H4CBD - not just hydrogenated? Not isomerizable through missing atom?

[Soulfake]

I've been thinking about what would happen if you tried to isomerize H4-CBD the way you would regular CBD. One would expect to simply obtain HHC and various variants thereof, depending on the reaction details, instead of d8/9-THC.

Then I took a closer look at the molecule and noticed that there is a difference other than the ring being hydrogenated. A carbon atom is missing from the position required for isomerization. Is this a problem? I hope some knowledgeable people can help me, I'm still a layman after so many years of "research" ^^'

 

[Skorpio]

That lack of a double bond will make acid catalyzed ring closure harder for sure. I view electronegative things like double bonds to be kind of like compressed springs, waiting to react with some preturbation (also nucleophiles). The lack of that will make this cannabinoid inert unless some lengthy bond migrations occur

 

[Skorpio]

Also not to double post (and to be extremely pedantic), H4 cbd isn't lacking a carbon atom, as much as it is lacking the double bond in normal cbd (so it actually has 1 extra hydrogen in that position).

 

[AlsoTapered]

That lack of a double bond will make acid catalyzed ring closure harder for sure. I view electronegative things like double bonds to be kind of like compressed springs, waiting to react with some preturbation (also nucleophiles). The lack of that will make this cannabinoid inert unless some lengthy bond migrations occur

Looks like a job for 'superbase' ;-)

 

[Skorpio]

Looks like a job for 'superbase' ;-)

You think that would be selective, and not prefer like a tertiary carbon or something a little more stable?

 

[AlsoTapered]

I'm sure it WOULD prefer to deprotonate a tertiary C but that will delocalize the protons of neighbouring carbons and of course it doesn't even take a superbase to deprotonate a phenol. But to form an ether with any C other than one of those on the tail of the T would induce ring-strain.

It's something that would require quite a lot of calculation but it's also worth considering that superbases actually cover a lot of quite bulky compounds and the bulk can be used to limit what CAN be attacked.

I think it's possible to select a superbase that won't deprotonate the terminal C of a long alkyl and use of sufficient solvent bulk will minimize the intermolecular ether formation.

If it's got commercial potential, you can be sure that those who work in that narrow field will be carefully looking to see what is practical.