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Author: Subject: Under what conditions do alkyl azides rearrange to imines?
Loptr
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[*] posted on 15-12-2018 at 19:43
Under what conditions do alkyl azides rearrange to imines?


Under what conditions do alkyl azides rearrange to imines? I am having some difficulty finding details on this one. I know that reactions involving free HN3 are unsavory, but I was unaware of its reaction with alkenes, and was also wondering if it can be radicalized to affect to affect anti-Markovnikov addition using light or peroxide, similar to how addition with HX is affected.

http://organicreactions.org/index.php?title=Schmidt_reaction...
Screen Shot 2018-12-15 at 10.38.33 PM.png - 332kB

https://www.organic-chemistry.org/namedreactions/schmidt-rea...
Screen Shot 2018-12-15 at 10.37.04 PM.png - 40kB




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Nakhimov
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[*] posted on 18-12-2018 at 08:33


Here is a recent paper with some in-situ reactions of alkyl azides in the presence of copper catalysts: https://www.thieme.de/statics/bilder/thieme/final/de/bilder/...

Additionally, here's a proposed mechanism from the Hu paper:
http://advances.sciencemag.org/content/advances/3/8/e1700826...

(doi:10.1126/sciadv.1700826)

[Edited on 12-18-2018 by Nakhimov]
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[*] posted on 20-12-2018 at 05:01


Here is a pretty interesting overview of the Schmidt reaction.

Attachment: wrobleski2012.pdf (2.9MB)
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[*] posted on 20-12-2018 at 13:44


What bothers me about this is how weak of an acid HN3 is. How would it easily add to an alkene?



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