B. Estrine et al. / Tetrahedron Letters 42 (2001) 7055–7057
7057
Table 3. Catalyst recycling in the presence of Ma in telomerization of butadiene with MeOHa
Entry
‘Pd’-ligands (equiv./Pd)
Runs
T.O.F. (h−1
)
Conv. (%)
Selectivity (%)
Dimers
1
2
1b
2
Pd-dba+PPh3 (3)
Pd-dba+Ma (1)
+PPh3 (3)
1
1
2
3
4
1
1
2
3
4
1
1
2
3
4
920
1360
1760
1680
1700
1540
940
2000
1580
1800
2000
420
46
68
88
84
85
77
47
100
79
90
75
21
56
55
25
73
88
82
81
84
90
81
87
83
85
82
81
82
80
80
9
6
13
11
8
18
6
5
8
8
5
7
2
5
3
7
9
4
9
11
3
4
Pd-dba+P(p-tol)3 (3)
Pd-dba+Ma (1)
+P(p-tol)3 (3)
5
12
11
12
12
11
10
14
11
9
5b
6
Pd(OAc)2+PPh3 (3)
Pd(OAc)2+Ma (1)
+PPh3 (3)
1120
1100
500
a Reaction conditions of the first runs: 2.5×10−2 mmol of Pd; Pd/Ma/phosphane/MeOH/C4H6=1/1/3/6000/4000; 60°C; 1 h; starting butadiene
pressure=4 bar. The catalysts were recovered in each run after distillation of the products under reduced pressure. They were reused after adding
phosphane (3 equiv./Pd), methanol and butadiene in each recycling experiment.
b For clarity, the results of Table 1 have been mentioned.
same precursor system without added macrocycle (entry
1); furthermore the catalyst recycling was highly
efficient (entry 2, runs 2–4). Such an improvement of
the first run was not observed when PPh3 was
exchanged for P(p-tol)3 (entries 3/4) or when Pd-dba
was replaced by Pd(OAc)2 (entries 5/6); however, effec-
tive catalyst recycling has also been observed.
Man˜as, M.; Parella, T.; Pleixats, R.; Torrejo´n, J.; Vallrib-
era, A. Eur. J. Inorg. Chem. 2001, 1999–2006.
2. Corte´s, J.; Moreno-Man˜as, M.; Pleixats, R. Eur. J. Org.
Chem. 2000, 239–243.
3. Reviews: (a) Tsuji, J. Adv. Organomet. Chem. 1979, 17,
141–193; (b) Tsuji, J. Palladium Reagents and Catalysis;
Wiley: Chichester, 1995; pp. 422–449.
4. Reviews: Tsuji, J. Pure Appl. Chem. 1979, 51, 1235–1241
and 1981, 53, 2371–2378.
5. For recent examples: (a) Camargo, M.; Dani, P.; Dupont,
J.; de Souza, R. F.; Pfeffer, M.; Tkatchenko, I. J. Mol.
Catal. A: Chem. 1996, 109, 127–131; (b) Bouachir, F.;
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J. Organomet. Chem. 1998, 569, 203–215; (c) Benvenutti,
F.; Carlini, C.; Marchionna, M.; Patrini, R.; Raspolli
Galetti, A. M.; Sbrana, G. J. Mol. Catal. A: Chem. 1999,
140, 139–155; (d) Basato, M.; Crociani, L.; Benvenutti, F.;
Raspolli Galetti, A. M.; Sbrana, G. J. Mol. Catal. A:
Chem. 1999, 145, 313–316.
Work is currently underway to determine the nature of
the active species. Nevertheless, we have already
observed that after four runs (Table 3, entry 2) distilla-
tion of the telomerization products, refluxing of the
resulting solid for 12 h in THF and concentrating, the
introduced palladium is quantitatively recovered as Pd-
Ma, as indicated by NMR.
Acknowledgements
6. Vollmu¨ller, F.; Krause, J.; Klein, S.; Ma¨gerlein, W.; Beller,
This work was supported by the European Community
(COST D12/0028/99), by Europol’Agro (Glycoval pro-
gram) and by Socrates institution (studentship to C.P.).
We are grateful to ‘Conseil ge´ne´ral de la Marne’ for a
PhD studentship to B.E. The Spanish group is grateful
to MEC (Project PB98-0902) and ‘Generalitat de
Catalunya’ (Project SGR2000-0062).
M. Eur. J. Inorg. Chem. 2000, 1825–1832.
7. (a) Kaneda, K.; Kurosaki, H.; Terasawa, M.; Imanaka, T.;
Teranishi, S. J. Org. Chem. 1981, 46, 2356–2362; (b)
Benvenutti, F.; Carlini, C.; Marchionna, M.; Patrini, R.;
Raspolli Galetti, A. M.; Sbrana, G. J. Mol. Catal. A:
Chem. 1999, 139, 177–187.
8. Benvenutti, F.; Carlini, C.; Raspolli Galetti, A. M.;
Sbrana, G.; Marchionna, M.; Patrini, R. J. Mol. Catal. A:
Chem. 1999, 137, 49–63.
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