Suggestion of an organometallic intermediate in an intramolecular dechlorination reaction involving copper(I) and a ArCH2Cl moiety.
A copper(I)-mediated reductive dechlorination reaction involving an "internal" chloromethylene substrate at the pyridyl 6-position of one TMPA arm (TMPA triple bond TPA triple bond tris(2-pyridylmethyl)amine) leads to a 1:1 ratio of the starting ligand 6ClCH2-TMPA and a new methyl-TMPA product, 6CH2H-TMPA. On the basis of observed product distributions and a kinetic study, a reaction mechanism involving intramolecular oxidative insertion of Cu(I) to the C-Cl substrate is suggested. The resulting organometallic intermediate is then protonated, leading to the observed products.
Maiti
Debabrata
D
Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.
Narducci Sarjeant
Amy A
AA
Itoh
Shinobu
S
Karlin
Kenneth D
KD
D003300:Copper / Q000737:chemistry*; D054879:Halogenation; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands; D008752:Methylene Chloride / Q000031:analogs & derivatives*; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry
D006841:Hydrocarbons, Aromatic; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; C431843:tris(2-pyridylmethyl)amine; D008752:Methylene Chloride; D003300:Copper; C023666:pyridine