Allylic oxidation of olefins in the presence of Cu-Na-HSZ-320 zeolite as reusable solid catalyst

Article abstract of DOI:10.1016/S0040-4039(00)01587-2

The Cu-Na-HSZ-320 zeolite can be utilised as an efficient and reusable catalyst in the allylic oxidation of olefins with tert-butyl perbenzoate to give the corresponding allylic esters in good yield and excellent selectivity. (C) 2000 Elsevier Science Ltd

Full text of DOI:10.1016/S0040-4039(00)01587-2

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 41 (2000) 8947–8950
Allylic oxidation of olefins in the presence of
Cu-Na-HSZ-320 zeolite as reusable solid catalyst
Silvia Carloni, Bettina Frullanti, Raimondo Maggi, Alessandro Mazzacani, Franca Bigi
and Giovanni Sartori*
Dipartimento di Chimica Organica e Industriale dell’Universita`, Parco Area delle Scienze 17A, I-43100 Parma, Italy
Received 3 August 2000; revised 8 September 2000; accepted 14 September 2000
Abstract
The Cu-Na-HSZ-320 zeolite can be utilised as an efficient and reusable catalyst in the allylic oxidation
of olefins with tert-butyl perbenzoate to give the corresponding allylic esters in good yield and excellent
selectivity. © 2000 Elsevier Science Ltd. All rights reserved.
Keywords: catalysis; copper and compounds; olefins; oxidation; zeolites.
The allylic oxidation of olefins is recognised as one of the most useful routes to produce allylic
alcohols, esters and ethers.1 In particular, oxidation of CꢀH bonds by copper catalysed reaction
with an organic peroxyester (the Kharasch–Sosnovsky reaction) represents an easy and general
methodology for the synthesis of esters of allylic alcohols.2 Moreover, considerable attention has
been devoted recently to the asymmetric Kharasch–Sosnovsky reaction in the presence of chiral
copper complexes.3
Recent years have seen an increasing interest into the catalysis by solid materials for fine
chemicals preparation4 since this approach frequently results in an improvement of the produc-
tive process from both an economical and ecological point of view.5
Our interest in the preparation and use of solid catalysts for the production of fine chemicals6
prompted us to reinvestigate the Kharasch–Sosnovsky reaction over copper-exchanged zeolites.
The catalysts utilised were Cu-Na-HSZ-320 and Cu-Na-ZSM-5 prepared by a conventional
ion-exchange method7 in which commercially available zeolites Na-HSZ-3208 or H-ZSM-59 were
treated with an aqueous solution of Cu(II) nitrate at 90°C for 2 hours, washed with deionised
water, filtered, dried and calcined at 500°C for 15 hours in air.10 Although the effective catalyst
in the Kharasch–Sosnovsky reaction has been suggested to be a Cu(I) species,11 we decided to
use Cu(II)-exchanged zeolites on the basis of recent results from literature12 and previous
* Corresponding author. Tel: +39 0521 905551; fax: +39 0521 905472; e-mail: sartori@unipr.it
0040-4039/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(00)01587-2

8948
experience from our laboratory suggesting that both Cu(I)- and Cu(II)-exchanged Na-HSZ-320
zeolites showed similar catalytic efficiency.
A first series of experiments was performed by reacting tert-butylperbenzoate 2 with various
cycloalkenes 1a–c in the presence of the two Cu(II)-exchanged zeolites with different pore
dimensions. Results reported in Table 1 suggest that despite the quite similar copper content the
two zeolites show a dramatically different catalytic efficiency.
Table 1
Allylic oxidation of cycloalkenes using two different Cu(II)-exchanged zeolitesa
Entry
n
3 Yield (%)
Cu-Na-HSZ-320 [Cu (% wt): 2.8]
Cu-Na-ZSM-5 [Cu (% wt): 2.0]
a
b
c
1b
2
4
60
70
68
7
4
5
a 1a–c (0.030 mol), 2 (0.010 mol), cat. (0.1 g).
b Reaction temperature=45°C (cyclopentene bp=44°C).
These results can be rationalised assuming that the diffusion of reagents and products through
,
the zeolite Cu-Na-HSZ-320 (pore dimension 7.4 A) is almost completely unrestricted whereas
,
Cu-Na-ZSM-5 (pore dimension 5.1–5.6 A) can suffer from some diffusion resistance which
hampers the accessibility to the surface active sites of the catalyst.
The reaction with the zeolite Cu-Na-HSZ-320 can be successfully applied to different olefins
giving allylic benzoates in satisfactory to good yields13 (Table 2).
The mildness of the reaction conditions makes it possible to use both cyclic and linear olefins
giving the corresponding allylic benzoates without formation of any side products such as
isomeric compounds obtained by allylic rearrangement frequently observed when the reaction is
carried out under homogeneous catalysis.14
The possible leaching of copper catalyst was then examined by using the standard procedure
suggested by R. A. Sheldon.15 Thus, the model reaction mixture between 1b and 2 in the
presence of Cu-Na-HSZ-320 was filtered at 80°C after 10 hours when 3b was produced in 44%
yield. An additional amount of reagents 1b (30 mmol, 2.5 g, 3.0 ml) and 2 (10 mmol, 1.6 g, 1.9
ml) was added to the solution and the solid catalyst, and both reaction mixtures were heated at
80°C for a further 10 hours. Production of 3b in 42% yield with the solid catalyst and in about
3% yield with the solution confirms that the reaction mainly occurs on the surface of the solid
catalyst.
Finally, the zeolite Cu-Na-HSZ-320 has been recycled almost 10 times in the model reaction
between 1b and 2 showing a modest increase in efficiency: from 70% in the first cycle to 79% in
the last cycle.

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Table 2
Synthesis of various allylic benzoates 3 promoted by Cu-Na-HSZ-320 zeolite
Acknowledgements
The authors thank the Ministero dell’Universita` e della Ricerca Scientifica e Tecnologica
(MURST), Italy and the University of Parma (National Project ‘Processi Puliti per la Chimica
Fine’) for financial support. The authors are also grateful to the Centro Interfacolta` Misure
(CIM) for the use of NMR and mass spectroscopy instruments and to Pier Antonio Bonaldi for
technical assistance.
References
1. Bulman Page, P. C.; McCarthy, T. J. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, J.; Heathcock,
C. H., Eds.; Pergamon: Oxford, 1991; Vol. 7, Chapter 2.1, pp. 83–117.
2. (a) Kharasch, M. S.; Sosnovsky, G. J. Am. Chem. Soc. 1958, 80, 756; (b) Kharasch, M. S.; Sosnovsky, G.; Yang,
N. C. J. Am. Chem. Soc. 1959, 81, 5819; (c) Sosnovsky, G.; Yang, N. C. J. Org. Chem. 1960, 25, 899; (d)
Sosnovsky, G. Tetrahedron 1961, 13, 241; (e) Sosnovsky, G.; O’Neill, H. J. C. R. Hebd. Seances Acad. Sci. 1962,
254, 704; (f) Sosnovsky, G.; Rawlinson, D. J. In Organic Peroxides; Swern, D., Ed.; Wiley: New York, 1970; Vol.
1; (g) Rawlinson, J.; Sosnovsky, G. Synthesis 1972, 1.

8950
3. (a) Ievina, A.; Muzart, J. Tetrahedron: Asymmetry 1995, 6, 147; (b) Muzart, J. J. Mol. Catal. 1991, 64, 381; (c)
Andrus, M. B.; Chen, X. Tetrahedron 1997, 53, 16229; (d) So¨dergren, M. J.; Andersson, P. G. Tetrahedron Lett.
1996, 37, 7577; (e) Zorrdervan, C.; Feringa, B. L. Tetrahedron: Asymmetry 1996, 7, 1895; (f) Kawasaki, K.;
Katsuki, T. Tetrahedron 1997, 53, 6337; (g) Andrus, M. B.; Argade, A. B.; Chen, X.; Pammnet, M. G.
Tetrahedron Lett. 1995, 36, 2945.
4. (a) Hutchings, G. J. J. Chem. Soc., Chem. Commun. 1999, 301; (b) Corma, A. Chem. Rev. 1995, 95, 559; Balogh,
M.; Laszlo, P. Organic Chemistry Using Clays; Springer Verlag: New York, 1993.
5. (a) Clark, J. H.; Macquarrie, D. J. Chem. Soc. Rev. 1996, 303; (b) Sheldon, R. A. Chem. Ind. (London) 1997, 12;
(c) Sheldon, R. A. J. Mol. Catal. A. 1996, 107, 75; Thomas, J. M.; Zamaraev, K. I. Angew. Chem., Int. Ed. Engl.
1994, 33, 308.
6. (a) Bigi, F.; Maggi, R.; Sartori, G.; Zambonin, E. J. Chem. Soc., Chem. Commun. 1998, 513; (b) Bigi, F.;
Frullanti, B.; Maggi, R.; Sartori, G.; Zambonin, E. J. Org. Chem. 1999, 64, 1004; (c) Ballabeni, M.; Ballini, R.;
Bigi, F.; Maggi, R.; Parrini, M.; Predieri, G.; Sartori, G. J. Org. Chem. 1999, 64, 1029.
7. Hayashibara, H.; Nishiyama, S.; Tsuruya, S.; Masai, M. J. Catal. 1995, 153, 254.
2
,
8. Na-HSZ-320 is an FAU zeolite with 5.6 SiO2/Al2O3 molar ratio, pore size 7.4 A and surface area 570 10 m /g.
2
,
9. H-ZSM-5 is an MFI zeolite with 28.2 SiO2/Al2O3 molar ratio, pore size 5.1–5.6 A and surface area 410 10 m /g
It was converted into Na-ZMS-5 according to Ref. 7.
10. Herron, N. Inorg. Chem. 1986, 25, 4714. The Cu content (% weight) in the Cu-Na-HSZ-320 and Cu-Na-ZSM-5
was 2.8 and 2.0, respectively (determined by AAS).
11. Sosnovsky, G. Angew. Chem., Int. Ed. Engl. 1964, 3, 269.
12. Sekar, G.; Datta Gupta, A.; Singh, V. K. Tetrahedron Lett. 1996, 37, 8435.
13. The general procedure for the preparation of allyl benzoates 3 is as follows: a mixture of the selected alkene 1
(30 mmol) and Cu-Na-HSZ-320 (0.1 g) was heated at 80°C and then tert-butylperbenzoate 2 (10 mmol, 1.9 g, 1.9
ml) was added dropwise over a 20 hour period. After an additional 2 hours, the mixture was cooled to rt, the
catalyst was removed by filtration, washed with methylene chloride (40 ml) and acetone (20 ml) and the crude was
treated with a saturated solution of NaHCO3 (2×25 ml) and water (2×25 ml). The organic phase was dried
(NaSO4), the excess olefin was recovered unchanged by distillation and the products purified by flash chromatog-
1
raphy using a mixture of hexane/ethyl acetate 95/5 as eluant. All products 3a–f were characterised (IR, H NMR
and MS) and their bps compared with reported literature bps. Physical data of 3d: pale yellow oil, bp
1
135–140°C/0.1 mmHg; H NMR (CDCl3, 300 MHz): l=1.5–1.3 (m, 6H, 3CH2), 5.4–5.8 (m, 4H, H-2, H-3, H-6
and H-7), 6.1–6.3 (m, 1H, H-1), 7.40 (t, 2H, J=7.6, H-3% and H-5%), 7.51 (tm, 1H, J=7.6, H-4%), 8.05 (dm, 2H,
J=7.6, H-2% and H-6%); IR (NaCl): 1717 cm−1; MS (CI): m/z 228 (M+, 3%), 105 (100), 77 (49); Anal. calcd for
C15H16O2: C, 78.9, H, 7.1; found: C, 79.1, H, 7.3. Physical data of 3e: pale yellow oil, bp 124–128°C/0.1 mmHg;
1H NMR (CDCl3, 300 MHz): l=0.87 (t, 3H, J=7.0, CH3), 1.1–1.9 (m, 12H, 6CH2), 5.20 (dt, 1H, J=10.5 and
1.2, H-1trans), 5.32 (dt, 1H, J=17.1 and 1.2, H-1cis), 5.49 (qm, 1H, J=6.4, H-3), 5.90 (ddd, 1H, J=17.1, 10.5 and
6.4, H-2), 7.44 (tm, 2H, J=7.5, H-3% and H-5%), 7.55 (tt, 1H, J=7.5 and 1.4, H-4%), 8.06 (dm, 2H, J=7.5, H-2%
and H-6%); IR (NaCl): 1718 cm−1; MS (CI): m/z 260 (M+, 3%), 105 (100), 77 (23); Anal. calcd for C17H24O2: C,
78.4, H, 9.3; found: C, 78.2, H, 9.2.
14. See for example: (a) Kochi, J. K. J. Am. Chem. Soc. 1961, 83, 3162; (b) Denney, D. Z.; Appelbaum, A.; Denney,
C. B. J. Am. Chem. Soc. 1962, 84, 4969; (c) Kochi, J. K. J. Am. Chem. Soc. 1962, 84, 774; (d) Walling, C.;
Zavitsas, A. A. J. Am. Chem. Soc. 1963, 85, 2084; (e) Rawlinson, J.; Sosnovsky, G. Synthesis 1972, 567.
15. Lempers, H. E. B.; Sheldon, R. A. J. Catal. 1998, 175, 62.
.