Paper
Catalysis Science & Technology
are the correspondingly isomerized olefins, which could be
converted back to the starting olefins along with the con-
sumption of feed-stocks because of the equilibrium of the
isomerized olefins and starting olefins. Terminal olefins,
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1
-hexene, 1-heptene and 1-octene, were converted to the cor-
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responding linear aldehydes with good activity and regio-
selectivity. The ratios of linear to branched aldehydes were as
high as 96 : 4–98 : 2, while the conversions were more than
9
7%. Notably, the biggest advantage of the Rh/CPOL-bp&PPh
3
catalyst was the conversion of internal olefins to the corre-
sponding linear aldehydes. Tandem isomerizing hydro-
formylation of internal olefins, 2-heptene, 2-octene and trans-
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3
-hexene, to linear aldehydes could also be conducted effec-
tively with the catalyst with ratio of l/b as high as 92 : 8–93 : 7.
The catalyst can be easily recovered by simple filtration or by
a centrifugation procedure.
1
-Octene was chosen to test the stability of the catalyst. It
was shown that the Rh/CPOL-bp&PPh catalyst can be reused
at least 6 cycles with high activity and selectivity (Table 6).
The Rh leaching from the Rh/CPOL-bp&PPh catalyst is negli-
3
3
gible after 6 runs according to the ICP investigations (Table
S1, ESI†), which may be ascribed to the strong multi-
coordinate bonds between the Rh species and the exposed P
1
1b,16
species of high concentration in the catalyst.
Conclusions
Vinyl biphephos has been successfully synthesized, based on
which we developed an efficient Rh/CPOL-bp&PPh heteroge-
3
neous catalyst. The catalyst showed good performance in
converting terminal olefins to the corresponding aldehydes
with high regioselectivity (l/b = 96 : 4–98 : 2), activity and stabil-
ity. Isomerizing hydroformylation of internal olefins was also
conducted with high regioselectivity (l/b = 92 : 8–93 : 7) using
this heterogeneous catalyst. Moreover, it was shown that the
2
014, 4, 2097; (g) M. C. de Freitas, K. C. B. de Oliveira, A. de
Camargo Faria, E. N. dos Santos and E. V. Gusevskaya,
Catal. Sci. Technol., 2014, 4, 1954.
9
(a) S. Güven, B. Hamers, R. Franke, M. Priske, M. Becker
and D. Vog, Catal. Sci. Technol., 2014, 4, 524; (b) S. Yu, X.
Zhang, Y. Yan, C. Cai, L. Dai and X. Zhang, Chem. – Eur. J.,
Rh/CPOL-bp&PPh heterogeneous catalyst exhibited even bet-
3
ter performance than the comparable homogeneous Rh + vinyl
biphephos system. We envision that this copolymerization
strategy may be one of the most promising platforms for the
deployment of highly efficient heterogeneous catalysts.
2
010, 16, 4938; (c) X. Jia, Z. Wang, C. Xia and K. Ding, Catal.
Sci. Technol., 2013, 3, 1901; (d) G. M. Torres, R. Frauenlob,
R. Franke and A. Börner, Catal. Sci. Technol., 2015, 5, 34; (e)
G. Liu, K. Huang, C. Cai, B. Cao, M. Chang, W. Wu and X.
Zhang, Chem. – Eur. J., 2011, 17, 14559.
Acknowledgements
1
0 (a) O. Diebolt, C. Müller and D. Vogt, Catal. Sci. Technol.,
012, 2, 773; (b) K. Takahashi, M. Yamashita and K. Nozaki,
2
This study was supported by the National Natural Science
Foundation of China (21273227 and 21303190).
J. Am. Chem. Soc., 2012, 134, 18746; (c) L. Obrecht, P. C. J.
Kamer and W. Laan, Catal. Sci. Technol., 2013, 3, 541; (d) U.
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