[cheemstudent]

Hey there,
this is my first time posting, so i don't really know how it works..
Here is my problem: i got this article given by a teacher, and we have to write a report about it. the thing is, i can't figure out the mechanism that are taking place for the reaction. I was only able to figure out steps 5-6, 6-7, 7-8, 10-11.
but for the 3-4,4-5,8-9,9-10, i am stuck... i am not sure which of the given starting material take part in the actual reaction, or if they are just there their various properties.
If anyone could help me figure out any of the mechanism described above it would be great!
Here is the link to the article:
http://pubs.acs.org/doi/full/10.1021/jo100936f
Thank you!

[Dan]

1. You must show you have attempted the question, this is a Forum Rule. Do you have any ideas? e.g. For steps 3-4 and 8-9 the authors provide references to a papers that explains what is happening in more detail - start by looking up these articles.

2. It is better if you post ChemDraw schemes. Not all of our users will have free access to the paper and will therefore not be able to help you.

[cheemstudent]

I tried looking up the cited article, unfortunately the mechanism aren't specified. it indicates Paraformaldehyde with phenol --> and you got the benzofurane... but i don't know how it got to that point ...
I will try to post chemdraw sketchs once i've made them!
thanks

[cheemstudent]

For exemple:
in reaction 3-4, they indicate that during the reaction, we have MgCL2, triEthylamine, paraformaldehyde and our 2-ethyl phenol.
So the reaction really takes place between the phenol and the paraformaldehyde right?

[Dan]

Well, they also give the name of the reaction: Casiraghi formylation. If I google that, the first hit has the full mechanism...

[cheemstudent]

I already had looked up the first hit: it gives an article, but no mechanism...
But the second one does for this reaction!

Thanks

[cheemstudent]

I believe to have found every mechanism in the article, except for the steps 8-9... i can't figure out the mechanism to transform an alcool into an acetate.
Does the CO3^- déprotonate the alcool, then there is a substitution on the isopropenyl acetate?

[Dan]

Basically yes, it is an enzyme-catalysed acetylation.

The Ru catalyst is important, you should make sure you know what it does (follow ref 10a in the paper you posted). Maybe look up the concept of dynamic kinetic resolution as well.

[cheemstudent]

Ok thank you.
i did look up DKR and i think i should describe thoroughly the method in my report.
Thanks again for the help,
a french chem student