DOI: 10.1002/cctc.

201100108

Intramolecular CH Oxidative N-Allylation of CHomoallylhydrazones to 5-Vinyl-2-pyrazolines Catalyzed by the [Pd(OAc)2]/BIMINAP System

Thanh-Tung Dang,[a, b] Ibrahim Abdellah,[a, b] Yves Canac,*[a, b] and Remi Chauvin*[a, b]
Dedicated to Dr. Christian Bruneau on the occasion of his 60th birthday.

A catalytic procedure is described for intramolecular benzoquinone-mediated CH oxidative N-allylation of C-homoallylhydrazones to 5-vinyl-2-pyrazolines. Depending on the steric and electronic demand of the substituents at the allylic moiety of the substrate, other six or seven membered cyclic hydrazones were obtained in moderate yields. As compared to other Pd(OAc)2/phosphine combinations, the optimal catalytic conditions are based on the Pd(OAc)2/BIMINAP system [BIMINAP = formal contraction of the acronyms BIMIP = 2,2-bis(diphenyl-

phosphino)-1,1-bibenzimidazole and BINAP = 2,2-bis(diphenylphosphino)-1,1-binaphthyl in a 10 % ratio. In a preliminary attempt, the use of the enantiopure (R)-BIMINAP ligand was shown to provide the corresponding 5-vinyl-2-pyrazoline in 75 % yield and 30 % ee in the (+)-enantiomer, whereas the analogous (R)-BINAP ligand afforded the same product in only 47 % yield and 10 % ee. The results highlight the specific value of the electron-poor atropochiral BIMINAP ligand in catalysis and, in particular, oxidative catalysis.

Introduction
Similar to other endocyclic hydrazones, 2-pyrazolines present a wide range of biological properties, such as anticancer, anti-inflammatory, antibacterial, and antiviral activities,[1] and they also exhibit valuable chromophoric properties.[2] From a retrosynthesis standpoint, 2-pyrazolines are tautomerization products of 1-pyrazolines generated by 1,3-dipolar [3+2] cycloaddition of diazoalkanes with electrophilic alkenes, such as acrylate derivatives.[3] They can also be directly generated by 1,3-dipolar [3+2] cycloaddition of nitrilimines with the same alkenes.[4] More generally, as was demonstrated by Fischer, 2-pyrazolines are [2+3] cyclo-condensation products of hydrazines with aenals or a-enones.[5] This method, based on a Michael addition process, remains the most widely used,[6] and the same principle applies to a recently disclosed asymmetric version based on an acid-catalyzed cycloisomerization of a,b-unsaturated hydrazones.[7] Nevertheless, alternative [2+3] processes have been devised for the synthesis of 2-pyrazolines with specific substitution patterns from hydrazine equivalents and other three carbon electrophiles, such as homopropargylic alcohols,[8] ynones (giving hydrated pyrazoles),[9] 1,3-dihaloalkanes (through concomitant oxidation of the primary pyrazolidine product),[10] or 2-acylaziridines.[11] Although 5-carbonyl, 5-cyano, and 5-aryl-2-pyrazolines have been extensively studied,[1] only a few vinyl-substituted pyrazolines have been prepared, for example by [3+2] cycloaddition of diazoalkanes with Fischer carbene analogues of acrylic C=C double bonds.[12] In a more specific and systematic manner, 5-vinyl-2-pyrazolines could be envisioned by intramolecular oxidative N-allylation of suitable substrates. Indeed, selective transition-metal catalyzed formation of CN bonds through CH activation proved to be a powerful tool for the preparation of other nitrogen heterocycles.[13] The first example was reported by
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Buchwald et al. in 2005 for the preparation of carbazoles from amides.[14] Application of this process to other substrates, such as hydrazones,[15] enamines,[16] phenylacetamides,[17] and arylethylamines,[18] allowed for the preparation of indazoles, indoles, oxindoles, and indolines, respectively. Along this line, White et al. recently described the formation of oxazolidinones from allylic N-tosylcarbamates by palladium catalyzed intramolecular C-H amination using a bis-sulfoxide ligand.[19] In this report, the latter approach was applied on N-sulfonylhydrazones of homoallylketones for the preparation of 5-alkenyl-2-pyrazolines using catalytic systems based on PdX2/L2/oxidizing agent (X = OCOCF3, OAc; L = phosphine ligands) combinations. Although most catalytic procedures for allylic oxidation rely on the use of sulfoxide or nitrogen ligands, the use of phosphine ligands (L) is investigated here.

Results and Discussion

Various C-homoallylhydrazones were first prepared in two steps from the corresponding ketone, sulfonyl-hydrazine, and allylic bromide (Scheme 1).[20] As in the analogous oxime
[a] Dr. T.-T. Dang, Dr. I. Abdellah, Dr. Y. Canac, Prof. R. Chauvin CNRS; LCC (Laboratoire de Chimie de Coordination) 205, route de Narbonne, F-31077 Toulouse (France) Fax: (+ 33) 5-61-55-30-03 E-mail: yves.canac@lcc-toulouse.fr chauvin@lcc-toulouse.fr [b] Dr. T.-T. Dang, Dr. I. Abdellah, Dr. Y. Canac, Prof. R. Chauvin Universit de Toulouse; UPS, INP; LCC F-31077 Toulouse (France) Supporting Information for this article is available on the WWW under http://dx.doi.org/10.1002/cctc.201100108.

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Y. Canac, R. Chauvin et al. the absence of a phosphine ligand, only Pd(OAc)2 as a precatalyst and benzoquinone as an oxidizing agent in THF afforded some pyrazoline (2 a) in 10 % yield after 24 h at 90 8C (Table 1, entry 5). Addition of two equivalents with respect to Pd(OAc)2 of a monophosphine ligand led to a higher yield of 2 a while decreasing the temperature to 45 8C (55 % yield with L = PCy3, 25 % yield with L = PPh3 ; entries 6 and 7, Table 1). Addition of a diphosphine was then attempted. Although the use of 1,2-(diphenylphosphino)benzene (L2 = o-dppb) resulted in lower activity (the reaction had to be carried out for 60 h to give 2 a in 35 % yield; Table 1, entry 8), the use of the BIMINAP ligand (in the racemic form, Scheme 2) afforded 2 a in 75 % yield after 36 h at 45 8C (Table 1, Scheme 1. Preparation of C-homoallylhydrazones 1 ak from ketones. entry 9). As suggested by its acronym, BIMINAP[23] is a C1-symmetric hybrid of the 2,2-bis(diphenylphosphino)-1,1-biseries,[21] two equivalents of a base, n-butyl lithium (nBuLi), were required in the second step to generate the hydrazidonaphthyl (BINAP)[24] and 2,2-bis(diphenylphosphino)-1,1-bibenenamide intermediate, which reacted with the allylic bromide zimidazole (BIMIP)[25] ligands. It has recently been reported to to give the C-homoallylhydrazones 1 ak in 4288 % yield (N-alpossess a moderately electron-poor character, and palladium lylation products were not isolated).[22] complexes thereof were shown to efficiently catalyze the Tsuji The C-homoallyl-N-phenylsulfonylhydrazone (1 a) was first Trost allylation.[26] As compared to o-dppb, the higher efficienselected as a test substrate for the determination of optimal cy of BIMINAP can be attributed to a greater chelating flexibiliconditions for the preparation of the 2-pyrazoline 2 a using ty (the palladacycle given by BIMINAP is seven membered, but various combinations of the palladium precatalyst (PdX2, in that given by o-dppb is five membered). 10 % catalytic ratio), ligand (L2), stoichiometric oxidizing agent, In a preliminary attempt at asymmetric catalysis, enantiosolvent, temperature, and reaction time (Scheme 2, Table 1). In pure (R)-BIMINAP was used as the ligand.[26a] Pyrazoline 2 a was thus obtained in a similar yield to reactions with the rac-BIMINAP ligand and 30 % ee in the (+)-2 a enantiomer (Table 1, entry 13). For comparison, the same procedure with the (R)-BINAP ligand afforded 2 a in a lower yield (47 %) and a lower ee (10 % for the same (+)-2 a enantiomer; Table 1, entry 14). These results deserved optimization efforts, and the search for an enlarged scope of the atropochiral BIMINAP ligand in Scheme 2. Pd-catalyzed intramolecular oxidative N-allylation of the homoallylhydrazone both catalysis and asymmetric catalysis. 1 a and the structure of BIMINAP, an optimal ligand (L) for this process (see Table 1). With these optimized reaction conditions in hand, the scope of the reaction was inTable 1. Reaction conditions used for the preparation of pyrazoline 2 a from hydrazone 1 a (Scheme 2).[a] vestigated with other substrates (1 bj, Scheme 1, Table 2). As [b] [c] [d] [e] Entry PdX2 salt L2 ligand Oxidant Solvent T [8C] t [h] Yield [%] ee [%] shown in Table 2, the selected 1 Pd(OCOCF3)2 AgOAc/CuCl2 DCE 90[f] 24 0 conditions could be applied to a benzoquinone THF 60 24 0 2 Pd(OCOCF3)2 wide range of other C-aryl hydra[f] 3 Pd(OAc)2 AgOAc/CuCl2 THF 90 24 0 zone substrates without a subPhI(OAc)2 THF 90[f] 24 0 4 Pd(OAc)2 benzoquinone THF 90[f] 24 10 5 Pd(OAc)2 stituent on the allyl fragment 2 PCy3[g] benzoquinone THF 45 36 55 6 Pd(OAc)2 (1 bg), providing the 5-vinyl-22 PPh3 benzoquinone THF 45 36 25 7 Pd(OAc)2 pyrazolines 2 bg in moderate 8 Pd(OAc)2 2 o-dppb benzoquinone THF 45 60 35 yields (Table 2, entries 27), rac-BIMINAP benzoquinone THF 45 36 75 9 Pd(OAc)2 rac-BIMINAP benzoquinone DCE 65 36 15 10 Pd(OAc)2 along with either unreacted rac-BIMINAP benzoquinone acetone 65 36 13 11 Pd(OAc)2 starting material or unidentified rac-BIMINAP benzoquinone EtOH 65 36 0 12 Pd(OAc)2 side products. [e] (R)-BIMINAP benzoquinone THF 45 36 70 30 [(+)-2 a] 13 Pd(OAc)2 In contrast, the hydrazone (R)-BINAP[e] benzoquinone THF 45 36 47 10 [(+)-2 a] 14 Pd(OAc)2 substrates 1 hj with substituted [a] DCE = 1,2-dichloroethane, EtOH = ethanol, OAc = acetate, o-dppb = 1,2-(diphenylphosphino)benzene, PCy3 = allyl moieties did not give the tricyclohexylphosphine, PPh3 = triphenylphosphine. [b] 10 % mol of the Pd/L2 catalyst. [c] AgOAc/CuCl2 (1 equiv/1 equiv); PhI(OAc)2 (2 equiv); 1,4-benzoquinone (2 equiv). [d] Yield of analytically pure isolated prodexpected 2-pyrazolines. Cyclic uct. [e] ee values were measured by using analytical HPLC (column AD-H 4.6 250 mm, 35 8C). [f] Reactions hydrazones 2 hj with six or were carried out under pressure in a tightly capped flask. [g] Generated in situ from [HPCy3],[PF6]. seven membered rings were ob-

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CH Oxidative N-Allylation The p-allyl-Pd intermediate of this mechanism provides an exYield [%][a] Entry Substrate Product Yield [%][a] Entry Substrate Product planation of the formation of endocyclic hydrazones with large ring sizes (2 hj) when the conditions are applied to homoallylhy1 1a 75 6 1f 50 drazone substrates with a substituted allylic moiety (1 hj). Whereas unsubstituted p-allyl fragments undergo nucleophilic attack at the substituted external 2 1b 55 7 1g 47 position (stabilizing an excess of local positive charge to give 2-pyrazoline through path A in Scheme 3), substituents at the terminal external positions of 3 1c 45 8 1h 37 the allyl ligand could orientate the attack by modified charge control (Scheme 3). A terminal phenyl substituent is indeed expected to polarize the allyl frag4 1d 52 9 1i 28 ment by an excess of positive charge at the opposite allylicbenzylic position (Scheme 3, B); N-allylation would thus occur at this remote, external position to give the seven membered hydra5 1e 42 10 1j 37 zone 2 h in 37 % yield (Table 2, entry 8). The proposed mechanism also [a] Yield in analytically pure isolated product. Reaction conditions: 10 % Pd(OAc)2, 10 % BIMINAP, 2 equiv of 1,4accounts for the formation of benzoquinone, 45 8C, THF, 36 h. the six-membered cyclic hydrazone 2 i (28 % yield; Table 2, entry 9). In the corresponding substrate (1 i), two different types of allylic sp3 CH bonds can tained instead. This reveals the occurrence of a delocalized p-allyl intermediate. It has indeed been previously suggested indeed be activated, and the most accessible ones on the that intramolecular allylic CH amination occurred through methyl substituents are preferred because of steric factors. The PdII-mediated heterolytic cleavage of an allylic CH bond, genresulting allyl ligand would then undergo nucleophilic attack erating a [Pd(p-allyl)(OAc)] (OAc = acetate) intermediate.[19b] In of the hydrazide anion at the substituted external position, stasuch a process, the acetate ligand would thus play the role of bilizing a local excess of positive charge (Scheme 3, A), as it a base for the allylic proton, which exhibits enhanced acidity occurs from C-homoallylhydrazone substrates (1 ag) without a after h2 coordination of the C=C double bond, possibly substituent at the allyl fragment (Scheme 3, A; see above). through a PdIV hydride intermediate (the trifluoroacetate ligand would thus not be basic enough for this initiating step; Table 1, entries 1 and 2). After dissociation of the remaining acetate ligand, which would deprotonate the sulfonylhydrazone, the resulting p-allyl ligand would then undergo a nucleophilic attack of the proximal nitrogen atom of the sulfonyl hydrazide. The alkenePd0 complex formed would finally dissociate to release the pyrazoline product. Simultaneously, the Pd0 center would be oxidized by benzoquinone and regenerate the Pd(OAc)2 precatalyst after protonation of the hydroquinone dianion by the released AcOH molecules. It is noteworthy that from analogous C-di-alkylhydrazone substrates, a Scheme 3. Possible outcomes of the intramolecular N-allylation step in the reaction was not observed: this lack of reactivity could be excatalytic cycle of intramolecular oxidative N-allylation of homoallylhydraplained by the decreased acidity of the hydrazone functionalizones 1 ah (R2 = H) and 1 j (left: R1,R2 = CH=CH(CH2)2) or 1 i (right). See [22] ty. Scheme 2.
Table 2. Screening of the reaction depicted in Scheme 2 using hydrazone substrates 1 aj.

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Y. Canac, R. Chauvin et al. Finally, the proposed mechanism suggests an explanation for the formation of the other six-membered cyclic hydrazone (2 j) from the C-homoallylhydrazone (1 j) derived from cyclohex-2-en-1-one (37 % yield; Table 2, entry 10). In this case, the allylic CH activation is regioselective, but the nucleophilic attack of the hydrazide anion at the substituted external position (Scheme 3, A) is disfavored by steric hindrance of the cyclohexenyl substituent at the homoallylic a-position. Path C would thus be preferred to give the bicyclic hydrazone (2 j) after migration of the internal CH proton to the exocyclic position. The steric inhibition of path A is confirmed by the lack of reactivity of hydrazone 1 k (R2 = CH3).
combined organic layers were dried by adding MgSO4, filtered, and the solvent of the filtrate was removed under vacuum. The residue was purified by performing flash column chromatography on silica (pentane/EtOAc).

General procedure for the preparation of pyrazoline derivatives or isomers 2 aj

To a round bottom flask (5 mL), the C-homoallylhydrazone 1 (1 mmol, 1 equiv), the benzoquinone (2 mmol, 2 equiv), BIMINAP (10 % mol), Pd(OAc)2 (10 % mol), a Teflon stirrer bar, and anhydrous THF (0.70 mL) were added successively. The reaction mixture was then stirred at 45 8C for 36 h. The solution was allowed to cool to room temperature, and the residue was separated by filtration. The organic layer was collected and evaporated under vacuum. The crude reaction mixture was directly purified by performing flash column chromatography on silica (EtOAc/pentane). Experimental procedures and spectroscopic characterization for all of the new compounds are detailed in the Supporting Information.

Conclusions
The described oxidative N-allylation method allows C-homoallylhydrazones to be converted to 5-vinyl-2-pyrazolines or other cyclic hydrazones of large ring sizes (six- or seven-membered), depending on the steric and electronic demand of the substituents at the allylic moiety of the substrate. Although the yields remained moderate, the results not only propose a novel reaction type, but also demonstrate the specific value of the BIMINAP diphosphine ligand in catalysis, and, in particular, under oxidizing conditions. Preliminary experiments show that the enantiopure atropochiral (R)-BIMINAP ligand exhibits promising properties for the synthesis of chiral 5-vinyl-2-pyrazolines by asymmetric catalysis (30 % ee in (+)-2 a). As in the previously reported case of the TsujiTrost allylation process,[26a] efforts towards the improvement of the enantioselectivity of the oxidative N-allylation process are currently in progress.

Acknowledgements
The French Ministre de lEnseignement Suprieur et de la Recherche, the French Centre National de la Recherche Scientifique, and, more generally, the French public finances are gratefully acknowledged for the support of this work, in particular for the post-doctoral fellowship of T.T.D (program ANR-08-JCJC-0137-01). Keywords: allylation BIMINAP CH activation cyclization palladium
[1] a) M. Johnson, B. Younglove, L. Lee, R. LeBlanc, H. Holt, Jr., P. Hills, H. Mackay, T. Brown, S. L. Mooberry, M. Lee, Bioorg. Med. Chem. Lett. 2007, 17, 5897; b) Z. zdemir, H. B. Kandilci, B. Guemuesel, U. Calis, A. A. Bilgin, Eur. J. Med. Chem. 2007, 42, 373; c) D. R. Spring, Chem. Soc. Rev. 2005, 34, 472; d) S. Kumar, S. Bawa, S. Drabu, R. Kumar, H. Gupta, Recent Pat. Anti-Cancer Drug Discovery 2009, 4, 154. [2] I. V. Beliak, V. G. Kravets, A. A. Kryuchin, Semiconductor Physics, Quantum Electronics & Optoelectronics 2007, 10, 33. [3] a) E. Buchner, M. Fritsch, A. Papendieck, H. Witter, Justus Liebigs Ann. Chem. 1893, 273, 214; b) H. von Pechmann, Ber. Dtsch. Chem. Ges. 1894, 27, 1888; c) G. Mass, in Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products (Eds.: A. Padwa, W. H. Pearson), Wiley, Hoboken, NJ, 2003, Chap. 8, p. 539; d) J. H. Ahn, H.-M. Kim, S. K. Kang, J. D. Ha, E. Kgun Yum, D. K. An, J.-K. Choi, S. S. Kim, Bull. Korean Chem. Soc. 2005, 26, 467. [4] N. M. Abunada, H. M. Hassaneen, N. G. Kandile, O. A. Miqdad, Molecules 2008, 13, 1011. [5] E. Fischer, O. Knoevenagel, Justus Liebigs Ann. Chem. 1887, 239, 194. [6] S. B. Jadhav, R. A. Shastri, K. V. Gaikwad, S. V. Gaikwad, Eur. J. Chem. 2009, 6, 183. [7] a) A. Lavai, J. Heterocycl. Chem. 2002, 39, 1; b) S. Mller, B. List, Angew. Chem. 2009, 121, 10160; Angew. Chem. Int. Ed. 2009, 48, 9975. [8] K. Alex, A. Tillack, N. Schwarz, M. Beller, Org. Lett. 2008, 10, 2377. [9] J. P. Waldo, S. Mehta, R. C. Larock, J. Org. Chem. 2008, 73, 6666. [10] Y. Ju, R. S. Varma, J. Org. Chem. 2006, 71, 135. [11] S. L. Cui, J. Wang, Y. G. Wang, Org. Lett. 2008, 10, 13. [12] J. Barluenga, F. Fernandez-mari, A. L. Viado, E. Aguilar, B. Olano, S. Garcia-Granda, C. Moya-Rubiera, Chem. Eur. J. 1999, 5, 883. [13] For recent review, see: F. Collet, R. H. Dodd, P. Dauban, Chem. Commun. 2009, 5061, and references therein. [14] W. C. Peter Tsang, N. Zheng, S. L. Buchwald, J. Am. Chem. Soc. 2005, 127, 14 560.

Experimental Section
General remarks
THF was dried and distilled over sodium and benzophenone. BIMINAP was prepared according to the described method.[23] All other reagents were used as commercially available. Column chromatography was carried out on silica gel (60 , C.C 70200 mm). The following analytical instruments were used. 1H and 13C NMR spectra were measured by using a Bruker AM 250 and DPX 300. Infrared spectra were obtained by using a PerkinElmer Spectrum 100 FT-IR spectrometer. It is, however, noteworthy that the absorption bands of the characteristic C=N bonds of hydrazone substrates and pyrazoline products are known to be weak and could not be unambiguously assigned.[27]

General procedure for the preparation of substituted hydrazones 1 am

To a THF solution (50 mL) of the starting hydrazone (2.0 mmol, 1 eq), n-butyl lithium (5.0 mmol, 2.5 eq, 2.5 m solution in hexane) was added at 78 8C. After stirring for 45 min at 78 8C, the mixture was warmed to room temperature and stirred for 15 min. The allybromide derivative (5.0 mmol, 2.5 eq) was then added at 78 8C. After warming to room temperature within 16 h, a saturated aqueous solution of NH4Cl (30 mL) was added to the reaction mixture. The organic and the aqueous layers were separated and the latter was extracted with ethyl acetate (EtOAc, 3 50 mL). The

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CH Oxidative N-Allylation
[15] K. Inamoto, T. Saito, M. Katsuno, T. Sakamoto, K. Hiroya, Org. Lett. 2007, 9, 2931. [16] K. Inamoto, T. Saito, K. Hiroya, T. Doi, Synlett 2008, 20, 3157. [17] T. Miura, Y. Ito, M. Murakami, Chem. Lett. 2009, 38, 328. [18] J. J. Li, T. S. Mei, J. Q. Yu, Angew. Chem. 2008, 120, 6552; Angew. Chem. Int. Ed. 2008, 47, 6452. [19] a) K. J. Fraunhoffer, M. C. White, J. Am. Chem. Soc. 2007, 129, 7274; b) G. T. Rice, M. C. White, J. Am. Chem. Soc. 2009, 131, 11707; c) X. Qi, G. T. Rice, M. S. Lall, M. S. Plummer, M. C. White, Tetrahedron 2010, 66, 4816. [20] a) J. Casanova, B. Waegell, Tetrahedron 1975, 31, 1035; b) M. S. Gordon, J. G. Krause, M. A. Linneman-Mohr Regis R. Parchue, Synthesis 1980, 244; c) M. J. Hearn, S. A. Lebold, A. Sinha, K. Sy, J. Org. Chem. 1989, 54, 4188; d) Z. Zhang, Y. Liu, M. Gong, X. Zhao, Y. Zhang, J. Wang, Angew. Chem. 2010, 122, 1157; Angew. Chem. Int. Ed. 2010, 49, 1139. [21] V. Karapetyan, S. Mkrtchyan, T. T. Dang, A. Villinger, H. Reinke, P. Langer, Tetrahedron 2008, 64, 8010. [22] Analogous hydrazones of alkylketones 1 l and 1 m were also prepared, but failed to react (see experimental section). [23] N. Debono, Y. Canac, C. Duhayon, R. Chauvin, Eur. J. Inorg. Chem. 2008, 2991. [24] A. Miyashita, A. Yasuda, H. Takaya, K. Toriumi, T. Ito, T. Souchi, R. Noyori, J. Am. Chem. Soc. 1980, 102, 7932. [25] T. Benincori, E. Brenna, F. Sannicol, L. Trimarco, P. Antognazza, E. Cesarotti, F. Demartin, T. Pilati, G. Zotti, J. Organomet. Chem. 1997, 529, 445. [26] a) I. Abdellah, N. Debono, Y. Canac, L. Vendier, R. Chauvin, Chem. Asian J. 2010, 5, 1225; b) I. Abdellah, C. Lepetit, Y. Canac, C. Duhayon, R. Chauvin, Chem. Eur. J. 2010, 16, 13095. [27] G. Tosi, L. Cardellini, G. Bocelli, Acta Crystallogr. Sect. B 1988, 44, 55.

Received: March 26, 2011 Published online on July 28, 2011

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