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DFT studies on the base-facilitated direct coupling of carbon dioxide with 2,2-dimethyl-1,3-propanediol
dataset
posted on 2018-10-03, 13:13 authored by Thomas McGuireThomas McGuire, Antoine BuchardAntoine BuchardDFT calculations to support the article 'Synthesis of 5-to 8- membered cyclic carbonates from diols and CO2: a one-step, atmospheric pressure and ambient temperature procedure'
DFT study comprises:
-DFT optimised geometries and computed enthalpies were used to calculate the thermodynamics and kinetics of the carbonation of 2,2-dimethyl-1,3-propanediol's alcohol moiety facilitated by NEt3, TMP, pyridine and DBU
into the hydroxyl via a ternary Lewis
base-CO2-diol mechanism.
-DFT optimised geometries and computed enthalpies were used to calculate the thermodynamics and kinetics of the cyclisation of 4,4-dimethyl-7-oxo-7-(tosyloxy)heptanoate
(BCI) to form 5,5-dimethyl-1,3-dioxan-2-one.
-DFT optimised geometries and computed enthalpies were used to calculate the thermodynamics and kinetics of the NEt3-facilitated direct coupling
of CO2 with 2,2-dimethyl-1,3-propanediol to form 5,5-dimethyl-1,3-dioxan-2-one via three competitive mechanistic pathways.
Protocol:
rωb97xD/6-31+g(d)/cpcm=acetonitrile/298K
Content:
-Gaussian09 rev D.01 output files
-CO2_insertion_comparison.pdf, illustrating the calculations made and summarising the enthalpies computed for NEt3, TMP, pyridine and DBU into the hydroxyl group of 2,2-dimethyl-1,3-propanediol via a ternary Lewis base-CO2-diol mechanism.
-BCI_cyclisation.pdf, illustrating the calculations made and summarising the enthalpies computed for the cyclisation of BCI to form 5,5-dimethyl-1,3-dioxan-2-one
- NEt3_mechanism, illustrating the calculations made and summarising the enthalpies computed for the direct coupling of CO2 with 2,2-dimethyl-1,3-propanediol to form 5,5-dimethyl-1,3-dioxan-2-one via three competitive mechanistic pathways.
