Mechanistic Study of Stereospecific Substitution of Hydroxyl group in Stereogenic Alcohols

SNIC 2018/3-322


SNAC Medium

Principal Investigator:

Joseph Samec


Stockholms universitet

Start Date:


End Date:


Primary Classification:

10405: Organic Chemistry



We will perform a DFT study of a novel catalyst that Samec's group has developed that can substitute the hydroxyl group in allylic alcohols without prior derivatization. In this procedure, only water is generated as a by-product. This reaction is one of the most waste generating transformations in chemical industries today. The catalytic system developed in our group is noteworthy as a broad scope of nucleophiles are tolerated. We have previously found experimental results (Chem. Eur. J. 2014, 20, 1520–1524) that can not be explained by a reaction mechanism that has previously been proposed based on computations (J. Am. Chem. Soc., 2006, 128, 14306–14317). Therefore, we would need to confirm a novel reaction mechanism by computations. In addition to this we intend to start a study of a novel reaction that is catalyzed by iron. For this reason, we will need to expand our current allocation from 20 000 core hours to at least 60 000, as different spin states of iron have to be considered. Current allocation has not been enough and we have been forced to cue every month. Now with triple amount of calculations for each structure this will not be enough.