title: DFT studies of conversion of methyl chloride and three substituted chloromethyl tetrahydrofuran derivatives during reaction with trimethylamine.
abstract: B3LYP/6-31+G level computations were performed for the formation of four trimethylammonium salts in the reaction of methyl chloride (1a), (S)-1,4-andydro-5-chloro-2,3,5-trideoxypentitol (2a), (2S,5S)-2,5-andydro-6-chloro-1,3,4,6-tetradeoxyhexitol (3a) and methyl 5-chloro-2,3,5-trideoxy-β-D-pentofuranoside (4a) with trimethylamine. All the structures were fully optimized in the gas phase, in chloroform and water. In addition, B3LYP/6-311++G and MPW1K/6-31+G level calculations were carried out to estimate activation barrier heights in the gas phase. A detailed description of all stationary points is presented, and the conformational behavior of the THF ring is discussed. B3LYP and MPW1K activation barriers indicate the reaction between methyl chloride and trimethylamine to be the fastest, whereas reaction 4 is the slowest one, both in the gas phase and in solvents. THF ring conformation changes were observed for reactions 2 and 3 along the reaction pathway, whereas it was almost unchanged for reaction 4, in the gas phase. In the case of reactions 2 and 3, different shapes of the THF ring were found for the transition state geometry in the gas phase and in water. The (5) E→E 4 and (3) E→E 5 conformational changes were observed for reactions 2 and 3, respectively.
authors.affiliation: Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, 80-952, Gdańsk, Poland.
authors.forename: Dominik
authors.initials: D
authors.lastname: Walczak
authors.forename: Andrzej
authors.initials: A
authors.lastname: Nowacki
references.citation: J Phys Chem B. 2010 Jul 1;114(25):8425-30
references.pmid: 20527873
references.citation: J Org Chem. 2002 Jul 12;67(14):4647-51
references.pmid: 12098271
references.citation: Carbohydr Res. 2006 Aug 14;341(11):1916-21
references.pmid: 16729990
references.citation: J Comput Aided Mol Des. 2000 Feb;14(2):123-34
references.pmid: 10721501
references.citation: Carbohydr Res. 2004 Jun 1;339(8):1537-44
references.pmid: 15178398
references.citation: Acc Chem Res. 2010 Jan 19;43(1):142-51
references.pmid: 19728702
references.citation: J Am Chem Soc. 1972 Nov 15;94(23):8205-12
references.pmid: 5079964
references.citation: J Phys Chem B. 2006 Feb 2;110(4):1877-88
references.pmid: 16471759
references.citation: J Org Chem. 2009 Nov 20;74(22):8522-30
references.pmid: 19908910
references.citation: J Mol Model. 2013 Aug;19(8):3015-26
references.pmid: 23571822
references.citation: Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
references.pmid: 9944570
references.citation: J Phys Chem A. 2005 Mar 31;109(12):2937-41
references.pmid: 16833612
references.citation: J Am Chem Soc. 2010 Aug 18;132(32):11071-82
references.pmid: 20698673
references.citation: Carbohydr Res. 2004 Oct 4;339(14):2355-62
references.pmid: 15388350
references.citation: J Org Chem. 2005 Dec 9;70(25):10238-46
references.pmid: 16323832