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Topic: Azide click: cyclization though nitrile vs enolate  (Read 1724 times)

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Azide click: cyclization though nitrile vs enolate
« on: September 02, 2014, 11:35:04 PM »
So I have to keep this vague based on IP and publishing reasons.

This paper http://pubs.acs.org/doi/abs/10.1021/jo00798a035?journalCode=joceah

Has the reaction of ethyl cyanoacetate with benzyl azide under basic conditions, giving the 1-benzyl-4-carboxyethyl-5-amino-1,2,3-triazole.

I believe this is a result of the NC-CH2-COOEt going to the enolate NC-CH=CO(-)OEt, which can then tautomerize to (-)N=C=CH-COOEt, and the cyclization occurring through the CC double bond.

But I am trying this on a different system, and instead of the substituted azide going through the C=C giving a triazole, it seems to go through the C=N giving the tetrazole instead. 

Does anyone have any suggestions for how to get it to go through the C=C, despite me being deliberately vague?  Should I attempt to add metal catalysts to the reaction?'


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