Journal of the American Chemical Society
Page 6 of 8
these catalysts realize the homogeneous catalysis under
the heterogeneous medium state. Therefore, these
porous polymers provide new perspectives for
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1
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4
4
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5
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5
5
5
5
6
synthesizing
heterogeneous
catalysts
with
the
2
.
homogeneous catalytic character.
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METHOD
Synthesis of vinyl-functionalized diphosphine
monomers. As representative sample, 1,2ꢀ
bis(dichlorophosphino)ethane (15 mmol in 30 mL of
THF) was added slowly at °C to (4ꢀ
a
4
887.
0
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
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6
7
8
9
0
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8
9
0
1
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3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3. (a) Palkovits, R.; Antonietti, M.; Kuhn, P.; Thamas, A.; Schüth,
F. Angew. Chem. Int. Ed. 2009, 48, 6909; (b) Kundu, D. S.;
Schmidt, J.; Bleschke, C.; Thomas, A.; Blechert, S. Angew.
Chem. Int. Ed. 2012, 51, 5456; (c) Wang, G.ꢀH.; Hilgert, J.;
Richter, F. H.; Wang, F.; Bongard, H.ꢀJ.; Spliethoff, B.; Weiꢀ
denthaler, C.; Schcüth, F. Nat. Mater. 2014, 13, 293ꢀ300; (d)
Su, D. S.; Perathoner, S.; Centi, G.; Chem. Rev. 2013, 113,
5782ꢀ5816; (e) Zheng, Y.; Jiao, Y.; Ge, L.; Jaroniec, M.; Qiao, S.
Z. Angew. Chem. Int. Ed. 2013, 52, 3110ꢀ3110; (f) Fang, Q.;
Gu, S.; Zheng, J.; Zhuang, Z.; Qiu, S.; Yan, Y. Angew. Chem.
Int. Ed. 2014, 53, 2878ꢀ2882; (g) Qiao, Z.ꢀA.; Zhang, P.; Chai,
S.ꢀH.; Chi, M.; Veith, G. M.; Gallego, N. C.; Kidder, M.; Dai, S.
J. Am. Chem. Soc. 2014, 136, 11260ꢀ11263; (h) Li, B.; Zhang,
Y.; Ma, D.; Ma, T.; Shi, Z.; Ma, S. J. Am. Chem, Soc. 2014, 136,
vinylphenyl)magnesium bromide solution, which was
synthesized from 4ꢀbromostyrene (60 mmol) and magꢀ
nesium powder (70 mmol). After stirring at RT for 2 h,
5
0 mL of saturated NH Cl aqueous was added to quench
4
the reaction. The organic phase was separated, and water
phase was extracted with an excess of diethyl ether. The
combined organic phase was washed with brine, dried
over MgSO , filtered, and concentrated in vacuum. The
4
obtained crude product was purified by silica gel chroꢀ
matography (5%EtOAc/Petroleum ether) to afford vinylꢀ
functionalized dppe monomer as a white solid.
Synthesis of diphosphine ligand constructed
porous polymers. One typical example, 2.0 g of vinylꢀ
functionalized dppe monomer was dissolved in 20 mL of
THF, followed by addition of 50 mg of azobisisobuꢀ
tyronitrile (AIBN). The mixture was transferred into an
autoclave at 100 °C for 24 h. After evaporation of THF
under vacuum, a solid monolith was obtained and deꢀ
noted as POLꢀdppe.
1
202; (i) Gao, W.ꢀY.; Chen, Y.; Niu, Y.; Williams, K.; Cash, L.;
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Chem. Int. Ed. 2014, 53, 2615.
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ASSOCIATED CONTENT
Supporting Information
3
038; (f) Adint, T. T.; Landis, C. R. J. Am. Chem. Soc. 2014,
Synthesis, characterization and catalytic data details. This
material is available free of charge via the Internet at
http://pubs.acs.org.
136, 7943ꢀ7953; (g) Bianchini, C.; Burnaby, D. G.; Evans, J.;
Frediani, P.; Meli, A.; Oberhauser, W.; Psaro, R.; Sordelli, L.;
Vizza, F. J. Am. Chem. Soc. 1999, 121, 5961ꢀ5971; (h)
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1
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AUTHOR INFORMATION
mentin, S.; Woisel, P.; Monflier, E.; Hapiot, F. ACS Catal.
2012, 2, 1417ꢀ1420; (j) Shylesh, S.; Hanna, D.; Mlinar, A.;
Kǒ ng, X.ꢀQ.; Reimer, J. A.; Bell, A. T. ACS Catal. 2013, 3,
Corresponding Author
3
48ꢀ357; (k) Arya, P.; Panda, G.; Rao, N. V.; Alper, H.;
Bourque, S. C.; Manzer, L. E. J. Am. Chem. Soc. 2001, 123,
2889ꢀ2890.
Arhancet, J. P.; Davis, M. E.; Merola, J. S.; Hanson, B. E.
Nature 1989, 339, 454ꢀ455.
Notes
The authors declare no competing financial interests.
5.
ACKNOWLEDGMENT
6
.
(a) Mehnert, C. P.; Cook, R. A.; Dispenziere, N. C.; Afeworki,
M. J. Am. Chem. Soc. 2002, 124, 12932ꢀ12933; (b) Schneider,
M. J.; Lijewski, M.; Woelfel, R.; Haumann, M.; Wasserscheid,
P. Angew. Chem. Int. Ed. 2013, 52, 6996ꢀ6999; (c) Riisager,
A.; Fehrmann, R.; Flicker, S.; van Hal, R.; Haumann, M.;
Wasserscheid, P. Angew. Chem. Int. Ed. 2005, 44, 815ꢀ819.
Mecking, S.; Thomann, R. Adv. Mater. 2000, 12, 953ꢀ956.
(a) Wang, F.; Mielby, J.; Herrmann, F.; Wang, G.; Prieto, G.;
Kasama, T.; Weidenthaler, C.; Bongard, H.ꢀJ.; Kegnæs, S.;
Fürstner, A.; Schüth, F. Angew. Chem. Int. Ed. 2014, 53,
8645ꢀ8648; (b) Fischer, S.; Schmidt, J.; Strauch, P.; Thomas,
A. Angew. Chem. Int. Ed. 2013, 52, 12174ꢀ12178; (c) Kuhn, P.;
Antonietti. M.; Thomas. A. Angew. Chem. Int. Ed. 2008, 47,
This work was supported by the National Natural Science
Foundation of China (21273197, 21333009 and 21422306)
and National HighꢀTech Research and Development
program of China (2013AA065301).
7
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