TY - JOUR
T1 - CO 2 as versatile carbonation agent of glycosides: Synthesis of 5- and 6-membered cyclic glycocarbonates and investigation of their ring-opening
AU - Pati, Debasis
AU - Feng, Xiaoshuang
AU - Hadjichristidis, Nikolaos
AU - Gnanou, Yves
N1 - KAUST Repository Item: Exported on 2020-04-23
Acknowledged KAUST grant number(s): BAS/1/1374-01-01
Acknowledgements: This research work is supported by KAUST under baseline funding (BAS/1/1374-01-01).
PY - 2018/3/15
Y1 - 2018/3/15
N2 - This study demonstrates the successful use of CO as versatile carbonation agent for the synthesis of 5-membered and 6-membered bicyclic glycocarbonates from methyl α-d-mannopyranoside (MDM) and methyl α-d-galactopyranoside (MDG). On the one hand, these two sugars were cyclized into 5-membered glycocarbonates by mere reaction of CO with their hydroxyls either at cis-2,3 or cis-3,4 positions and without resorting to phosgene or its derivatives. The reactivity of the obtained 5-membered cyclic glycocarbonates were further tested with hexyl- and dodecyl amine. The self-assembling behavior of the formed alkyl glycosides in water was investigated and characterized by transmission electron microscope (TEM). On the other hand, secondary hydroxyls at 2- and 3- positions in MDM and MDG were first protected by a ketal group and by two ether, respectively before subjecting their respective 6-position hydroxyl to bromination. Their respective 6-bromo and 4-hydroxyl functions were subsequently reacted in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and CO. The resulting 6-membered cyclic glycocarbonates were then polymerized using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) or DBU as organocatalyst. All the synthesized 5- and 6-membered cyclic glycocarbonates and polyglycocarbonates were thoroughly characterized by FT-IR, H, C NMR and MALDI-ToF and Gel Permeation Chromatography (GPC).
AB - This study demonstrates the successful use of CO as versatile carbonation agent for the synthesis of 5-membered and 6-membered bicyclic glycocarbonates from methyl α-d-mannopyranoside (MDM) and methyl α-d-galactopyranoside (MDG). On the one hand, these two sugars were cyclized into 5-membered glycocarbonates by mere reaction of CO with their hydroxyls either at cis-2,3 or cis-3,4 positions and without resorting to phosgene or its derivatives. The reactivity of the obtained 5-membered cyclic glycocarbonates were further tested with hexyl- and dodecyl amine. The self-assembling behavior of the formed alkyl glycosides in water was investigated and characterized by transmission electron microscope (TEM). On the other hand, secondary hydroxyls at 2- and 3- positions in MDM and MDG were first protected by a ketal group and by two ether, respectively before subjecting their respective 6-position hydroxyl to bromination. Their respective 6-bromo and 4-hydroxyl functions were subsequently reacted in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and CO. The resulting 6-membered cyclic glycocarbonates were then polymerized using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) or DBU as organocatalyst. All the synthesized 5- and 6-membered cyclic glycocarbonates and polyglycocarbonates were thoroughly characterized by FT-IR, H, C NMR and MALDI-ToF and Gel Permeation Chromatography (GPC).
UR - http://hdl.handle.net/10754/627358
UR - https://www.sciencedirect.com/science/article/pii/S2212982017307047
UR - http://www.scopus.com/inward/record.url?scp=85043272457&partnerID=8YFLogxK
U2 - 10.1016/j.jcou.2018.02.008
DO - 10.1016/j.jcou.2018.02.008
M3 - Article
AN - SCOPUS:85043272457
SN - 2212-9820
VL - 24
SP - 564
EP - 571
JO - Journal of CO2 Utilization
JF - Journal of CO2 Utilization
ER -