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(Angew. Chem. Int. Ed.) Ring-Opening Metathesis Polymerization of a Macrobicyclic Olefin bearing a Sacrificial Silyloxide Bridge
作者:Yu, Z.; Wang, M.; Chen, X.; Huang, S.; Yang, H.*
關(guān)鍵字:Ring-Opening Metathesis Polymerization
論文來源:期刊
具體來源:Angewandte Chemie International Edition, 2022, 61, e202112526.
發(fā)表時(shí)間:2022年

Ring-opening metathesis polymerization (ROMP)

has been regarded as a powerful tool for sequence-controlled

polymerization. However, the traditional entropy-driven

ROMP of macrocyclic olefins suffers from the lack of ring

strain and poor regioselectivity, whereas the relay-ring-closing

metathesis polymerization inevitably brings some unnecessary

auxiliary structure into each monomeric unit. We developed

a macrobicyclic olefin system bearing a sacrificial silyloxide

bridge on the a,b’-positions of the double bond as a new class

of sequence-defined monomer for regioselective ROMP. The

monomeric sequence information is implanted in the macroring,

while the small ring, a 3-substituted cyclooctene structure

with substantial ring tension, can provide not only narrow

polydispersity, but also high regio-/stereospecificity. Besides,

the silyloxide bridge can be sacrificially cleaved by desilylation

and deoxygenation reactions to provide clean-structured, nonauxiliaried

polymers.

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