Synthesis, regioselective hydrogenolysis, partial hydrogenation, and conformational study of dioxane and dioxolane-type (9′-anthracenyl)methylene acetals of sugars

Zsolt Jakab, Attila Mándi, A. Borbás, A. Bényei, I. Komáromi, László Lázár, S. Antus, A. Lipták

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Abstract

Dioxane-type (9′-anthracenyl)methylene acetal of methyl 2,3-di-O-methyl-α-d-glucopyranoside was cleaved with LiAlH4/AlCl3 (3:1) or with Na(CN)BH3-HCl regioselectively to provide the 4- or 6-O-(9′-anthracenyl)methyl ether, respectively. Hydrogenolytic reaction of the exo and endo isomers of dioxolane-type acetals proved to be directed by the configuration of the acetalic carbon as well as by the intramolecular participation of the adjacent-free hydroxyl; ring-opening reaction of the endo isomer of the methyl 2,3-O-(9′-anthracenyl)methylene-α-l-rhamnopyranoside took place with complete selectivity resulting in the axial (9′-anthracenyl)methyl ether, whereas a 1:1 mixture of the axial and equatorial ethers was formed upon the same reaction of the exo isomer. Catalytic hydrogenation of the sugar acetals resulted in (9′,10′-dihydro-9′-anthracenyl)methylene derivatives without affecting the acetalic center. High-temperature molecular dynamics simulations and DFT (Density Functional Theory) geometry optimizations were carried out to study the conformation of the dioxane-type (9′,10′-dihydro-9′-anthracenyl)methylene acetal.

Original languageEnglish
Pages (from-to)2444-2453
Number of pages10
JournalCarbohydrate Research
Volume344
Issue number18
DOIs
Publication statusPublished - Dec 14 2009

Fingerprint

Acetals
Hydrogenolysis
Hydrogenation
Sugars
Isomers
Methyl Ethers
Ethers
Molecular Dynamics Simulation
Hydroxyl Radical
Density functional theory
Conformations
Molecular dynamics
Carbon
Derivatives
Temperature
Geometry
formal glycol
1,4-dioxane
Computer simulation

Keywords

  • (9′-Anthracenyl)methylene acetal
  • DFT
  • High-temperature MD
  • Hydrogenolysis
  • Regioselective

ASJC Scopus subject areas

  • Biochemistry
  • Analytical Chemistry
  • Organic Chemistry

Cite this

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title = "Synthesis, regioselective hydrogenolysis, partial hydrogenation, and conformational study of dioxane and dioxolane-type (9′-anthracenyl)methylene acetals of sugars",
abstract = "Dioxane-type (9′-anthracenyl)methylene acetal of methyl 2,3-di-O-methyl-α-d-glucopyranoside was cleaved with LiAlH4/AlCl3 (3:1) or with Na(CN)BH3-HCl regioselectively to provide the 4- or 6-O-(9′-anthracenyl)methyl ether, respectively. Hydrogenolytic reaction of the exo and endo isomers of dioxolane-type acetals proved to be directed by the configuration of the acetalic carbon as well as by the intramolecular participation of the adjacent-free hydroxyl; ring-opening reaction of the endo isomer of the methyl 2,3-O-(9′-anthracenyl)methylene-α-l-rhamnopyranoside took place with complete selectivity resulting in the axial (9′-anthracenyl)methyl ether, whereas a 1:1 mixture of the axial and equatorial ethers was formed upon the same reaction of the exo isomer. Catalytic hydrogenation of the sugar acetals resulted in (9′,10′-dihydro-9′-anthracenyl)methylene derivatives without affecting the acetalic center. High-temperature molecular dynamics simulations and DFT (Density Functional Theory) geometry optimizations were carried out to study the conformation of the dioxane-type (9′,10′-dihydro-9′-anthracenyl)methylene acetal.",
keywords = "(9′-Anthracenyl)methylene acetal, DFT, High-temperature MD, Hydrogenolysis, Regioselective",
author = "Zsolt Jakab and Attila M{\'a}ndi and A. Borb{\'a}s and A. B{\'e}nyei and I. Kom{\'a}romi and L{\'a}szl{\'o} L{\'a}z{\'a}r and S. Antus and A. Lipt{\'a}k",
year = "2009",
month = "12",
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TY - JOUR

T1 - Synthesis, regioselective hydrogenolysis, partial hydrogenation, and conformational study of dioxane and dioxolane-type (9′-anthracenyl)methylene acetals of sugars

AU - Jakab, Zsolt

AU - Mándi, Attila

AU - Borbás, A.

AU - Bényei, A.

AU - Komáromi, I.

AU - Lázár, László

AU - Antus, S.

AU - Lipták, A.

PY - 2009/12/14

Y1 - 2009/12/14

N2 - Dioxane-type (9′-anthracenyl)methylene acetal of methyl 2,3-di-O-methyl-α-d-glucopyranoside was cleaved with LiAlH4/AlCl3 (3:1) or with Na(CN)BH3-HCl regioselectively to provide the 4- or 6-O-(9′-anthracenyl)methyl ether, respectively. Hydrogenolytic reaction of the exo and endo isomers of dioxolane-type acetals proved to be directed by the configuration of the acetalic carbon as well as by the intramolecular participation of the adjacent-free hydroxyl; ring-opening reaction of the endo isomer of the methyl 2,3-O-(9′-anthracenyl)methylene-α-l-rhamnopyranoside took place with complete selectivity resulting in the axial (9′-anthracenyl)methyl ether, whereas a 1:1 mixture of the axial and equatorial ethers was formed upon the same reaction of the exo isomer. Catalytic hydrogenation of the sugar acetals resulted in (9′,10′-dihydro-9′-anthracenyl)methylene derivatives without affecting the acetalic center. High-temperature molecular dynamics simulations and DFT (Density Functional Theory) geometry optimizations were carried out to study the conformation of the dioxane-type (9′,10′-dihydro-9′-anthracenyl)methylene acetal.

AB - Dioxane-type (9′-anthracenyl)methylene acetal of methyl 2,3-di-O-methyl-α-d-glucopyranoside was cleaved with LiAlH4/AlCl3 (3:1) or with Na(CN)BH3-HCl regioselectively to provide the 4- or 6-O-(9′-anthracenyl)methyl ether, respectively. Hydrogenolytic reaction of the exo and endo isomers of dioxolane-type acetals proved to be directed by the configuration of the acetalic carbon as well as by the intramolecular participation of the adjacent-free hydroxyl; ring-opening reaction of the endo isomer of the methyl 2,3-O-(9′-anthracenyl)methylene-α-l-rhamnopyranoside took place with complete selectivity resulting in the axial (9′-anthracenyl)methyl ether, whereas a 1:1 mixture of the axial and equatorial ethers was formed upon the same reaction of the exo isomer. Catalytic hydrogenation of the sugar acetals resulted in (9′,10′-dihydro-9′-anthracenyl)methylene derivatives without affecting the acetalic center. High-temperature molecular dynamics simulations and DFT (Density Functional Theory) geometry optimizations were carried out to study the conformation of the dioxane-type (9′,10′-dihydro-9′-anthracenyl)methylene acetal.

KW - (9′-Anthracenyl)methylene acetal

KW - DFT

KW - High-temperature MD

KW - Hydrogenolysis

KW - Regioselective

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U2 - 10.1016/j.carres.2009.09.007

DO - 10.1016/j.carres.2009.09.007

M3 - Article

VL - 344

SP - 2444

EP - 2453

JO - Carbohydrate Research

JF - Carbohydrate Research

SN - 0008-6215

IS - 18

ER -