Mechanism of the Platinum(II)-Catalyzed Hydroamination of 4-Pentenylamines
Journal Article (Journal Article)
The mechanism of the platinum(II)-catalyzed intramolecular hydroamination of benzyl 4-pentenylamines has been evaluated under stoichiometric and catalytic conditions. Reaction of a benzyl 2,2-disubstituted 4-pentenylamine with [(PPh )Pt(μ-Cl)Cl] forms a thermally sensitive platinum amine complex that undergoes irreversible, intramolecular ligand exchange with the pendant C=C bond to form a reactive platinum π-alkene complex. The π-alkene complex undergoes rapid, outer-sphere C-N bond formation, evidenced by the anti addition of Pt and N across the complexed C=C bond, to form a thermally stable zwitterionic platinamethylpyrrolidinium complex. The zwitterionic complex is rapidly and exergonically deprotonated by free amine to form a neutral, bicyclic azaplatinacyclobutane complex that likely exists as a discrete 1:1 adduct with ammonium salt in the nonpolar reaction medium and that represents the resting state of the catalytic cycle. Turnover-limiting intramolecular protodemetalation of the azaplatinacyclobutane-ammonium adduct followed by ligand exchange releases the 2-methylpyrrolidine product. 3 2
Full Text
Duke Authors
Cited Authors
- Bender, CF; Brown, TJ; Widenhoefer, RA
Published Date
- January 25, 2016
Published In
Volume / Issue
- 35 / 2
Start / End Page
- 113 - 125
Electronic International Standard Serial Number (EISSN)
- 1520-6041
International Standard Serial Number (ISSN)
- 0276-7333
Digital Object Identifier (DOI)
- 10.1021/acs.organomet.5b00821
Citation Source
- Scopus