The conformational behavior, geometry and energy parameters of Menshutkin-like reaction of O-isopropylidene-protected glycofuranoid mesylates in view of DFT calculations

DFT studies on the mechanism of the formation of "gemini" quaternary ammonium salts in the reaction of 1,4:3,6-dianhydro-D-mannitol ditriflate derivative with trimethylamine and its subsequent conversion to tertiary amine through the methyl-transfer reaction are discussed. Two alternative reaction pathways are presented in the gas phase and in ethanol. Additionally, the transformation of the monotriflate derivative of 1,4:3,6-dianhydro-D-mannitol into the single quaternary ammonium salt is presented. Two functionals (B3LYP, M062X) and two basis sets (6-31+G** and 6-311++G**) were used for the calculations. The effect of the substituent attached to the five-membered rings at the C2 (and/or C5) carbon atom on the activation barrier is described. The trimethylammonium group bond to the five-membered ring greatly reduces the activation barrier height. The preferred reaction pathway for the conversions was established. Including the London dispersion in the calculations increases the stabilization of all the points on the potential energy surface in relation to individual reactants.

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Theoretical studies on the reaction of mono- and ditriflate derivatives of 1,4:3,6-dianhydro-d-mannitol with trimethylamine—Can a quaternary ammonium salt be a source of the methyl group?

Bednarko

Wielińska

Sikora

et al. 2015

J Comput Aided Mol Des

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DFT studies of the formation of furanoid derivatives of ammonium chlorides

Wielińska

Liberek

Nowacki

2015

Journal of Molecular Graphics and Modelling

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Threocytidines: Insight into the Conformational Preferences of Artificial Threose Nucleic Acid (TNA) Building Blocks in B3LYP Studies

Bednarko

Stachurski

Wielińska

et al. 2018

Journal of Molecular Graphics and Modelling

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The conformational behavior, geometry and energy parameters of Menshutkin-like reaction of O-isopropylidene-protected glycofuranoid mesylates in view of DFT calculations

Cited by 4 publications

References 47 publications

Theoretical studies on the reaction of mono- and ditriflate derivatives of 1,4:3,6-dianhydro-d-mannitol with trimethylamine—Can a quaternary ammonium salt be a source of the methyl group?

Theoretical studies on the reaction of mono- and ditriflate derivatives of 1,4:3,6-dianhydro-d-mannitol with trimethylamine—Can a quaternary ammonium salt be a source of the methyl group?

DFT studies of the formation of furanoid derivatives of ammonium chlorides

Threocytidines: Insight into the Conformational Preferences of Artificial Threose Nucleic Acid (TNA) Building Blocks in B3LYP Studies

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