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Author: Subject: stereoisomerisation of amines with an alpha branch
majortom
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[*] posted on 13-9-2010 at 14:32
stereoisomerisation of amines with an alpha branch


I know I am probably going get flamed for bringing up this much rehashed topic but I think I found something interesting. I am just going to say that this is most likely going to be wrong if it hasn't been done already. It's really just speculation and I haven't been able to dig up much of anything related to it with out some strange catalysts.

While recalling that ketones isomerise in basic or acidic conditions due to enol formation I thought about the possibility that a stereo-specific amine with an alpha branched carbon chain (think R-2-aminobutane) might be oxidised to an imine which could be reduced by formic acid to produce a racemic mixture of the formerly stereo specific isomer.

That might be possible, but another option yielding a racemic mixture but from a different starting chemical would be something akin to what is done with alkynes and their conversion to vinyl alcohols and subsequent ketone formation. I wonder if that could be done with an imine.

I was thinking that the first option could be done by reaction of the amine with an alkali metal in a polar apriotic solvent, perhaps with the corresponding alkali hydroxide as well, that may disassociate the anionic amide and possibly allow for very brief lose of a proton at the carbon alpha to the anionic amide. Of course it would come back, but in a racemic fashion just as with enols.

Yes I know everyone is going to flame me for lack of research, but I have searched everywhere for a convenient method of doing either but in the case of the first I came up with exotic catalysts and in the latter nothing.
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[*] posted on 13-9-2010 at 17:55


what are the exotic catalyst and conditions that you lit review uncovered?



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Nicodem
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14-9-2010 at 04:14
majortom
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[*] posted on 29-9-2010 at 17:51


Sorry for the slow reply. I found some information of a dinuclear copper ligand whose science is beyond my understanding (http://www.ncbi.nlm.nih.gov/pubmed/20536143). also N-tert-Butylphenylsulfinimidoyl Chloride (http://www.jstage.jst.go.jp/article/cl/30/5/30_390/_article/...). then there was phenyl hypoiodate and some ruthenium halide phenylphosphine ligand (http://tiny.cc/kv2pe). There were a few reactions with reagents just as strange. I don't have any idea how you would begin to get these compounds, at the end of the day it seems easier just to go through the trouble of making a alkene or alkyne from scratch and making it into a ketone.

Its all possible to do, but the difficulty involved seems to outweigh any benefits this route could have. It seems like such a rudimentary concept analogous to oxidation of alcohols.
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