TY - JOUR
T1 - Stereoselective Synthesis of Iminosugar 2-Deoxy(thio)glycosides from Bicyclic Iminoglycal Carbamates Promoted by Cerium(IV) Ammonium Nitrate and Cooperative Brønsted Acid-Type Organocatalysis
AU - Herrera-González, Irene
AU - Sánchez-Fernández, Elena M
AU - Sau, Abhijit
AU - Nativi, Cristina
AU - García Fernández, José M
AU - Galán, M Carmen
AU - Ortiz Mellet, Carmen
PY - 2020/4/3
Y1 - 2020/4/3
N2 - The first examples of iminosugar-type 2-deoxy(thio)glycoside mimetics are reported. The key step is the activation of a bicyclic iminoglycal carbamate to generate a highly reactive acyliminium cation. Cerium(IV) ammonium nitrate efficiently promoted the formation of 2-deoxy S-glycosides in the presence of thiols, probably by in situ generation of catalytic HNO3, with complete α-stereoselectivity. Cooperative phosphoric acid/Schreiner's thiourea organocatalysis proved better suited for generating 2-deoxy O-glycosides, significantly broadening the scope of the approach.
AB - The first examples of iminosugar-type 2-deoxy(thio)glycoside mimetics are reported. The key step is the activation of a bicyclic iminoglycal carbamate to generate a highly reactive acyliminium cation. Cerium(IV) ammonium nitrate efficiently promoted the formation of 2-deoxy S-glycosides in the presence of thiols, probably by in situ generation of catalytic HNO3, with complete α-stereoselectivity. Cooperative phosphoric acid/Schreiner's thiourea organocatalysis proved better suited for generating 2-deoxy O-glycosides, significantly broadening the scope of the approach.
U2 - 10.1021/acs.joc.0c00324
DO - 10.1021/acs.joc.0c00324
M3 - Article (Academic Journal)
C2 - 32159355
SN - 0022-3263
VL - 85
SP - 5038
EP - 5047
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 7
ER -