End capping ring-opening olefin metathesis polymerization polymers with vinyl lactones.
The selective placement of a functional group at the chain end of a ring-opening metathesis polymer using ruthenium carbene initiators has been a significant limitation. Here we demonstrate a highly effective and facile end-capping technique for ROMP with living ruthenium carbene chain ends using single-turnover olefin metathesis substrates. Vinylene carbonate and 3H-furanone are introduced as functionalization and termination agents for the ruthenium-initiated ring-opening metathesis polymerization. This leads directly to the formation of functional polymer end groups without further chemical transformation steps. Aldehyde and carboxylic acid end groups can be introduced by this new method which involves the decomposition of acyl carbenes to ruthenium carbides. The high degrees of chain-end functionality obtained are supported by (1)H NMR spectroscopy, MALDI-ToF mass spectrometry, and end-group derivatization.
Hilf
Stefan
S
Institut für Organische Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, D-55099 Mainz, Germany.
Grubbs
Robert H
RH
Kilbinger
Andreas F M
AF
D000475:Alkenes / Q000737:chemistry*; D004149:Dioxoles / Q000737:chemistry; D007783:Lactones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008697:Methane / Q000031:analogs & derivatives / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D012015:Reference Standards; D012428:Ruthenium / Q000737:chemistry; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods; D013237:Stereoisomerism; D013997:Time Factors
D000475:Alkenes; D004149:Dioxoles; D007783:Lactones; D009942:Organometallic Compounds; D011108:Polymers; C030011:carbene; D012428:Ruthenium; C031134:vinylene carbonate; D008697:Methane