Talk:Curtius rearrangement

With regards to the reaction mechanism, it is said that the intermediate results from loss of nitrogen to form the nitrene when then goes after the sigma bond. Advanced organic chemistry, Jerry March, Third edition states:

However, in this case (the Curtius Rearrangement), there is no evidence for a free nitrene and it is probable that the steps are concerted.

This is from the third edition of this text (1985), does anyone have a more recent reference that follows this thinking or points to the nitrene being the intermediate? Although it is easy to follow believing the nitrene is the intermediate, it leaves one wondering why the reaction is so clean (yields are so high) with such a reactive species if it does in fact give the nitrene as one of its steps. Lonelychemist (talk) 01:29, 4 July 2009 (UTC)[reply]

The nitrene point is highly contentious, and needs opening up to wider debate. Highlyinoffensive (talk) 20:29, 30 March 2010 (UTC)[reply]

Well, ^[1] compared thermolytic and photolytic reactions, and found neither the thermal nor the photoinduced Curtius rearrangements can involve a nitrene intermediate. So, that's pretty definitive. Image should be updated. Hansonrstolaf (talk) 13:36, 7 April 2011 (UTC)[reply]

Further, ^[2] performed more recently kinetic experiments and DFT computational studies and found that the dominant mechanism in the Curtius Rearrangement is in fact the concerted one. The image should show the concerted mechanism, with maybe a history of the debate over the mechanism?

References

^ Linke, S. (1967). "Curtius and Lossen Rearrangements. II. Pivaloyl Azide". J. Amer. Chem. Soc. 89 (24): 6308–6310. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
^ Tarwade, V (2008). "The Curtius Rearrangement of Cyclopropyl and Cyclopropenoyl Azides. A Combined Theoretical and Mechanistical Study". J. Org. Chem. 73 (21): 8189–8197. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)

[1] Linke, S. (1967). "Curtius and Lossen Rearrangements. II. Pivaloyl Azide". J. Amer. Chem. Soc. 89 (24): 6308–6310. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)

[2] Tarwade, V (2008). "The Curtius Rearrangement of Cyclopropyl and Cyclopropenoyl Azides. A Combined Theoretical and Mechanistical Study". J. Org. Chem. 73 (21): 8189–8197. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)

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