Probing the influence of stereoelectronic effects on lithium affinity in 1,3- and 1,4-dioxa systems

Bishwajit Ganguly; Benzion Fuchs

doi:10.1002/poc.397

Probing the influence of stereoelectronic effects on lithium affinity in 1,3- and 1,4-dioxa systems

Bishwajit Ganguly, Benzion Fuchs^*

^*Corresponding author for this work

School of Chemistry

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

Abstract

A combined computational and structural study of the lithium affinity (LA) of OCO systems exhibiting the anomeric effect and of O CCO systems exhibiting the gauche effect is presented. QM ab initio calculations using the MP2/6-31G* basis set were carded out on the gas-phase lithium affinities of dimethoxymethane (DMOM), dimethoxyethane (DMOE), 1,3-dioxane (DOX) and cis- and trans-tetraoxadecalin (TOD), along with that of dimethyl ether and of its dimer as reference compounds. Structural parameters were retrieved from the Cambridge Structural Database (CSD) for diethyl ether dimer and OCCO lithium complexes and these agreed well with the calculated data. The computed lithium affinities of dimethoxymethane and dimethoxyethane were found to be conformationally dependent. The LAs are conformationally dependent (wherever applicable) and decrease in the order: (Me₂O)₂ > DMOE > DMOM > DOD > DOX > trans-TOD, but cis-TOD restores the high LA (better than DMOE) by virtue of multiple coordination.

Original language	English
Pages (from-to)	488-494
Number of pages	7
Journal	Journal of Physical Organic Chemistry
Volume	14
Issue number	7
DOIs	https://doi.org/10.1002/poc.397
State	Published - Jul 2001

Keywords

Acetals
Anomeric effect
Gauche effect
Lithium affinity
Stereoelectronic effects
Tetraoxadecalin

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10.1002/poc.397

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title = "Probing the influence of stereoelectronic effects on lithium affinity in 1,3- and 1,4-dioxa systems",

abstract = "A combined computational and structural study of the lithium affinity (LA) of OCO systems exhibiting the anomeric effect and of O CCO systems exhibiting the gauche effect is presented. QM ab initio calculations using the MP2/6-31G* basis set were carded out on the gas-phase lithium affinities of dimethoxymethane (DMOM), dimethoxyethane (DMOE), 1,3-dioxane (DOX) and cis- and trans-tetraoxadecalin (TOD), along with that of dimethyl ether and of its dimer as reference compounds. Structural parameters were retrieved from the Cambridge Structural Database (CSD) for diethyl ether dimer and OCCO lithium complexes and these agreed well with the calculated data. The computed lithium affinities of dimethoxymethane and dimethoxyethane were found to be conformationally dependent. The LAs are conformationally dependent (wherever applicable) and decrease in the order: (Me2O)2 > DMOE > DMOM > DOD > DOX > trans-TOD, but cis-TOD restores the high LA (better than DMOE) by virtue of multiple coordination.",

keywords = "Acetals, Anomeric effect, Gauche effect, Lithium affinity, Stereoelectronic effects, Tetraoxadecalin",

author = "Bishwajit Ganguly and Benzion Fuchs",

year = "2001",

month = jul,

doi = "10.1002/poc.397",

language = "אנגלית",

volume = "14",

pages = "488--494",

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AU - Fuchs, Benzion

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N2 - A combined computational and structural study of the lithium affinity (LA) of OCO systems exhibiting the anomeric effect and of O CCO systems exhibiting the gauche effect is presented. QM ab initio calculations using the MP2/6-31G* basis set were carded out on the gas-phase lithium affinities of dimethoxymethane (DMOM), dimethoxyethane (DMOE), 1,3-dioxane (DOX) and cis- and trans-tetraoxadecalin (TOD), along with that of dimethyl ether and of its dimer as reference compounds. Structural parameters were retrieved from the Cambridge Structural Database (CSD) for diethyl ether dimer and OCCO lithium complexes and these agreed well with the calculated data. The computed lithium affinities of dimethoxymethane and dimethoxyethane were found to be conformationally dependent. The LAs are conformationally dependent (wherever applicable) and decrease in the order: (Me2O)2 > DMOE > DMOM > DOD > DOX > trans-TOD, but cis-TOD restores the high LA (better than DMOE) by virtue of multiple coordination.

AB - A combined computational and structural study of the lithium affinity (LA) of OCO systems exhibiting the anomeric effect and of O CCO systems exhibiting the gauche effect is presented. QM ab initio calculations using the MP2/6-31G* basis set were carded out on the gas-phase lithium affinities of dimethoxymethane (DMOM), dimethoxyethane (DMOE), 1,3-dioxane (DOX) and cis- and trans-tetraoxadecalin (TOD), along with that of dimethyl ether and of its dimer as reference compounds. Structural parameters were retrieved from the Cambridge Structural Database (CSD) for diethyl ether dimer and OCCO lithium complexes and these agreed well with the calculated data. The computed lithium affinities of dimethoxymethane and dimethoxyethane were found to be conformationally dependent. The LAs are conformationally dependent (wherever applicable) and decrease in the order: (Me2O)2 > DMOE > DMOM > DOD > DOX > trans-TOD, but cis-TOD restores the high LA (better than DMOE) by virtue of multiple coordination.

KW - Acetals

KW - Anomeric effect

KW - Gauche effect

KW - Lithium affinity

KW - Stereoelectronic effects

KW - Tetraoxadecalin

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JO - Journal of Physical Organic Chemistry

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Probing the influence of stereoelectronic effects on lithium affinity in 1,3- and 1,4-dioxa systems

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Keywords

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