ChemComm
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COMMUNICATION
DOI: 10.1039/C5CC01329A
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To investigate the mechanism occurring during the tandem
catalysis, a series of the crude mixture of the reaction was analyzed
1
o
1
by H NMR spectroscopy in CDCl3 at 20 C (Figure 3). Five H
NMR spectra were recorded at regular intervals over a period of 1 h
during the reaction of LacꢀOCA and PO in the presence of
(salen)CoCl/[PPN]Cl (Figure 3). These 1H NMR spectra and
1
conversion vs time curves of the tandem reaction from H NMR
(Figure S8) clearly indicated a twoꢀsteps sequential reaction. The
formation of the polyesters was followed by the cycloaddition of
CO2 to epoxide. Possibly, the cyclization reaction started when an
epoxide coꢀmonomer replaced a metalꢀbound polymeric chain. By
nucleophilic attack of Clꢀ group on epoxide, which was activated by
the Lewis acidic metal center, an alkoxide active species was
generated in situ, and the reaction of epoxide and CO2 proceeded
simultaneously to form a carbonate. Then, cyclic carbonate was
produced by the backbiting of a metalꢀcarbonate into an adjacent
alkoxide linkage.27
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In conclusion, we demonstrated the first tandem catalytic system
that allowed oneꢀpot synthesis of bioꢀrenewable polyesters and
cyclic carbonates in high yields, through the incorporation of CO2
released from the initial step. This process provided access to a range
of wellꢀdefined polyesters with narrow molecular weight
distributions. To our knowledge, these binary catalyst systems
offered unprecedented opportunities for the atomꢀefficient
production of two relevant compounds.
We acknowledge the financial support from National Natural
Science Foundation of China (21304085 & 51321062).
Notes and references
aKey Laboratory of Polymer Ecomaterials, Changchun Institute of Applied
Chemistry, Chinese Academy of Sciences, Renmin Street 5625, Changchun
130022, People’s Republic of China. bUniversity of Chinese Academy of
Sciences, Beijing 100039, People’s Republic of China. Eꢀmail:
youhua.tao@ciac.ac.cn,
xhwang@ciac.ac.cn;
Web:
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/c000000x/
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