[curiouscat]

A follow up to my previous thread (*): If I wanted to introduce more -OH groups into this molecule below, what might be good strategies? i.e. What are some intuitive targets that might be coupled onto this molecule to give a resultant molecule rich in -OH groups, preferably phenolic -OH groups?




I see either the ketonic (too sterically hindered?) or the hydroxyl groups as potential targets for a coupling. Perhaps there are other better possibilities? I am currently exploring esterification but any coupling candidate that has both a -COOH & -OH tends to couple internally, so that's one drawback, though not a fatal one.


* http://www.chemicalforums.com/index.php?topic=74053.msg268598#new

[kriggy]

What about nitration -> reduction -> diazotation -> substitution? The nitration might oxidize the whole molecule so not sure if it works.
Maybe reduction of the carbonyl group?

[Eloquentia]

In your case I would look at the ketone.  If I needed to connect phenols, I would think of condensation reactions, which would increase the electron conjugation in the product and thus stabilize it.  I know that anilines are generally not very reactive, but explore a possibility to get an imine, conjugated to a ring. Trimethyl borate could help you push the system towards the imine by reacting with water. 
Another possibility is to go for reductive alkylation of say a benzylamine derivative with the ketone (but then you have to deal with a chiral center). You could also try and prepare an imine from a benzylamine derivative without reducing it. It might be stable due to conjugation to the rings existing in your starting material.

[discodermolide]

Why not try a partial polymerisation with formaldehyde? Thing is I don't know how you would control this.
The is also the possibility of some sort of oxidative coupling.

[curiouscat]

Why not try a partial polymerisation with formaldehyde? Thing is I don't know how you would control this.

I'll give this a shot! Control would be tricky I guess, or I'll end up with a mass of bakelite like goo.

[curiouscat]

Another possibility is to go for reductive alkylation of say a benzylamine derivative with the ketone (but then you have to deal with a chiral center).

Thanks for the ideas! For now, I'm  ignoring chirality. I'll be happy with either isomer or even a mixture.

[curiouscat]

The is also the possibility of some sort of oxidative coupling.

@disco

Can you elaborate more on how to do this? I'm not sure how to go about this.

[discodermolide]

This is usually Fe catalysed see
http://pubs.acs.org/doi/abs/10.1021/ja901391u

try a google search on oxidative coupling of penols.

[curiouscat]

This is usually Fe catalysed see
http://pubs.acs.org/doi/abs/10.1021/ja901391u

try a google search on oxidative coupling of penols.

Thanks! Will do.