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Abstract
Many terpene glycosides exhibit contrasteric patterns of 1,2-diol glycosylation in which the more hindered alcohol bears a sugar; protection of the less hindered alcohol only increases steric repulsion. Here we report a method for contrasteric glycosylation using a new sugar-linker that forms a cleavable, 10-membered ring with high efficiency, leading to syntheses of cotylenin E, J, and ISIR-050. Linker selection was aided by DFT calculations of side reactions and stereoselectivity, as well as conformational analysis using autoDFT, a Python script that converts SMILES strings to DFT-optimized conformational ensembles.
Supplementary materials
Title
Supporting Information
Description
Experimental procedures, characterization data, structural assignments, computational details.
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Title
coordinates files
Description
xyz coordinates from dft calculations
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Supplementary weblinks
Title
autoDFT code and instructions
Description
A program for automated conformer searching and DFT calculations, designed to be user-friendly for experimentalists with no computational background.
Conformer searching is performed using CREST (Pract, P.; Bohle, F.; Grimme, S. Phys. Chem. Chem. Phys. 2020, 22, 7169). The lowest energy conformations within a user-specified window are then optimized with DFT using Gaussian. Scripts are provided to check the progress of Gaussian jobs and extract key thermodynamic data with Goodvibes (Luchini, G.; Alegre-Requena, J. V.; Funes-Ardoiz, I.; Paton, R. S. F1000 Research, 2020, 9, 291.).
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