Functional Metathesis Catalyst Through Ring Closing Enyne Metathesis: One Pot Protocol for Living Heterotelechelic Polymers

Abstract

Enyne ring closing metathesis has been used to synthesize functional group carrying metathesis catalysts from a commercial (Ru-benzylidene) Grubbs' catalysts. The new Grubbs-type ruthenium carbene was used to synthesize living heterotelechelic ROMP polymers without any intermediate purification. Olefin metathesis with a mono substituted alkyne followed by ring closing metathesis with an allylic ether provided efficient access to new functional group carrying metathesis catalysts. Different functional benzylidene and alkylidene derivatives have been investigated in the synthesis of heterotelechelic polymers in one pot.

Oxanorbornenes: promising new single addition monomers for the metathesis polymerization

“…Much progress has been made regarding the precise placement of end functional groups in ROMP polymers. 6,11 Within the broad eld of reactive polymer chain ends, the thiol group has received signicant attention. From bioconjugation to transition metal complexation, thiols are oen superior over their oxo-derivatives.…”

Catalytic living ring-opening metathesis polymerization with Grubbs’ second- and third-generation catalysts

“…Recently, tandem ring-opening/ring-closing polymerizations of cycloalkenes attached to other cycloalkenes 19 or a terminal alkyne [20][21][22] have been reported. Over the past decade, a variety of methods for the preparation of mono and bis-end-functional (telechelic) ROMP polymers have been developed [23][24][25][26][27] . ROMP polymers have also been prepared for biological/medicinal applications [28][29][30] , electronics [31][32][33] , battery separators 34 , anion exchange membranes 35 and many others.…”

A versatile living polymerization method for aromatic amides

“…Phenyl 4-((2,4-dimethoxybenzyl)amino)benzoate (I3), phenyl 4-((2-ethylhexyl)amino)benzoate, 2, 4-bis((2-ethylhexyl)oxy)benzaldehyde, exo-Nethylhexylnorbornene imide were synthesized as reported previously. 48,49,50 Deuterated solvents (CD2Cl2, CDCl3 and DMSO-d6) were purchased from Cambridge Isotope Laboratories, Inc. All polymerization reactions were performed in flame-dried glassware under inert atmosphere utilizing standard Schlenk line techniques.…”