifying that the low-energy linear conformation plays a significant role in this unusual behavior of these rodlike mannose derivatives.
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