[Borek]

408 has troubles posting, so he (?) asked me to help:

Hi everyone.

I have an oxime compound which I am wanting to turn into some nifty products.

My substrate contains an easily-destroyed heterocycle, and borohydride reduction of the oxime to the amine destroys this heterocycle.  Does anyone have some pet, mild reactions that they prefer when reducing an oxime to an amine?

Secondly, I am also trying to oxidize this oxime to a nitro group.  I have tried oxidation with sodium perborate, which I am waiting on my characterization to tell me if the poor yield I obtained is actually my product... 
Again, I was wondering if anyone had any favorite, mild oxidizing reactions for oxime to nitro that they prefer. 
I have a reference that I have not tried yet that uses urea-hydrogen peroxide in TFAA for this oxidation. Does anyone have any experience with it?

Thank-you in advance.

[orgopete]

It is always difficult to predict the reactions of unknown structures. However, based upon the information provided, I am guessing the amine participates with opening the heterocycle. Other ring opening of heterocycles are not unusual.

The question being asked is ambiguous. Is the amine desired or g
the nitro compound? If it were the amine, I would go back to the carbonyl compound and convert it into a halide and displace it with a protected nitrogen. Then deprotect/convert it to the amine. 

[sjb]

Similarly, there are a number of ideas in Magnesium-Catalyzed Reduction of Oximes to Amines Using Ammonium Formate
K. Abiraj; D. Channe Gowda Synthetic Communications 34(4), 599-605(2004).

[Borek]

Apologies for the ambiguity, I am under a non-disclosure agreement regarding my chemistry.

I want both the amine and the nitro compound.

[408]

Anyway, I can only post from work, home does not work for whatever reason.  I cannot detail the exact heterocycle I am using. 

So while the amine would be interesting, the nitro compound is my main target.  So, any mild reaction conditions for oxidation of an oxime to a nitro?  The perborate in GAA route I have been working with has been regularly failing.

[sjb]

Any of the (other) ideas at http://preview.tinyurl.com/oximetonitro any use?

[cpncoop]

If the reduction is destroying the heterocycle due to attack by the amine, you can get around this easily by running the reduction under a slightly acidic pH.  I've done this successfully (using AcOH or citric acid, etc...) on numerous occasions with Pd on C or the like.

For the Nitro group, mCPBA is pretty mild, but I'm not sure whether or not it will have enough "oomph" to get the job done depending on the molecule.