title: Hydrazides as tunable reagents for alkene hydroamination and aminocarbonylation.
abstract: 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.
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, Canada, K1N 6N5.
authors.forename: Jean-Grégoire
authors.initials: JG
authors.lastname: Roveda
authors.forename: Christian
authors.initials: C
authors.lastname: Clavette
authors.forename: Ashley D
authors.initials: AD
authors.lastname: Hunt
authors.forename: Serge I
authors.initials: SI
authors.lastname: Gorelsky
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Whipp
authors.forename: André M
authors.initials: AM
authors.lastname: Beauchemin
mesh_terms: 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
chemical_list: D000475:Alkenes; D001565:Benzoates; D006834:Hydrazines; D007202:Indicators and Reagents