title: 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?
abstract: 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.
authors.affiliation: Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, 80-308, Gdańsk, Poland.
authors.forename: Justyna
authors.initials: J
authors.lastname: Bednarko
authors.affiliation: Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, 80-308, Gdańsk, Poland.
authors.forename: Justyna
authors.initials: J
authors.lastname: Wielińska
authors.affiliation: Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, 80-308, Gdańsk, Poland.
authors.forename: Karol
authors.initials: K
authors.lastname: Sikora
authors.affiliation: Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, 80-308, Gdańsk, Poland.
authors.forename: Beata
authors.initials: B
authors.lastname: Liberek
authors.affiliation: Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, 80-308, Gdańsk, Poland. andrzej.nowacki@ug.edu.pl.
authors.forename: Andrzej
authors.initials: A
authors.lastname: Nowacki
mesh_terms: D008353:Mannitol / Q000031:analogs & derivatives*; D008744:Methylamines / Q000737:chemistry*; D008745:Methylation; D008958:Models, Molecular; D011789:Quantum Theory; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D012492:Salts / Q000737:chemistry
chemical_list: D008744:Methylamines; D000644:Quaternary Ammonium Compounds; D012492:Salts; D008353:Mannitol; C023336:trimethylamine
keywords: B3LYP; DFT; M062X; Menshutkin reaction; Methyl transfer; NBO