15-Membered macrocyclic triolefin: Role in recovering active palladium catalyst for the telomerization of butadiene with methanol

Article abstract of DOI:10.1016/S0040-4039(01)01464-2

The 15-membered macrocyclic triolefin Ma stabilizes a Pd(0) catalyst, active and recyclable in telomerization of butadiene with methanol. This Pd catalyst is generated from different Pd(0) or Pd(II) sources associated with phosphanes.

Full text of DOI:10.1016/S0040-4039(01)01464-2

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 42 (2001) 7055–7057
15-Membered macrocyclic triolefin: role in recovering active
palladium catalyst for the telomerization of butadiene
with methanol
Boris Estrine,a Bele´n Blanco,b Sandrine Bouquillon,a Franc¸oise He´nin,a,* Marcial Moreno-Man˜as,b
Jacques Muzart,a Carolina Penaa,b and Roser Pleixatsb
aUnite´ Mixte de Recherche ꢀRe´actions Se´lectives et Applicationsꢁ, CNRS, Universite´ de Reims Champagne, Ardenne,
BP 1039, 51687 Reims Cedex 2, France
bDepartment of Chemistry, Universitat Auto`noma de Barcelona, Cerdanyola, 08193 Barcelona, Spain
Received 19 June 2001; accepted 6 August 2001
Abstract—The 15-membered macrocyclic triolefin Ma stabilizes a Pd(0) catalyst, active and recyclable in telomerization of
butadiene with methanol. This Pd catalyst is generated from different Pd(0) or Pd(II) sources associated with phosphanes. © 2001
Elsevier Science Ltd. All rights reserved.
Recently, palladium(0) complexes of 15-membered
macrocyclic triolefins, represented in Fig. 1 as Pd-Ma,
have been synthezised1 and shown to be efficient and
recoverable catalysts for Suzuki-type cross-coupling
reactions.2 We were interested in using such a recover-
able catalytic system in telomerization of butadiene in
the presence of nucleophiles such as methanol3 (Eq.
seems to be reported. Only polymer-bound palladium
complexes could be easily separated from a reaction
mixture and reused with some loss of the activity7 or
with its preservation.8 We present here our first results
in recycling a soluble catalyst starting from different
palladium sources associated with the free triolefinic
macrocycle Ma.
"Pd"
butadiene
dimers
+
+
OMe
(1)
OMe
MeOH
1
2
(1)); this transformation remains of interest due to the
possible use of linear octadienyl derivates as building
blocks in the synthesis of natural products.4 Many
homogeneous zerovalent and bivalent palladium com-
plexes excel in efficiency and selectivity in telomeriza-
tion,3,5 whose mechanism has been recently revisited.6
However, no example of soluble recyclable systems
We started our studies with Pd-Ma as catalyst (Table 1,
entries 1–7) and compared the results with those
observed by using Pd2(dba)3·CHCl3 (noted below Pd-
dba) as catalytic precursor (Table 1, entries 8–11), or
Pd(OAc)2 (Table 1, entry 12). Pd-Ma exhibited no
efficiency without added phosphane (entry 1). The
butadiene conversion was enhanced in the presence of
SO2Ar
SO2Ar
N
Pd-Ma:
N
Ma:
Ar =
2,4,6-tri-i-propylphenyl
Pd
N
N
N
N
ArO2S
ArO2S
SO2Ar
SO2Ar
Figure 1. Structures of Pd-catalyst and macrocyclic ligand.
* Corresponding author. Fax: 33 3 26 91 31 66; e-mail: francoise.henin@univ-reims.fr
0040-4039/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(01)01464-2

7056
B. Estrine et al. / Tetrahedron Letters 42 (2001) 7055–7057
Table 1. Telomerization of butadiene with methanol in the presence of Pd catalystsa
Entry
‘Pd’-phosphane (equiv./Pd)
Time (h)
T.O.N.
T.O.F. (h−1
)
Conv. (%)
Selectivity (%)
Dimersb
1
2
1
2
3
4
5
6
7
8
Pd-Ma
1
1
2
3
1
1
0.75
1
1
60
980
60
980
690
3
49
69
72
59
68
59
71
46
95
95
75
16
81
86
88
76
72
78
86
73
89
88
82
0
8
8
6
14
16
17
8
9
3
7
11
84
11
6
Pd-Ma-PPh3 (1)
Pd-Ma-PPh3 (1)
Pd-Ma-PPh3 (1)
Pd-Ma-PPh3 (2)
Pd-Ma-PPh3 (3)
Pd-Ma-P(p-tol)3 (3)
Pd-dbac-PPh3 (2)
Pd-dbac-PPh3 (3)
Pd-dbac-P(o-tol)3 (2)
Pd-dbac-P(p-tol)3 (2)
Pd(OAc)2-PPh3 (3)
1380
1440
1180
1360
1180
1420
920
1900
1900
1500
480
6
1180
1360
1573
1420
920
1520
2533
2000
10
12
5
6
18
8
9
10
11
12
1.25
0.75
0.75
5
7
a Reaction conditions: Pd/MeOH/C4H6=1/6000/4000; 2.5×10−2 mmol Pd, starting butadiene pressure=4 bar, 60°C.
b 1,3,7-Octatriene and 4-vinylcyclohexene constitute essential dimers.
c Pd-dba=Pd2(dba)3·CHCl3.
triphenylphosphane: when PPh3/Pd=1, the reaction
took place but needed more than 1 h (entries 2–4). A
ratio PPh3/Pd=3 seemed a good compromise to reach
a fair butadiene conversion (entries 2/5/6). The conver-
sion was similar by using Pd-Ma/3PPh3 or Pd-dba/
2PPh3, but the selectivity to the linear ether was lower
with the former catalyst (entries 6/8). As already men-
tioned,3,6 we observed in all these experiments, the
crucial effect of the added phosphane and of its amount
on the course of the reaction. The performance of the
second catalytic system (with Pd-dba as precursor) was
higher for PPh3/Pd=2 (entries 8/9) and the order of
efficiency of phosphanes was P(p-tolyl)3]P(o-tolyl)3>
PPh3 (Table 1, entries 8/10/11), which could probably
be correlated with the ligand basicity.9 The use of
Concerning recycling, the systems based on Pd-dba or
Pd(OAc)2 lost their activity and selectivity, even in the
presence of added phosphane in the recycling experi-
ment (Table 2, entries 3–5). The activity of Pd-Ma also
dropped in the absence of added phosphane in each run
(Table 2, entry 1); but in the presence of added phos-
phane (entry 2), the activity was recovered and even
enhanced when compared to the first run. This could
suggest an effect of Ma in the formation of new telom-
erization active species.
This latter observation led us to test the possibility of
recycling by association of Pd-dba or Pd(OAc)2 with
both a phosphane and the free macrocycle Ma (Table
3). We were delighted to observe the ability of Ma in
the recovering of active Pd(0) species. With Pd-dba/Ma/
3PPh3, conversion and selectivity were higher in the
first run (Table 3, entry 2) compared to that of the
Pd(II) as Pd(OAc)2 associated with
3 equiv. of
triphenylphosphane was also quite satisfying (Table 1,
entry 12).
Table 2. Catalyst recycling in telomerization of butadiene with methanola
Entry
‘Pd’-phosphane (equiv./Pd)b
Runs
T.O.F. (h−1
)
Conv. (%)
Selectivity (%)
1
2
Dimers
1
2
Pd-Ma-PPh3 (0)
Pd-Ma-PPh3 (3)
1c
2
1360
820
1360
1740
1400
1500
1420
100
920
180
20
68
41
68
87
70
75
71
5
46
9
1
75
15
0
72
85
72
80
79
81
86
63
73
67
0
16
7
12
8
12
6
7
5
1c
2
16
14
14
14
8
8
9
10
0
11
7
3
4
3
4
Pd-dba-PPh3 (2)
Pd-dba-PPh3 (3)
1c
2
6
29
18
23
100
7
1c
2
3
5
Pd(OAc)2-PPh3 (3)
1c
2
2000
300
0
82
80
–
13
–
3
–
a Reaction conditions of Table 1, except the catalysts, which were recovered after distillation under reduced pressure of the products of first runs
and directly reused.
b Added phosphane (2 or 3 equiv./Pd except entry 1) in each recycling experiment.
c For clarity, results of Table 1 have been mentioned.

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.
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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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