DFT study of the ring-closing reaction by nucleophilic attack of the free hydroxyl group at the tosylated carbonate of 3-N-methyl thymidine, mannose and glucose derivatives

Data to support article:

CO₂-driven stereochemical inversion of sugars to create thymidine-based polycarbonates by ring-opening polymerisation

DOI: 10.6084/m9.figshare.4309559


Authors:

Georgina L. Gregory,^a Elizabeth M. Hierons,^a Gabriele Kociok-Köhn,^a Ram Sharma^b and Antoine Buchard^a,*

^a Department of Chemistry, University of Bath, Bath BA2 7AY

^b Department of Chemical Engineering, University of Bath, Bath BA2 7AY

DFT study:

- DFT optimised geometries and computed free enthalpies of local minima (intermediates) and local maxima (transition states)  were used to investigate the mechanism of ring-closing by nucleophilic attack of the free hydroxyl group at the tosylated carbonate of derivatives from N-methylthymidine, D-mannose (from Gregory et al., Macromolecules 2016, 49, 7165) and D-glucose (from Mikami et al., J. Am. Chem. Soc. 2013, 135, 6826), so as to evaluate the formation of cyclic carbonate monomer trans-1.

 

Protocol:
rwB97XD/6-31+G(d)/cpcm=acetonitrile/T=298.15K

 

Content:

- Gaussian09 rev D.01 output files

- Ring_Closing_NucAddElim.pdf, illustrating the calculations made and summarising the enthalpies computed.