title: Iron(II)-catalyzed amidation of aldehydes with iminoiodinanes at room temperature and under microwave-assisted conditions.
abstract: A method for the amidation of aldehydes with PhI=NTs/PhI=NNs as the nitrogen source and an inexpensive iron(II) chloride + pyridine as the in situ formed precatalyst under mild conditions at room temperature or microwave assisted conditions is described. The reaction was operationally straightforward and accomplished in moderate to excellent product yields (20-99%) and with complete chemoselectivity with the new C-N bond forming only at the formylic C-H bond in substrates containing other reactive functional groups. By utilizing microwave irradiation, comparable product yields and short reaction times of 1 h could be accomplished. The mechanism is suggested to involve insertion of a putative iron-nitrene/imido group to the formylic C-H bond of the substrate via a H-atom abstraction/radical rebound pathway mediated by the precatalyst [Fe(py)(4)Cl(2)] generated in situ from reaction of FeCl(2) with pyridine.
authors.affiliation: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
authors.forename: Thi My Uyen
authors.initials: TM
authors.lastname: Ton
authors.forename: Ciputra
authors.initials: C
authors.lastname: Tejo
authors.forename: Stefani
authors.initials: S
authors.lastname: Tania
authors.forename: Joyce Wei Wei
authors.initials: JW
authors.lastname: Chang
authors.forename: Philip Wai Hong
authors.initials: PW
authors.lastname: Chan
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D003300:Copper / Q000737:chemistry; D054879:Halogenation; D007097:Imines / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008872:Microwaves; D015394:Molecular Structure; D013696:Temperature
chemical_list: D000447:Aldehydes; D007097:Imines; D003300:Copper; D007501:Iron