Communication
ChemComm
(b) Y. M. A. Yamada, Y. Yuyama, T. Sato, S. Fujikawa and Y. Uozomi,
Angew. Chem., Int. Ed., 2014, 53, 127; (c) T. Iwai, T. Harada, K. Hara
and M. Sawamura, Angew. Chem., Int. Ed., 2013, 52, 12322;
(d) T. Iwai, R. Tanaka, T. Harada and M. Sawamura, Chem. – Eur.
J., 2014, 20, 1057.
4 (a) M. Waki, Y. Maegawa, K. Hara, Y. Goto, S. Shirai, Y. Yamada,
N. Mizoshita, T. Tani, W.-J. Chun, S. Muratsugu, M. Tada,
A. Fukuoka and S. Inagaki, J. Am. Chem. Soc., 2014, 136, 4003;
(b) D. Astruc and F. Chardac, Chem. Rev., 2001, 101, 2991.
5 (a) G.-j. ten Brink, I. W. C. E. Arends and R. A. Sheldon, Science,
2000, 287, 1636; (b) I. T. Horvath and J. Rabai, Science, 1994, 266, 72.
6 M. Guino and K. K. Hii, Chem. Soc. Rev., 2007, 36, 608.
7 (a) C. Bianchini, D. G. Burnaby, J. Evans, P. Frediani, A. Meli,
W. Oberhauser, R. Psaro, L. Sordelli and F. Vizza, J. Am. Chem.
Soc., 1999, 121, 5961; (b) P. Barbaro, C. Bianchini, V. Dal Santo,
A. Meli, S. Moneti, R. Psaro, A. Scaffidi, L. Sordelli and F. Vizza,
J. Am. Chem. Soc., 2006, 128, 7065.
8 R. A. Findeis and L. H. Gade, Eur. J. Inorg. Chem., 2003, 99.
9 P. Schober, G. Huttner, L. Zsolnai and A. Jacobi, J. Organomet.
Chem., 1998, 571, 279.
10 R. A. Findeis and L. H. Gade, Dalton Trans., 2003, 249.
11 (a) J.-C. Hierso, R. Amardeil, E. Bentabet, R. Broussier, B. Gautheron,
P. Meunier and P. Kalck, Coord. Chem. Rev., 2003, 236, 143;
(b) H. A. Mayer and W. C. Kaska, Chem. Rev., 1994, 94, 1239.
the polyphosphane-based heterogeneous catalysts and their stability
were demonstrated, in general, efficient recycling of the catalysts
after six runs has not been established, this is mainly due to
accumulative loss of material during filtration. For the insoluble
catalysts used at 0.5 mol%, ICP-AES analysis of the filtrate indicated
no significant leaching (o10 ppm, less than 0.1% of the initial Pd
loading). Accordingly, the hot filtration test showed the termination
of the cross-coupling reactions by use of the filtrate recharged with
reagents and bases. The resulting cumulative TONs (270–1700) of
the catalysts compares favorably to their homogeneous counterparts.
The supported triphosphine 19a-PS was investigated in the
coupling of chloroarenes to furane, thiophene, and pyrrole
substrates by direct C2 C–H functionalization. These reactions
were inspired by the performance of the ferrocenyltriphosphines
reported in these relevant reactions that eliminate the need for
pre-functionalization of substrates for coupling.12
We were glad to observe that these direct arylation reactions of
heteroaromatics, which are typically promoted by triphosphines
under homogeneous conditions, were also achievable under hetero-
geneous conditions. The arylation of 2-n-butylfurane with 4-chloro-
benzonitrile (68%) and the coupling of 2-n-butylthiophene to
4-chloronitrobenzene (49%) were achieved more efficiently than the
C2 arylation of 1-methyl-2-formylpyrrole with 4-chlorobenzaldehyde
(23%). All these coupling tolerate the functionalization of the chloro-
arene and heteroaromatic substrates, and represent promising results
towards difficult C–H functionalization with demanding chloroarenes
under ‘‘greener’’ heterogeneous conditions.
´
12 (a) D. Roy, S. Mom, M. Beauperin, H. Doucet and J.-C. Hierso, Angew.
Chem., Int. Ed., 2010, 49, 6650; (b) D. Roy, S. Mom, D. Lucas,
H. Cattey, J.-C. Hierso and H. Doucet, Chem. – Eur. J., 2011, 17, 6453.
13 (a) J.-C. Hierso, A. Fihri, R. Amardeil, P. Meunier, H. Doucet, M. Santelli
and V. V. Ivanov, Org. Lett., 2004, 6, 3473; (b) J.-C. Hierso, A. Fihri,
R. Amardeil, P. Meunier, H. Doucet, M. Santelli and B. Donnadieu,
Organometallics, 2003, 22, 4490.
14 (a) M. Sophal, M. Platon, H. Cattey, H. J. Spencer, P. J. Low and
J.-C. Hierso, Catal. Commun., 2014, 51, 10; (b) M. Platon, J. Roger,
S. Royer and J.-C. Hierso, Catal. Sci. Technol., 2014, 4, 2072.
15 M. Platon, L. Cui, S. Mom, P. Richard, M. Saeys and J.-C. Hierso, Adv.
Synth. Catal., 2011, 353, 3403.
16 (a) J.-C. Hierso, A. Fihri, V. V. Ivanov, B. Hanquet, N. Pirio,
In summary, we have delivered a general strategy for synthe-
sizing localized high density of donor atoms on a support. This may
be additionally useful for organophosphorus catalysis,24 and general
surface modification.25 Heterogeneous functional systems based on
metal complexes with coordinating ligands have also been con-
structed for applications as photosensitizers and for solar energy
conversion.4a Accordingly, we introduced the conceptual novelty of
controlling both the implantation and conformational arrangement of
donors in immobilized catalysts,26 which has not been achieved
with other )classical ligands*. The demonstration regarding the
control of conformation is supported by high resolution 31P-NMR in
solution, for which the proximity of phosphino groups, and their
interaction, is evidenced by intense nonbonded )through-space*
spin–spin couplings. Additionally, this study provides proof-of-
concept of supported catalytic materials built from modular poly-
phosphines for the formation of efficient and recyclable polydentate
heterogeneous palladium catalysts.
`
B. Donnadieu, B. Rebiere, R. Amardeil and P. Meunier, J. Am. Chem.
Soc., 2004, 126, 11077; (b) O. L. Malkina and V. G. Malkin, Angew.
Chem., Int. Ed., 2003, 42, 4335; (c) T. Wiegand, H. Eckert, J. Ren,
G. Brunklaus, R. Froehlich, C. G. Daniliuc, G. Luebbe, K. Bussmann,
G. Kehr, G. Erker and S. Grimme, J. Phys. Chem. A, 2014, 118, 2316.
17 (a) J.-C. Hierso, Chem. Rev., 2014, 114, 4838; (b) J.-C. Hierso, in High
Resolution Nuclear Magnetic Resonance Parameters: Understanding
Molecules and their Electronic Structures, ed. R. H. Contreras, Else-
vier, Amsterdam, 2014.
18 M. Bu¨hl, F. R. Knight, A. Kristkova, I. Malkin Ondik, O. L. Malkina,
R. A. M. Randall, A. M. Z. Slawin and J. D. Woollins, Angew. Chem.,
Int. Ed., 2013, 52, 2495.
19 (a) W. Wang, M. Fujiki and K. Nomura, J. Am. Chem. Soc., 2005,
127, 4582; (b) A. Gansaeuer, C. Kube, K. Daasbjerg, R. Sure,
S. Grimme, G. D. Fianu, D. V. Sadasivam and R. A. Flowers, J. Am.
Chem. Soc., 2014, 136, 1663.
¨
20 (a) S. Knuppel, G. Erker and R. Frohlich, Angew. Chem., Int. Ed.,
1999, 38, 1923; (b) B. Bosch, G. Erker, R. Froehlich and O. Meyer,
Organometallics, 1997, 16, 5449; (c) G. Erker, G. Kehr and
¨
R. Frohlich, J. Organomet. Chem., 2004, 689, 1402.
21 J. A. Pool, E. Lobkovsky and P. J. Chirik, J. Am. Chem. Soc., 2003,
125, 2241.
22 (a) P. B. Hitchcock, M. F. Lappert and S. Tian, Organometallics, 2000,
19, 3420; (b) M. R. Douglass and T. J. Marks, J. Am. Chem. Soc., 2000,
122, 1824.
23 Polyphosphines L1–L3 can be used as palladium auxiliary ligands
under homogeneous conditions, and are commercially available
under the name HiersoPHOS (Strem Chemicals).
The work was supported by the ANR program for Sustain-
able Chemistry Development (ANR-09-CP2D-03 CAMELOT), the
´
Region Bourgogne-CNRS (3MIM program), and the Procore
France-Hong-Kong program.
24 J. Lu and P. H. Toy, Pure Appl. Chem., 2013, 85, 543.
25 A. Huber, A. Kuschel, T. Ott, G. Santiso-Quinones, D. Stein, J. Braeuer,
R. Kissner, F. Krumeich, H. Schoenberg, J. Levalois-Gru¨tzmacher and
H. Gru¨tzmacher, Angew. Chem., Int. Ed., 2012, 51, 4648.
Notes and references
1 (a) C. W. Jones, Top. Catal., 2010, 53, 942; (b) Heterogenized Homogeneous
Catalysts for Fine Chemicals Production: Materials and Processes, ed.
P. Barbaro and F. Liguori, Springer, Dordrecht, 2010; (c) Recoverable 26 Modular functionalized polyphosphines, the methods for high local
and Recyclable Catalysts, ed. M. Benaglia, Wiley, Chichester, 2009.
2 N. E. Leadbeater and M. Marco, Chem. Rev., 2002, 102, 3217.
3 For recent exciting examples: (a) D. T. Genna, A. G. Wong-Foy,
A. J. Matger and M. S. Sanford, J. Am. Chem. Soc., 2013, 135, 10586;
density implantation of P-donors on supports and their applications
´
are patented: J.-C. Hierso, M. Beauperin and P. Meunier, FR Pat.,
2961813 A1 20111230, 2011; WO 2012001601 A1 20120105, 2012;
US2013158219 (A1).
9508 | Chem. Commun., 2014, 50, 9505--9508
This journal is ©The Royal Society of Chemistry 2014