10.1002/chem.201604780
Chemistry - A European Journal
FULL PAPER
reaction mixture was evaporated to dryness and the crude reaction
mixture was further purified by column chromatography with a mixture of
petroleum ether and ethyl acetate.
Chem. 2010, 3, 615-621; h) A. J. Sandee, J. N. H. Reek, Dalton Trans.
2006, 3385-3391; i) S. Carboni, C. Gennari, L. Pignataro, U. Piarulli,
Dalton Trans. 2011, 40, 4355-4373.
[4]
a) D. Schroeder, S. Shaik, H. Schwarz, Acc. Chem. Res. 2000, 33,
139-145; b) W. Kaim, Eur. J. Inorg. Chem. 2012, 343-348; c) V.
Lyaskovskyy, B. de Bruin, ACS Catal. 2012, 2, 270-279; d) K. Hindson,
B. de Bruin, Eur. J. Inorg. Chem. 2012, 340-342; e) P. J. Chirik, Inorg.
Chem. 2011, 50, 9737-9740; f) O. R. Luca, R. H. Crabtree, Chem. Soc.
Rev. 2013, 42, 1440-1459.
General
procedure
for
ruthenium-catalyzed
C-H
bond
functionlization: A Schlenk tube under an argon atmosphere was filled
with 2-phenylpyridine (0.5 mmol, 1 eq), bromobenzene (1.25 mmol, 2.5
eq), anhydrous potassium carbonate (1.5 mmol, 3 eq), A (0.5 mmol, 1
eq) -if applied-, [RuCl2(p-cymene)]2 (0.0125 mmol, 2.5 mol%), 2,4,6-
trimethylbenzoic acid (0.15 mmol, 30 mol%) and toluene (2 mL). The
reaction mixture was placed in a preheated oil bath at 120 oC and stirred
during 24 hours. Back at room temperature, water (30 mL) was added
and the crude reaction mixture was extracted with ethyl acetate (3 x 20
mL). The combined organic layers were dried over MgSO4, filtrated and
concentrated in vacuum. The 1H NMR, GC/MS and TLC analysis of the
crude reaction mixture indicated the exclusive formation of the bis-
arylated product which was further isolated in >95% yield by column
chromatography on silica gel (petroleum ether/ethyl acetate).
[5]
[6]
a) S. Kuwata, T. Ikariya, Chem. Eur. J. 2011, 17, 3542-3556; b) S.
Schneider, J. Meiners, B. Askevold, Eur. J. Inorg. Chem. 2012, 412-
429; c) B. Zhao, Z. Han, K. Ding, Angew. Chem. Int. Ed. 2013, 52,
4744-4788; Angew. Chem. 2013, 125, 4844-4889.
a) C. J. Brown, F. D. Toste, R. G. Bergman, K. N. Raymond, Chem.
Rev. 2015, 115, 3012-3035; b) S. H. A. M. Leenders, R. Gramage-
Doria, B. de Bruin, J. N. H. Reek, Chem. Soc. Rev. 2015, 44, 433-448;
f) S. Zarra, D. M. Wood, D. A. Roberts, J. R. Nitschke, Chem. Soc. Rev.
2015, 44, 419-432; g) L. Catti, Q. Zhang, K. Tiefenbacher, Synthesis
2016, 48, 313-328.
[7]
a) P. W. N. M. van Leeuwen, Supramolecular Catalysis (Wiley-VCH,
Weinheim, Germany, 2008); b) M. Raynal, P. Ballester, A. Vidal-Ferran,
P. W. N. M. van Leeuwen, Chem. Soc. Rev. 2014, 43, 1660-1733; c) P.
Dydio, J. N. H. Reek, Chem. Sci. 2014, 5, 2135-2145.
Supporting Information. Further experimental details including NMR
data, UV-vis titration studies (including Job-Plot analysis),
crystallographic details and calibration curves are provided in the
supporting information. The supplementary crystallographic data for 2•A
(CCDC-1509179), 5•A (CCDC-1509180), 6•A (CCDC-1509181), 2•B
(CCDC-1509182), 4•B (CCDC-1509183) and 5•B (CCDC-1509178) can
be obtained free of charge from The Cambridge Crystallographic Data
[8]
[9]
R. H. Crabtree, Chem. Rev. 2015, 115, 127-150.
a) T. Eicher, S. Hauptmann, A. Speicher, H. Suschitzky, The Chemistry
of Heterocycles: structure, reactions, synthesis and applications (Wiley-
VCH, Weinheim, Germany, 2008); b) G. Jones, Comprehensive
Heterocyclic Chemistry II, Vol. 5 (Eds. A.R. Katritzky, C.W. Rees, E.F.V.
Scriven, A. McKillop, Pergamon, Oxford 1996, pp. 167-243); c) J.A.
Joule, K. Mills, Hetrocyclic Chemistry 4th ed. (Blackwell Science,
Cambridge, 2000, pp. 63-120).
Acknowledgements
[10] J. Liu, X. Zhang, H. Yi, C. Liu, R. Liu, H. Zhang, K. Zhuo, A. Lei, Angew.
Chem. Int. Ed. 2015, 54, 1261-1265; Angew. Chem. 2015, 127, 1277-
1281.
C.B. and R.G.-D. acknowledge the CNRS and Université de
Rennes 1 for providing financial support. The Université Kasdi
[11] a) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483; b) R.
Martin, L. Buchwald, Acc. Chem. Res. 2008, 41, 1461-1473; c) A. F.
Littke, G. C. Fu, Angew. Chem. Int. Ed. 2002, 41, 4176-4211; Angew.
Chem. 2002, 114, 4350-4386.
Merbah (Ouargla, Algeria) is acknowledged for
scholarship to M.K.
a visiting
[12] a) V. Farina, Adv. Synth. Catal. 2004, 346, 1553-1582; b) N. T. S. Phan,
M. Van der Sluys, C. W. Jones, Adv. Synth. Catal. 2006, 348, 609-679.
[13] a) Y.-G. Zhou, Acc. Chem. Res. 2007, 40, 1357-1366; b) D.-S. Wang,
Q.-A. Chen, S.-M. Lu, Y.-G. Zhou, Chem. Rev. 2012, 112, 2557-2590;
c) F. Glorius, Org. Biomol. Chem. 2005, 3, 4171-4175; d) R. Kuwano
Heterocycles 2008, 76, 909-922; e) N. Fleury-Brégeot, V. de la Fuente,
S. Castillón, C. Claver, ChemCatChem 2010, 2, 1346-1371; f) H.-U.
Blaser, C. Malan, B. Pugin, F. Spindler, H. Steiner, M. Studer, Adv.
Synth. Catal. 2003, 345, 103-151.
Keywords: palladium catalysis • weak interactions • pyridine •
porphyrin • salphen
[1]
a) R. Noyori, Nat. Chem. 2009, 1, 5-6; b) K. Sanderson, Nature 2011,
469, 18-20; c) R. A. Sheldon, Chem. Soc. Rev. 2012, 41, 1437-1451; d)
G. Rothenberg, Catalysis: Concepts and Green Applications (Wiley-
VCH, Weinheim, Germany, 2008); e) M. Beller, Chem. Soc. Rev. 2011,
40, 4891-4892.
[2]
a) J. F. Hartwig, Organotransition Metal Chemistry: From Bonding to
Catalysis, University Science Books, Sausalito, CA, USA 2009; b) M.
Beller, C. Bolm, Transition Metals for Organic Synthesis (Wiley-VCH,
Weinheim, Germany, 2004); c) A. de Meijere, F. Diederich, Metal-
[14] a) L.-C. Campeau, S. Rousseaux, K. Fagnou, J. Am. Chem. Soc. 2005,
127, 18020-18021; b) J.-P. Leclerc, K. Fagnou, Angew. Chem. Int. Ed.
2006, 45, 7781-7786, Angew. Chem. 2006, 118, 7945-7950; c) K. S.
Kanyiva, Y. Nakao, T. Hiyama, Angew. Chem. Int. Ed. 2007, 46, 8872-
8874, Angew. Chem. 2007, 119, 9038-9030.
Catalyzed Cross-Coupling Reactions, 2nd
, Completely Revised and
Enlarged Edition (Wiley-VCH, Weinheim, Germany, 2004); d) A. de
Meijere, S. Braese, M. Oestreich, Metal-Catalyzed Cross-Coupling
Reactions and More (Wiley-VCH, Weinheim, Germany, 2014).
[15] a) K.M. Kadish, K.M. Smith, R. Guilard, Handbook of Porphyrin Science
Vol 1-35, World Scientific Publishing; b) T. Imamura, K. Fukushima,
Coord. Chem. Rev. 2000, 198, 133-156; c) S. Belanger, M. H. Keefe, J.
L. Welch, J. T. Hupp, Coord. Chem. Rev. 1999, 190-192, 29-45; d) H. E.
Thoma, K. Araki, Coord. Chem. Rev. 2000, 196, 307-329; e) J.
Wojaczynksi, L. Latos-Grazynski, Coord. Chem. Rev. 2000, 204, 113-
171; f) S. Durot, J. Taesch, V. Heitz, Chem. Rev. 2014, 114, 8542-
8578; g) I. Beletskaya, V. S. Tyurin, A. Y. Tsivadze, R. Guilard, C. Stern,
Chem. Rev. 2009, 109, 1659-1713; h) J. A. A. W. Elemans, V. F. Slagt,
A. E. Rowan, R. J. M. Nolte, Isr. J. Chem. 2005, 45, 271-279; i) A. W.
Kleij, J. N. H. Reek, Chem. Eur. J. 2006, 12, 4218-4227; j) K. S. Suslick,
N. A. Rakow, M. E. Kosal, J.-H. Chou, J. Porphyrins Phtalocyanines
2000, 4, 407-413; k) K. M. Kadish, D. J. Leggett, D. Chang, Inorg.
[3]
a) P. W. N. M. van Leeuwen, Homogeneous Catalysis: Understanding
the Art (Kluwer Academic Publishers, Dordrecht, The Netherlands,
2004); b) P. C. J. Kamer, P.W.N.M. van Leeuwen, Phosphorus(III)
Ligands in Homogeneous Catalysis: Design and Synthesis (Wiley-VCH,
Weinheim, Germany, 2012); c) R. H. Crabtree, New. J. Chem. 2011, 35,
18-23; d) W. I. Dzik, J. I. van der Vlugt, J. N. H. Reek, B. de Bruin,
Angew. Chem. Int. Ed. 2011, 50, 3356-3358; Angew. Chem. 2011, 123,
3416-3418; e) H. Grützmacher, Angew. Chem. Int. Ed. 2008, 47, 1814-
1818; Angew. Chem. 2008, 120, 1838-1842; f) J. I. van der Vlugt, Eur.
J. Inorg. Chem. 2012, 363-375; g) J. Meeuwissen, J. N. H. Reek, Nat.
This article is protected by copyright. All rights reserved.