Regioselective Termination Reagents for Ring-Opening Alkyne Metathesis Polymerization

Alkyne
cross-metathesis of molybdenum carbyne complex [TolCMo­(OCCH3(CF3)2)3]·DME with 2
equiv of functional ynamines or ynamides yields the primary cross-metathesis
product with high regioselectivity (>98%) along with a molybdenum
metallacyclobutadiene complex. NMR and X-ray crystal structure analysis
reveals that ynamides derived from 1-(phenylethynyl)­pyrrolidin-2-one
selectively cleave the propagating molybdenum species in the ring-opening
alkyne metathesis polymerization (ROAMP) of ring-strained 3,8-dihexyloxy-5,6-dihydro-11,12-didehydrodibenzo­[a,e]­[8]­annulene and irreversibly deactivate
the diamagnetic molybdenum metallacyclobutadiene complex through a
multidentate chelate binding mode. The chain termination of living
ROAMP with substituted ethynylpyrrolidin-2-ones selectively transfers
a functional end-group to the polymer chain, giving access to telechelic
polymers. This regioselective carbyne transfer strategy gives access
to amphiphilic block copolymers through synthetic cascades of ROAMP
followed by ring-opening polymerization of strained ε-caprolactone.