Esters of 2,5-multisubstituted-1,3-dioxane-2-carboxylic acid: their conformational analysis and selective hydrolysis

Tetsuji Harabe; Takatoshi Matsumoto; Takayuki Shioiri

doi:10.1016/j.tet.2009.02.076

Esters of 2,5-multisubstituted-1,3-dioxane-2-carboxylic acid: their conformational analysis and selective hydrolysis

Tetsuji Harabe, Takatoshi Matsumoto, Takayuki Shioiri

Division of Organic- and Biomaterials Research

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	4044-4052
Number of pages	9
Journal	Tetrahedron
Volume	65
Issue number	20
DOIs	https://doi.org/10.1016/j.tet.2009.02.076
Publication status	Published - 2009 May 16

Keywords

1,3-Dioxane-2-carboxylic acid esters
Anomeric effect
Conformational analysis
Homoanomeric effect
Selective hydrolysis

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

Access to Document

10.1016/j.tet.2009.02.076

Fingerprint Dive into the research topics of 'Esters of 2,5-multisubstituted-1,3-dioxane-2-carboxylic acid: their conformational analysis and selective hydrolysis'. Together they form a unique fingerprint.

Cite this

@article{f2d7b2b180b94e04a8dd784fbda1615f,

title = "Esters of 2,5-multisubstituted-1,3-dioxane-2-carboxylic acid: their conformational analysis and selective hydrolysis",

abstract = "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.",

keywords = "1,3-Dioxane-2-carboxylic acid esters, Anomeric effect, Conformational analysis, Homoanomeric effect, Selective hydrolysis",

author = "Tetsuji Harabe and Takatoshi Matsumoto and Takayuki Shioiri",

year = "2009",

month = may,

day = "16",

doi = "10.1016/j.tet.2009.02.076",

language = "English",

volume = "65",

pages = "4044--4052",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier Limited",

number = "20",

}

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

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

UR - http://www.scopus.com/inward/record.url?scp=64249129071&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=64249129071&partnerID=8YFLogxK

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 -