Hydrazides as tunable reagents for alkene hydroamination and aminocarbonylation.
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.
Roveda
Jean-Grégoire
JG
Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, Canada, K1N 6N5.
Clavette
Christian
C
Hunt
Ashley D
AD
Gorelsky
Serge I
SI
Whipp
Christopher J
CJ
Beauchemin
André M
AM
D000475:Alkenes / Q000737:chemistry*; D000586:Amination; D001565:Benzoates / Q000737:chemistry; D006361:Heating; D006834:Hydrazines / Q000737:chemistry*; D007202:Indicators and Reagents / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D013816:Thermodynamics
D000475:Alkenes; D001565:Benzoates; D006834:Hydrazines; D007202:Indicators and Reagents