title: Palladium(II)-catalyzed direct alkoxylation of arenes: evidence for solvent-assisted concerted metalation deprotonation.
abstract: Density functional theory investigations on the mechanism of palladium acetate catalyzed direct alkoxylation of N-methoxybenzamide in methanol reveal that the key steps involve solvent-assisted N-H as well as C-H bond activations. The transition state for the critical palladium-carbon bond formation through a concerted metalation deprotonation (CMD) process leading to a palladacycle intermediate has been found to be more stable in the methanol-assisted pathway as compared to an unassisted route.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
authors.forename: Megha
authors.initials: M
authors.lastname: Anand
authors.forename: Raghavan B
authors.initials: RB
authors.lastname: Sunoj
mesh_terms: D001549:Benzamides / Q000737:chemistry*; D002384:Catalysis; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D000432:Methanol / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D001549:Benzamides; D004987:Ethers; D009942:Organometallic Compounds; D012997:Solvents; D010165:Palladium; D000432:Methanol