Hydrazides as tunable reagents for alkene hydroamination and aminocarbonylation.

Journal of the American Chemical Society

PubMedID: 19505097

Roveda JG, Clavette C, Hunt AD, Gorelsky SI, Whipp CJ, Beauchemin AM. Hydrazides as tunable reagents for alkene hydroamination and aminocarbonylation. J Am Chem Soc. 2009;131(25):8740-1.
Benzoic hydrazides (R = Ph), which are remarkably bench and thermally stable reagents (often up to 230 degrees C), afford intramolecular hydroamination products upon heating at high temperatures (120-235 degrees C). A concerted Cope-type hydroamination event, followed by a hydrazide-mediated proton transfer step of the hydrazinium ylide intermediate, is proposed and supported by DFT calculations. In contrast, a simple modification of the reagent structure (R = Ot-Bu or NH(2)) favors the formation of aminocarbonylation products at 200 degrees C, and the latter reaction is shown to be stereospecific.