Facile
synthesis
of high optically active
helical polymers from achiral monomers still remains a great challenge.
In this work, two chiral Ni(II) catalysts bearing chiral R- or S-2a ligands were facilely prepared
which can efficiently initiate the living/controlled polymerization
of allene monomers and afford well-defined polyallenes in high yields
with controlled molecular masses (M
ns)
and low molecular mass distributions (M
w/M
ns). The catalysts showed interesting
regioselectivity on the cumulated double bonds of allene monomers,
as the polymerizations were highly selective which occurred on 2,3-double
bonds. Moreover, the polymerization of achiral allene monomers using
chiral Ni(II) catalysts showed remarkable helix-sense selectivity.
The yielded polyallenes exhibited high optical activity due to the
formation of a predominant one-handed helix as revealed by circular
dichroism, UV–vis, and direct atomic force microscopy (AFM)
observations as well. The predominant one-handed helicity of the generated
polyallenes was solely determined by the chirality of the Ni(II) catalysts.
Carbonylative coupling reaction of aryl iodides with ferrocenylethyne catalyzed by PdCl 2 was carried out using sodium dodecyl sulphonate (SDS) as surfactant and water as solvent. The reaction gave much better yields of aryl ferrocenylethynyl ketones, which proceeded for 6 h at room temperature under a balloon pressure of carbon monoxide with Et 3 N as base.
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