Great!

[Ganesha]

This meens that sodium dithionite and Mg/ammonium formate could be used for the reduction of nitrostyrenes to amines via oximes. Would be great if someone also tried Mg/HCOOH as well.

Great find demorol!

[josef_k]

Wow, this seems very interesting. Good to be able to use cheap magnesium instead of palladium. Nice find!

[Sunlight]

It's fantastically interesting...

[amine]

hah nice, is the nitrogen atmosphere needed in the synth? or it is just being used as a precaution. Could be used to make mda, instead of going through the al/hg route. (may even be higher yielding).

and magnesium and formic acid are dirt cheap!!.

[Rhodium]

I have now uploaded this article to my page:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/oxime2amine.mg-af.html

A very similar article (strangely enough not referenced in this one) is the following:

Post 477266 (missing)

(Lego: "Reduction of oximes with zinc/ammonium formate", Novel Discourse)

Ref 10:

https://www.thevespiary.org/rhodium/Rhodium/pdf/electroreduction-chem.rev.62.19-40.1962.pdf

Ref 19:

https://www.thevespiary.org/rhodium/Rhodium/pdf/heterogenous.cth.review.pdf

Ref 21:

Post 353051

(foxy2: "Raney Nickel CTH Reduction of Nitro/Nitrile Groups", Methods Discourse)
Ref 23:

https://www.thevespiary.org/rhodium/Rhodium/pdf/cth.oximes.formate.pdf

Ref 24:

https://www.thevespiary.org/rhodium/Rhodium/pdf/cth.review.pdf

Ref 25: (below)

Magnesium/hydrazinium monoformate:
A new hydrogenation method for removal of some commonly used protecting groups in peptide synthesis
D. Channe Gowda

Tetrahedron Letters 43, 311–313 (2002)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/cth.hydrazine-formate.magnesium.pdf)
 
Abstract
Removal of some commonly used protecting groups in peptide synthesis by catalytic transfer hydrogenation employing hydrazinium monoformate and magnesium is described. This method is equally competitive with other methods in deblocking most of the commonly used protecting groups in peptide synthesis. tert-Butyl derived and base labile protecting groups were completely stable under these conditions. The use of Mg/NH₂–NH₂·HCOOH makes this a rapid, low-cost alternative to palladium and reduces the work-up to a simple and extraction operation.

[Barium]

4-Fluorophenylacetone oxime was not successfully reduced to the amine. Not even to the hydroxylamine. As a matter of fact I did not get any reaction with the oxime. I tried with both activated Mg and unactivated Mg. I tried with grignard magnesium as well as pyrograde magnesium. I tried with MeOH, EtOH and IPA. I thought my ammonium formate was perhaps a bit too wet and perhaps the water somehow hindered the reaction. So I dried the ammonium formate over P2O5. Just a waste of P2O5, but at least I have some bone dry ammonium formate. Then I tried the Mg/NH4COOH-system in MeOH on 1-(2,5-dimethoxyphenyl)-2-nitroethane and it worked like a charm.

Please, someone else try this system too since my track record for reducing oximes is not good.

[josef_k]

I tried with grignard magnesium

Did you try that when you reduced the nitro compound also? Semms like magnesium granules is much cheaper than powder. Although I guess the reaction would run slower?

Great that you proved that the reaction works for nitroalkanes also. The cost of Pd have always turned me off CTHs before, but now I might have to try one.

[Ganesha]

Could you run this oxime-reduction w/ Zn/NH4COOH instead of  Mg/NH4COOH and report back?

[Barium]

I will do that, just give me a little time to get a few other things finised first.