TY - JOUR
T1 - Unexpected Diastereomer Formation and Interconversions in Cyclohexane-1,2-diacetal Derivatization of a Glucuronic Acid Thioglycoside
AU - Alharthi, Fahad Ayesh
AU - Potter, Garrett T.
AU - Jayson, Gordon C.
AU - Whitehead, George F. S.
AU - Vitórica-Yrezábal, Iñigo J.
AU - Gardiner, John M.
PY - 2023/4/7
Y1 - 2023/4/7
N2 - Reactions of a glucuronic acid (GlcA) β-thioglycoside with cyclohexadione show initial formation of the two anticipated all-trans decalin-type O2,O3 and O3,O4 cyclohexane-1,2-diacetals (CDAs) along with an epimer of the main O2,O3 acetal. This trans–cis isomer is then interconverted leading to higher amounts of the two all-trans products. Isomerization studies indicate slow interconversion between the all-trans CDA acetals, with only one undergoing significant interconversion with the minor 2,3-diastereomer. Crystal structures of all three isomers are included. These findings are relevant to other uses of CDA protections where occurrence of apparently disfavored isomers may be occurring, along with interconversions between CDA isomers.
AB - Reactions of a glucuronic acid (GlcA) β-thioglycoside with cyclohexadione show initial formation of the two anticipated all-trans decalin-type O2,O3 and O3,O4 cyclohexane-1,2-diacetals (CDAs) along with an epimer of the main O2,O3 acetal. This trans–cis isomer is then interconverted leading to higher amounts of the two all-trans products. Isomerization studies indicate slow interconversion between the all-trans CDA acetals, with only one undergoing significant interconversion with the minor 2,3-diastereomer. Crystal structures of all three isomers are included. These findings are relevant to other uses of CDA protections where occurrence of apparently disfavored isomers may be occurring, along with interconversions between CDA isomers.
UR - https://doi.org/10.1021/acs.orglett.3c00255
U2 - 10.1021/acs.orglett.3c00255
DO - 10.1021/acs.orglett.3c00255
M3 - Article
SN - 1523-7052
SP - 2196
JO - Organic Letters
JF - Organic Letters
ER -