candida utilis biosynthesis - other uses?

[elfspice]

I have been rather interested in the subject of using candida utilis to do certain reactions to certain chemicals... specifically the benzaldehyde to phenylacetylcarbinol. I was talking with a friend and he somehow got me onto the topic of piperonal, which i found out was 3,4 methylenedioxy benzaldehyde...

since the reaction mechanism of the biosynth on aldehydes seems to be primarily about the aldehyde on a benzene ring, then substituted benzene rings might work too.

eg: piperonal to 3,4 methylenedioxy phenylacetylcarbinol (L isomer mind you) and from there via reductive amination to an alpha hydroxylated version of mdma, which probably could be reduced via HI...

[Polverone]

According to

https://www.thevespiary.org/rhodium/Rhodium/hyperlab/syntheses/other_bio_ephedrine.htm

, other aldehydes can be used in biosynthesis. But I don't read Russian and thus rely on imperfect machine translation. It seems like it could be interesting to experiment with vanillin first so as to develop technique with inexpensive, unsuspicious materials.

[Organikum]

This works on substituted benzaldehydes also, I posted a patent on this times ago I think......

The preferred yeast is saccharomyces cerevesiae aka bakers yeast btw. Dont know who brought this candida utilis BS up. Works, but is harder to obtain and has lower yields.

One of the nicest variations is IMHO: b-dehyde to L-PAC to norephedrine to 4-MAR.

[roger2003]

See:

Patent US3338796

[elfspice]

oh... is that different to brewers yeast?

I had the thought that one could aminate and then oxidise instead of reduce to perhaps somehow achieve methylone, or other variations (perhaps N substituents?)

[BOS]

Sorry for off topic.

Org,Can you give a brief run-down on how one might go from l-pac to PPA?
E.g what method did you use to aminate.
Did you use ammonia ect ect.?

Cheers.

[n00dle]

4-hydroxy-3-methoxybenzaldehyde (vanillin) would yeild 4-hydroxy-3-methoxymethamphetamine, no? Which is HMMA, a metabolite of MDMA. One does not know if this is active or not, assumes not, and can't seem to find decent information on it. How would one go about testing for HMMA yeild/prescence as a mock-run for piperonal?

[Vitus_Verdegast]

Phenylalkylamines substituted with a phenolic group are not lipophilic enough to cross the blood-brain barrier efficiently.

[n00dle]

Thought so. Can anyone suggest a way to confirm the presence of HMMA and in what proportion?

[stratosphere]

as far as characterizing the results of a bio synth experiment on vanillin, i would think the usual polar-non-polar workup follwed by vacuum distillation would work for seperating unreacted vanillin from 3OH-4MeO-phenyl-a-hydroxy acetone, if their boiling points are somewhat seperated.
you could then use some sort of paper chromotagraphy or other similiarly lowtech procedure to check that the fraction that is supposed to be 3OH-4MeO-phenyl-a-hydroxy acetone is indeed just one substance.

if their boiling points are too close, then to get a quantitative test, youd proobly have to vacuum distill vanillin/3OH-4MeO-phenyl-a-hydroxy acetone fraction, then you could perhaps find conditions that would selectivly oxidize the vanillin to vannillic acid, which could then presumably be seprated from the 3OH-4MeO-phenyl-a-hydroxy acetone .

[stratosphere]

eg: piperonal to 3,4 methylenedioxy phenylacetylcarbinol (L isomer mind you) and from there via reductive amination to an alpha hydroxylated version of mdma, which probably could be reduced via HI...   
  


HI (and HBr) react with ethers (R-0-R + HI --> ROH + RI), so its possible that this method of reduction would injure the methylenedioxy ring.
the a-hydroxy version of mdma has its own merits though, if you can get that far.

[n00dle]

Journal of Fermentation and Bioengineering 84, 487-492 (1997) Pure and Applied Chemistry 1997, vol 69, ppgs 2371-2385 says that "sadly when ring substituted benzaldehydes are used the yield falls off badly" in regards to biosynthesis as mentioned here. i do not have this journal and can't confirm it. However, anyone care to estimate yeilds obtained with a ring substituted benzaldehyde in this biosynthesis?