TY - JOUR
T1 - Esters of 2,5-multisubstituted-1,3-dioxane-2-carboxylic acid
T2 - their conformational analysis and selective hydrolysis
AU - Harabe, Tetsuji
AU - Matsumoto, Takatoshi
AU - Shioiri, Takayuki
N1 - Funding Information:
This work was financially supported in part by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.
PY - 2009/5/16
Y1 - 2009/5/16
N2 - The carbomethoxy group at the C2 position of the 2,5-multisubstituted 1,3-dioxanes prefers the axial conformation rather than the equatorial one due to an anomeric effect. The trans isomers of the 5-monosubstituted compounds are more selectively hydrolyzed than the cis isomers. Based on the calculated results, hydrolysis to the trans isomers is attributed to the larger carbonyl charges of the trans than those of the cis isomers. The anomeric and homoanomeric effects will explain the axial preference of the carbomethoxy group and selective hydrolysis to the trans isomers. Furthermore, the calculated stability between the cis and trans isomers is in good agreement with the experimental results in the equilibrium state.
AB - The carbomethoxy group at the C2 position of the 2,5-multisubstituted 1,3-dioxanes prefers the axial conformation rather than the equatorial one due to an anomeric effect. The trans isomers of the 5-monosubstituted compounds are more selectively hydrolyzed than the cis isomers. Based on the calculated results, hydrolysis to the trans isomers is attributed to the larger carbonyl charges of the trans than those of the cis isomers. The anomeric and homoanomeric effects will explain the axial preference of the carbomethoxy group and selective hydrolysis to the trans isomers. Furthermore, the calculated stability between the cis and trans isomers is in good agreement with the experimental results in the equilibrium state.
KW - 1,3-Dioxane-2-carboxylic acid esters
KW - Anomeric effect
KW - Conformational analysis
KW - Homoanomeric effect
KW - Selective hydrolysis
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U2 - 10.1016/j.tet.2009.02.076
DO - 10.1016/j.tet.2009.02.076
M3 - Article
AN - SCOPUS:64249129071
VL - 65
SP - 4044
EP - 4052
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 20
ER -