Diaminocarbenes have been much in the news lately, as many of them are stable at room twemperature. Even the occasional monoaminocarbene is stable. That stability owes to the p donation from the nitrogen lone pair. Being contrary, we decided to make an aminocarbene that couldn't p conjugate. Actually, the idea came from a seminar given by Professor Anthony Kirby of Cambridge on the properties of the related "amide." The quotes are there because this compound really isn't an amide, as Tony and his coworkers have beautifully shown. Amides are amides and not nitrgen-substituted ketones because of conjugation. Here are a couple of references to this " most twisted amide."


Kirby, A. J.; Komarov, I. V.; Wothers, P. D.; Feeder, N. Angew. Chem. Int. Ed. Engl. 1998, 37, 785. Kirby, A. J.; Komarov, I. V.; Feeder, N. J. Chem. Soc., Perkin Trans. 2 2001, 522.

Catherine made the tosylhydrazone salt, then photolyzed it directly to make the carbene. Those two short sentences dont sound like much, but they summarize a lot of tough, hard work. Studies of the stereochemistry of addition of the carbene, competition experiments, and a theoretical collaboration with Professor Marcel Nooijen (here at Princeton) show that the reacting state of this carbene is a somewhat nucleophilic singlet.


A full paper on this carbene should appear sometime in 2002.


Catherine just got married (September, 2001). Here is a picture of her and her new husband, Xiao Yang.