Cascade Alternating Metathesis Cyclopolymerization of Diynes and Dihydrofuran

Ruthenium alkoxymethylidene complexes have recently come into view as competent species for metathesis copolymerization reactions when coupled with appropriate comonomer targets. Here, we explore the ability of Fischer-type carbenes to participate in cascade alternating metathesis cyclopolymerizatio...

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Bibliographic Details
Published in:ACS macro letters 2022-05, Vol.11 (5), p.630-635
Main Authors: Sui, Xuelin, Gutekunst, Will R.
Format: Article
Language:English
Subjects:
Alkynes
Diynes
Polymerization
Polymers
Ruthenium
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Summary:Ruthenium alkoxymethylidene complexes have recently come into view as competent species for metathesis copolymerization reactions when coupled with appropriate comonomer targets. Here, we explore the ability of Fischer-type carbenes to participate in cascade alternating metathesis cyclopolymerization (CAMC) through facile terminal alkyne addition. The combination of diyne monomers and an equal feed ratio of low-strain dihydrofuran leads to a controlled chain-growth copolymerization with high degrees of alternation (>97% alternating diads) and produces degradable polymer materials with low dispersities and targetable molecular weights. When combined with enyne monomers, this method is amenable to the synthesis of alternating diblock copolymers that can be fully degraded to short oligomer fragments under aqueous acidic conditions. This work furthers the potential for the generation of functional metathesis materials via Fischer-type ruthenium alkylidenes.
ISSN:2161-1653
2161-1653
DOI:10.1021/acsmacrolett.2c00140