Comments on: Connections in chemistry. Anti-malaria drug ↔ organocatalysis. http://www.ch.imperial.ac.uk/rzepa/blog/?p=6998 Chemistry with a twist Thu, 13 Jun 2013 15:16:09 +0000 hourly 1 http://wordpress.org/?v=3.5.1 By: darren http://www.ch.imperial.ac.uk/rzepa/blog/?p=6998&cpage=1#comment-10527 darren Wed, 05 Sep 2012 15:33:24 +0000 http://www.ch.imperial.ac.uk/rzepa/blog/?p=6998#comment-10527 Will do.

Plan:

(i) do some geometry optimisations of the ethyl alcohol intermediate (with and without the -CF3) over the weekend

(ii) try and find the proposed transition states by having a 0deg dihedral angle between the oxygen and the ring

(iii) compare activation energies

(iv) dump results here?

(Hopefully I’ll get beyond the geometry optimisations)

]]> By: Henry Rzepa http://www.ch.imperial.ac.uk/rzepa/blog/?p=6998&cpage=1#comment-10525 Henry Rzepa Wed, 05 Sep 2012 12:16:50 +0000 http://www.ch.imperial.ac.uk/rzepa/blog/?p=6998#comment-10525 I think what you are referring to is a subtle pseudo-rotation process occuring at an iodine centre, which activates the Iodine reagent as an oxidant, and whether that pseudo-rotation might be expedited by the presence of an activating CF3 group. It is entirely possible, and indeed an interesting calculation to undertake. Go for it!

]]> By: darren http://www.ch.imperial.ac.uk/rzepa/blog/?p=6998&cpage=1#comment-10524 darren Wed, 05 Sep 2012 10:10:25 +0000 http://www.ch.imperial.ac.uk/rzepa/blog/?p=6998#comment-10524 After reading your note, I wonder whether or not the rate of this (http://pubs.acs.org/doi/abs/10.1021/ja054446x) sort of reaction would be increased/decreased by using something like this …

C1=CC2C=C(C3=CC=2C(=C1)C(F)(F)F)I(O)(OC3=O)=O

?

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