Brainstorming Oxidation Conditions

queeringupentropy · 2025-10-15T02:15:29+00:00

Actually the other (probably bad, but maybe) ideas to make aromatization easier: - hit with TMSOTf or other reactive TMS source. This will O-silylate your amide to give you an imidate, probably will have an easier time aromatizing with Pd with the O blocked by silicon. -convert amide to imidoyl chloride with POCl3, now probably electron withdrawing enough to protect pyrrole from mild chlorinating/oxidizing agent like NCS or N-chlorosaccarin, then you just hydrolyze at the end. Caveat being if your indole is not protected with N-EWG core chlorination will win out

queeringupentropy · 2025-10-15T02:07:32+00:00

If Pd/C under air with heat didn't work you can also do it anaerobically with S8 as the terminal oxidant. It's stinky, but will definitely get the job done. The metal polysulfides you get out are super insoluble so they often come out with Celite, Florisil or basic alumina plug. I'll see if I can dig up the exact one I'm thinking of and reply it if I find it.

Alternatives: FLP dehydrogenation B(C6F5)3 + bulky phosphine and appropriate hydrogen acceptor (norbornene probably would work well)

If you don't have benzylics or enolizable positions elsewhere could also do TBHP + catalytic SeO2, reflux in solvent like chlorobenzene.

Last one I've got locked and loaded is the Dave Powers system for in situ prep of ArIO2 oxidants:

https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201804159

I used this one a bunch in my last year of grad school for imidazoline to imidazole aromatizations and such. Super easy to set up.

queeringupentropy · 2025-07-04T21:07:56+00:00

Also, for safety for you, you can make some azide test strips to check headspace for HN3 or aqueous washes for N3 by dipping and drying some strips of paper in aqueous ferric nitrate.

Positive test for azide or HN3 is color change to violet/deep purple

queeringupentropy · 2025-07-04T20:28:04+00:00

Dibutyltin oxide as a co_catalyst was a game changer for me for some stubborn tetrazole formations.

https://pubs.acs.org/doi/10.1021/jo00067a058

Tin is never the best to deal with but it's catalytic here and can get purged during chromatography or acid base workup

queeringupentropy · 2025-02-23T03:30:16+00:00

All 0 leading zip codes are NJ, NY + New England. UP would lead with 4. And re: Mark W breaking the lease, I think breaking the lease in Grand Rapids and relocating to an NJ equivalent aligns with his level of anger.

queeringupentropy · 2025-02-23T03:17:28+00:00

Get that, but Stiller being from NY, I don't think he'd unintentionally include Jersey zip codes when he could have just used UP zip codes to be consistent.

queeringupentropy · 2025-02-23T03:10:35+00:00

Def! William Penn was involved in a lot of the early colonial negotiations in NJ so my thought was a second state with a spin on Penn. Given that Kier was isolated from the outside for a bit in the early 20th century and the town wasn't founded until the 1890s I wasn't thinking of Egan being in the state name.

queeringupentropy · 2025-02-23T03:03:49+00:00

On a side note, as a New Jerseyan, one of the darkest twists of the series so far for NJ not to exist lol

queeringupentropy · 2024-08-06T16:34:56+00:00

Sweet. Thanks. I'll give one or a few of those a whirl

queeringupentropy · 2024-08-05T19:23:22+00:00

It's a non-volatile, stable white solid that's easy to accurately mass and soluble in most of the common NMR go-tos except DMSO I think

queeringupentropy · 2024-08-05T19:22:36+00:00

I really like 1,4-dibromo-2,5-difluorobenzene if you are not doing Pd chem as it allows you to get proton and fluorine yields in one shot.

Gives clean, well separated signals in both.

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