Enantio- and diastereoselective polymerization: asymmetric allylic alkylation catalyzed by a planar-chiral Cp'Ru complex

In this study, we examined the regio-, diastereo-, and enantioselective polymerization using asymmetric allylic alkylation catalyzed by a planar-chiral cyclopentadienyl-ruthenium (Cp'Ru) complex ((S)-1). Achiral AB type monomers bearing 1,3-diketone and allylic chloride moieties were polymerize...

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Published inPolymer chemistry Vol. 7; no. 22; pp. 3691 - 3699
Main Authors Kanbayashi, Naoya, Hosoda, Kazuki, Okamura, Taka-aki, Aoshima, Sadahito, Onitsuka, Kiyotaka
Format Journal Article
LanguageEnglish
Published 01.05.2016
Subjects
Alkylation
Asymmetry
Conversion
Cotton
Coupling
Monomers
Optical activity
Polymerization
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Summary:In this study, we examined the regio-, diastereo-, and enantioselective polymerization using asymmetric allylic alkylation catalyzed by a planar-chiral cyclopentadienyl-ruthenium (Cp'Ru) complex ((S)-1). Achiral AB type monomers bearing 1,3-diketone and allylic chloride moieties were polymerized by (S)-1 with quantitative monomer conversion. The resulting polymer (3) was characterized by NMR analyses; the polymerization reaction catalyzed by (S)-1 proceeded with high regioselectivity, and the vicinal stereocenters of the monomer unit can be controlled. The polymer showed a Cotton effect at around 270 nm in its CD spectrum, which was ascribed to the bisignate coupling between the pi - pi * transition moment of each benzene chromophore. The results suggested that the polymerization proceeded in a stereoselective manner to give optically active polymers.
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ISSN:1759-9954
1759-9962
DOI:10.1039/c6py00484a