First Kumada reaction of alkyl chlorides using N-heterocyclic carbene/palladium catalyst systems

Article abstract of DOI:10.1016/S0022-328X(03)00723-X

For the first time it is shown that N-heterocyclic carbenes are suitable ligands for the palladium-catalyzed coupling of alkyl chlorides with aryl Grignard reagents. A variety of simple as well as functionalized primary alkyl chlorides provide the corresponding alkyl benzenes in general in good to very good yield. By comparing the 1,3-dimesitylimidazol-2-ylidene (IMes) palladium(0) naphthoquinone complex with the previously known palladium phosphine catalyst for the model coupling reaction of 1-chlorohexane with phenylmagnesium bromide it is demonstrated that the new catalyst system is superior.

Full text of DOI:10.1016/S0022-328X(03)00723-X

Journal of Organometallic Chemistry 687 (2003) 403Á409
/
www.elsevier.com/locate/jorganchem
First Kumada reaction of alkyl chlorides using N-heterocyclic
carbene/palladium catalyst systems
Anja C. Frisch, Franck Rataboul, Alexander Zapf, Matthias Beller *
Leibniz-Institut f ¨u r Organische Katalyse an der Universit ¨a t Rostock e.V., Buchbinderstr. 5-6, D-18055 Rostock, Germany
Received 2 June 2003; received in revised form 16 July 2003; accepted 16 July 2003
Dedicated to Prof. Jean-Pierre Gen eˆ t on the occasion of his 60th birthday
Abstract
For the first time it is shown that N-heterocyclic carbenes are suitable ligands for the palladium-catalyzed coupling of alkyl
chlorides with aryl Grignard reagents. A variety of simple as well as functionalized primary alkyl chlorides provide the
corresponding alkyl benzenes in general in good to very good yield. By comparing the 1,3-dimesitylimidazol-2-ylidene (IMes)
palladium(0) naphthoquinone complex with the previously known palladium phosphine catalyst for the model coupling reaction of
1
-chlorohexane with phenylmagnesium bromide it is demonstrated that the new catalyst system is superior.
2003 Elsevier B.V. All rights reserved.
#
Keywords: N-heterocyclic carbenes; Palladium-catalyzed coupling; Alkyl chlorides
1
. Introduction
palladium alkyl complexes in cases where the oxidative
addition has taken place. Nevertheless, already in the
early to mid 1990s Suzuki et al. [9] and Knochel et al.
[10] have demonstrated the possibility of palladium- and
nickel-catalyzed coupling of alkyl bromides with alkyl
boranes as well as with organozinc derivatives. We were
also able to show that palladium-catalyzed carbonyla-
tions of in situ generated a-amidoalkyl bromides
proceed in good yields to the corresponding amino
acid derivatives [11].
Organometallic cross coupling reactions have proven
to be extremely important for the synthesis of organic
building blocks, pharmaceuticals and agrochemicals in
derivatives in recent years. In this area, aryl and vinyl
chlorides are among the most useful starting materials
due to their low cost and easy availability, which allows
not only laboratory-scale syntheses but also industrial
applications [1]. Activation of CÁ
/Cl bonds and subse-
More recently, the first general method for catalytic
coupling reactions of alkyl halides was described by Fu
et al. [12] who performed palladium-catalyzed Suzuki
reactions, whereas Kambe et al. [13] reported on the
efficient nickel-catalyzed Kumada coupling of 1-chlor-
ooctane with n-butylmagnesium chloride in the presence
of 50 mol% of 1,3-butadiene. Our group has recently
reported the first palladium-catalyzed Kumada reaction
using tricyclohexylphosphine as ligand, which allows the
room-temperature coupling of various aryl magnesium
bromides with several functionalized and non-functio-
nalized alkyl chlorides [14].
quent CÁC coupling reactions are generally performed
/
using simple olefins, organoboronic or organomagne-
sium derivatives (Heck, Suzuki and Kumada reactions,
respectively). Important contributions have been made
in the last decade on this topic of current interest [2Á
/8].
Palladium-catalyzed coupling reactions of alkyl chlor-
3
ides (C(sp )ÁCl bonds) have been much less studied so
/
far. There are mainly two reasons, which explain the
difficulty of this catalytic transformation: (i) the slow
oxidative addition of the alkyl chloride to the palladium;
and (ii) the ease of b-hydride elimination reactions of the
In the last decade N-heterocyclic carbenes have been
shown to be alternative ligands to organophosphines for
organometallic and inorganic coordination chemistry.
*
E-mail address: matthias.beller@ifok.uni-rostock.de (M. Beller).
Corresponding author. Fax ꢀ49-381-46693-24.
/
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00723-X

404
A.C. Frisch et al. / Journal of Organometallic Chemistry 687 (2003) 403Á409
/
Table 1
Thus, palladium carbene complexes have become in-
creasingly important as catalysts for Heck, Suzuki and
Sonogashira coupling reactions, copolymerizations and
amination of aryl halides [15]. However, to the best of
our knowledge, no example of catalytic coupling reac-
tions with alkyl halides using N-heterocyclic carbenes as
ligands has been reported until now. Here, we wish to
describe the first successful development of such a
palladium-catalyzed method in the Kumada cross-
coupling reaction of alkyl chlorides.
Fig. 1. Carbene palladium dvds complexes (dvdsꢁ
/1,1,3,3-tetra-
methyl-1,3-divinyl-1,3-disiloxane).
2
. Results and discussion
this reaction. However, a screening of different sterically
hindered alkyl and aryl phosphines in our test reaction
of 1-hexyl chloride and phenylmagnesium bromide did
not lead to any improvement. On the other hand we
were surprised to find that palladium carbene complexes
catalyze this coupling process. While both dvds com-
During our ongoing efforts to develop novel molecu-
larly defined palladium(0) (pre)catalysts for CÁC cou-
/
pling reactions we found that carbene-palladium(0)
diene complexes such as 1 and 2 are excellent catalysts
for the telomerization reaction of 1,3-butadiene with
alcohols [16].
Carbene-palladium(0) quinone complexes 3 and 4
were found to be suitable as catalysts for Heck and
Suzuki reactions of aryl chlorides and aryl diazonium
salts [17].
plexes (dvdsꢁ1,1,3,3-tetramethyl-1,3-divinyl-1,3-disi-
/
loxane) are almost inactive (Table 1, entries 1 and 2),
the corresponding naphthoquinone complexes give the
desired product in moderate to excellent yield in the test
reaction (Table 1, entries 3 and 4) (Figs. 1 and 2). These
experiments show for the first time that N-heterocyclic
carbenes are suitable ligands for palladium-catalyzed
coupling reactions of alkyl chlorides. It is worth
After having demonstrated the general possibility of
palladium-catalyzed coupling reactions of alkyl chlor-
ides with Grignard reagents in the presence of PCy [14],
3
we wondered whether other ligands were also suited for

A.C. Frisch et al. / Journal of Organometallic Chemistry 687 (2003) 403Á
/409
405
Fig. 2. Carbene palladium naphthoquinone complexes.
mentioning that the activity of complex 3 is higher than
that of the previously known palladium/PCy system.
cyclohexyl or i-propyl chloride could not be coupled
with synthetically useful yields so far.
3
While the optimized palladium phosphine catalyst
needed 16 h for complete conversion at room tempera-
Because of the mild reaction conditions and fast
reaction rates for the desired coupling, functionalities
which are often incompatible with Grignard reagents are
tolerated by our system. Nitrile and ester groups are not
attacked to a significant amount (Table 2, entries 10 and
11), but the cyclic imide unit in N-(chloroalkyl)phtha-
limide leads to some side products, giving the desired
ture, the monocarbeneÁ
/
palladium catalyst 3 leads to full
conversion within 1 h.
The difference of reactivity of the dvds and naphtho-
quinone complexes is explained by the stronger binding
of dvds to the palladium center, which is thus blocking
the free coordination sites of the monocarbeneÁ
dium(0) fragment under our mild reaction conditions
room temperature). Quinones, in contrast, might be
attacked by the Grignard reagent, liberating the highly
reactive monocarbeneÁpalladium(0) unit. Unfortu-
nately, we have not been able to detect naphthoquinone
or an addition product with the Grignard reagent after
the reaction has been completed.
/
palla-
coupling products only in moderate yield (33Á
(Table 2, entries 12 and 13).
/
45%)
(
/
3. Summary and outlook
The usefulness of N-heterocyclic carbenes as ligands
for the palladium-catalyzed coupling of primary alkyl
chlorides with arylmagnesium bromides has been de-
monstrated for the first time. Functional groups on both
coupling partners can be tolerated. The defined mono-
Also in situ mixtures of imidazolium salts and
palladium(II) acetate do lead to active catalysts (Table
1
, entries 5Á
somewhat lower activity compared to the defined
monocarbeneÁpalladium(0) complex. Interestingly,
/
8). However, the in situ catalysts show a
carbeneÁpalladium(0) naphthoquinone complex 3 was
/
/
found to be the most efficient catalyst for this type of
reactions so far. Remarkable are the mild conditions
only a 1:1 mixture of 1,3-dimesitylimidazolium hydro-
chloride (IMesHCl) and Pd(OAc) gives a considerable
2
(
room temperature) and the fast reaction (B1 h) of this
/
yield of coupling product. Higher concentration of the
imidazolium salt leads to catalyst deactivation (Table 1,
entries 5 and 6), hence demonstrating the importance of
free coordination sites on the palladium center. A
comparison experiment of 1,3-dimesitylimidazolium
hydrochloride (IMesHCl) and 1,3-(2,6-diisopropylphe-
nyl)imidazolium hydrochloride (IPrHCl) (Table 1, en-
tries 5 and 7) showed that IMes is a more suitable ligand
than the sterically more demanding IPr.
coupling process. Further investigations using modified
carbene ligands for the non-precedented coupling of
secondary and tertiary alkyl chlorides are underway in
our laboratory.
4. Experimental
Next, complex 3 was used for further experiments,
demonstrating the generality of the new catalyst system
4.1. General
(
Table 2). Simple alkyl chlorides are coupled easily with
substituted and non-substituted aryl Grignard reagents
Table 2, entries 1Á4, 7 and 8). Ortho-substitutents on
the arene are tolerated to some extent (Table 2, entries 5
and 6). Arylalkyl chlorides can also be reacted under
standard conditions, leading to good yields (Table 2,
entry 9). Unfortunately, secondary alkyl chlorides like
All syntheses were carried out using standard Schlenk
techniques under an argon atmosphere. All chemicals
were used as received from commercial suppliers.
(
/
IMesHCl, IPrHCl [18] and NHCÁpalladium complexes
/
[17a,19] were prepared according to literature proce-
dures.

406
A.C. Frisch et al. / Journal of Organometallic Chemistry 687 (2003) 403Á409
/
Table 2

A.C. Frisch et al. / Journal of Organometallic Chemistry 687 (2003) 403Á
/409
407
4
.2. General procedure for Kumada reactions
4.6. 5-p-Tolylpentanenitrile
A Schlenk flask was charged with a mixture of
Pd(OAc) (0.018 g, 4 mol%) and imidazolium salt (4
mol%) or with the preformed palladium catalyst (4
mol%), sealed with a septum, and purged with argon.
NMP (5 ml) and alkyl chloride (2 mmol) were added by
Yellow liquid. IR (KBr): 3047 m, 3020 m, 2928 s, 2861
s, 2246 (CN) m, 1515 s, 1458 s, 1425 s, 809 s. MS (EI, 70
2
ꢀ
ꢀ
eV): 173 ([M] , 15%), 105 ([tolCH ] , 100%), 91
2
ꢀ
ꢀ
1
([Bn] , 8%), 77 ([Ph] , 10%). H-NMR (400 MHz,
3
CDCl ): 7.09 (d, JHH
ꢁ7.9 Hz, 2H, Ar), 7.04 (d,
/
3
3
3
syringe. Then, ArÁ
/
MgBr (3 mmol, 3 ml of a 1 M
JHH
ArÁCH ), 2.35Á
1.80Á
ꢁ
/
7.9 Hz, 2H, Ar), 2.60 (t, JHHꢁ
2.29 (m, 5H, ArÁCH2ÁCH , ArÁ
1.60 (m, 4H, CH2ÁCH2Á
/
7.3 Hz, 2H,
CH3),
CN). C{ H}-NMR
solution in THF) was added dropwise over 1 min to the
stirred mixture. After 1 h at room temperature, the
reaction was quenched with MeOH (1 ml) and water (1
ml). The product was isolated by column chromatogra-
phy (silica gel, heptane).
/
/
/
/
/
2
2
1
3
1
/
/
/
(101 MHz, CDCl ): 138.1, 135.5, 129.1, 128.2, 119.6,
34.5, 30.3, 24.8, 17.0, 21.0. Elemental Anal. Calc. for
C H N (187.28): C, 83.19; H, 8.73; N, 8.08. Found: C,
3
1
2
15
83.00; H, 8.52; N, 7.91%.
4
.3. 1-n-Hexyl-2-methylbenzene
4.7. 2-n-Hexyl-1-methoxybenzene
Colorless liquid. IR (KBr): 2956 s, 2928 s, 2858 s,
605 w, 1493 m, 1460 m, 1378 m, 740 s. MS (EI, 70 eV):
Yellow liquid. IR (KBr): 2955 s, 2926 s, 2856 s, 1494 s,
465 s, 1438 s, 1242 s, 1052 s, 1033 s, 751 s. MS (EI, 70
1
1
1
(
(
1
ꢀ
ꢀ
ꢀ
76 ([M] , 29%), 105 ([tolCH ] , 100%), 91 ([Bn] ,
2
ꢀ
ꢀ
eV): 192 ([M] , 21%), 121 ([MeOÁBr] , 100%), 108
/
1
4%), 79 (8%). H-NMR (400 MHz, CDCl ): 6.92Á
/
6.80
ꢀ
ꢀ
ꢀ
1
Ph ], 4%), 91 ([Br] , 51%), 77 ([Ph] , 7%). H-
3
(
[MeOÁ
/
m, 4H, Ar), 2.34 (t, JHH
s, 3H, ArÁCH ), 1.39Á1.27 (m, 2H, ArÁ
.15Á1.00 (m, 6H, (CH ) ÁCH ), 0.70Á0.63 (m, 3H,
CH2ÁCH3). C{ H}-NMR (101 MHz, CDCl ): 141.1,
ꢁ
/
7.9 Hz, 2H, ArÁ
/
CH ), 2.06
2
NMR (400 MHz, CDCl ): 7.20Á
.80 (m, 2H, Ar), 3.82 (s, 3H, OCH ), 2.61 (t, JHHꢁ
/
7.10 (m, 2H, Ar), 6.92Á
/
3
/
/
/
CH2Á
/
CH2),
3
3
6
/7.8
3
1
/
/
/
2
3
3
Hz, 2H, ArÁ
.41Á1.20 (m, 6H, (CH ) Á
CH2Á
/
CH ), 1.65Á
/
1.52 (m, 2H, ArÁ
/
CH2Á
/
CH2),
2
1
3
1
/
3
1
/
/
CH ), 0.94Á
/0.84 (m, 3H,
2
3
3
1
2
35.8, 130.1, 128.7, 125.8, 125.7, 33.3, 31.8, 30.3, 29.4,
2.6, 19.3, 14.1. Elemental Anal. Calc. for C H
20
13
1
/
CH3). C{ H}-NMR (101 MHz, CDCl ): 157.9,
3
1
3
131.8, 130.2, 127.2, 120.7, 110.6, 55.7, 32.2, 30.6, 30.3,
(
176.3): C, 88.57; H, 11.43. Found: C, 88.60; H, 11.33%.
2
9.8, 23.1, 14.6. Elemental Anal. Calc. for C H O
3
1
20
(192.30): C, 81.20; H, 10.48. Found: C, 81.47; H,
1
0.80%.
4
.4. 1-Isobutyl-4-methylbenzene
Colorless liquid. MS (EI, 70 eV): 148 ([M] , 41%),
ꢀ
4.8. 3-n-Hexyl-1-methoxybenzene
ꢀ
ꢀ
1
1
05 ([tolCH ] , 100%), 91 ([Bn] , 17%), 79 (10%). H-
2
Colorless liquid. IR (KBr): 2999 s, 2928 s, 2856 s,
1602 s, 1585 s, 1488 s, 1466 s, 1437 s, 1261 s, 1165 s, 1152
s, 1049 s, 776 s. MS (EI, 70 eV): 192 ([M] , 22%), 135
NMR (400 MHz, CDCl ): 7.10Á
/
7.00 (m, 4H, Ar), 2.43
3
3
(
1
d, JHHꢁ
/
7.1 Hz, 2H, ArÁ
/
CH ), 2.31 (s, 3H, ArÁCH3),
/
2
ꢀ
3
3
.89Á
/
1.77 (m, JHHꢁ
/
6.8 Hz, 1H, CH), 0.89 (d, JHHꢁ
/
ꢀ
ꢀ
1
(CH ) ). C{ H}-NMR (101 MHz,
3
1
(12%), 121 ([MeOÁ
9
/
Br] , 100%), 107 ([MeOÁ
/
Ph] , 8%),
1 ([Br] , 23%), 77 ([Ph] , 11%). H-NMR (400 MHz,
CDCl ): 7.15Á7.06 (m, 1H, Ar), 6.73Á6.60 (m, 3H, Ar),
7.7 Hz, 2H, ArÁ
CH2ÁCH ), 1.30Á1.15
0.74 (m, 3H, CH2ÁCH3).
6
CDCl ): 138.6, 134.9, 129.0, 128.7, 45.0, 30.3, 22.4, 21.0.
.7 Hz, 6H, CHÁ
/
3
2
ꢀ
ꢀ
1
3
/
/
3
3
3
.71 (s, 3H, OCH ), 2.50 (t, JHHꢁ
/
/
3
CH ), 1.59Á
/
1.47 (m, 2,H, ArÁ
/
/
/
2
2
4
.5. 1-Fluoro-4-n-hexylbenzene
(
1
m, 6H, (CH ) ÁCH ), 0.86Á
/
/
/
2
3
3
3
1
C{ H}-NMR (101 MHz, CDCl ): 159.6, 144.6, 129.1,
3
Colorless liquid. IR (KBr): 2957 s, 2929 s, 2857 s,
601 w, 1510 s, 1458 w, 1222 s, 1157 m, 824 m. MS (EI,
120.8, 114.2, 110.8, 55.1, 36.0, 31.7, 31.4, 29.0, 22.5,
1
7
ꢀ
ꢀ
14.1. Elemental Anal. Calc. for C H O (192.30): C,
13 20
0 eV): 180 ([M] , 33%), 109 ([FÁ
/
Bn] , 100%); 96 ([FÁ
7.07
6.90 (m, 2H, Ar), 2.58 (t, JHHꢁ7.7
CH ), 1.65Á1.50 (m, 2H, ArÁCH2ÁCH2),
6.8 Hz,
CH3). C{ H}-NMR (101 MHz, CDCl ):
/
ꢀ
1
81.20; H, 10.48. Found: C, 81.58; H, 10.57%.
Ph] H, 5%). H-NMR (400 MHz, CDCl ): 7.16Á
/
3
3
(
m, 2H, Ar), 7.00Á
Hz, 2H, ArÁ
.38Á
H, CH2Á
/
/
/
/
/
/
4.9. Methyl 6-phenylhexanoate
2
3
1
3
1
1
3
/
1.24 (m, 6H, (CH ) Á
/
CH ), 0.90 (t, JHHꢁ
/
2
1
3
3
1
3
ꢀ
/
Yellow liquid. MS (EI, 70 eV): 206 ([M] , 4%), 105
ꢀ
2 4
3
1
4
ꢀ
ꢀ
61.1 (d, JCFꢁ
/
242.2 Hz), 138.4 (d, JCFꢁ
/
2.9 Hz),
21.0 Hz), 35.1,
1.7, 31.6, 28.9, 22.6, 14.1. Elemental Anal. Calc. for
([PhÁC H ] , 100%), 91 ([Br] , 14%), 77 ([Ph] , 11%).
/
3
2
1
29.6 (d, JCFꢁ
/
7.9 Hz), 114.9 (d, JCFꢁ
/
H-NMR (400 MHz, C D ): 7.17Á
/
7.40 (m, 5H, Ar),
7.7 Hz, 2H, ArCH2),
6.7 Hz, 2H, CH CO ), 1.25Á1.59 (m, 6H,
CH2). C{ H}-NMR (101 MHz, C D ):
6
6
3
4.10 (s, 3H, OCH ), 2.54 (t, JHHꢁ
/
3
3
C H F (180.26): C, 79.96; H, 9.51. Found: C, 79.46; H,
1
1.84 (t, JHHꢁ
/
/
2
17
2
2
1
3
1
9
.84%.
(CH -CH ) Á
/
2
2 3
6
6

408
A.C. Frisch et al. / Journal of Organometallic Chemistry 687 (2003) 403Á409
/
(
(
d) J. Huang, G. Grasa, S.P. Nolan, Org. Lett. 1 (1999) 1307;
e) C. Zhang, J. Huang, M.L. Trudell, S.P. Nolan, J. Org. Chem.
4 (1999) 3804.
1
3
70.3 (CO), 142.8, 128.9, 128.8, 126.3, 64.5 (OCH3),
6.3, 31.6, 29.0, 26.0, 20.8.
6
[7] (a) Recent examples of our group: M. Sundermeier, A. Zapf, M.
Sateesh, M. Beller, Chem. Eur. J. 9 (2003) 1828;
(
b) W. M a¨ gerlein, A.F. Indolese, M. Beller, J. Organomet. Chem.
41 (2002) 30;
c) A. Ehrentraut, A. Zapf, M. Beller, Adv. Synth. Catal. 344
Acknowledgements
6
(
(
The authors thank the state of Mecklenburg-Western
Pomerania, the Bundesministerium f u¨ r Bildung und
Forschung (BMBF) and the Fond der Chemischen
Industrie (FCI) for financial support. Generous gifts of
palladium compounds from OMG are gratefully ac-
knowledged. Dr. W. Baumann, Mrs. H. Baudisch, Mrs.
A. Lehmann and Mrs. C. Mewes are thanked for
analytical support.
2002) 209;
(d) A. Ehrentraut, A. Zapf, M. Beller, J. Mol. Cat. 182Á
(2002) 515;
/
183
(
(
(
(
e) A. Zapf, M. Beller, Chem. Eur. J. 7 (2001) 2908;
f) W. M a¨ gerlein, A. Indolese, M. Beller, Angew. Chem. 113
2001) 2940; Angew. Chem. Int. Ed. 40 (2001) 2856;
g) M. Beller, W. M a¨ gerlein, A.F. Indolese, C. Fischer, Synthesis
(2001) 1098;
(h) M. G o´ mez Andreu, A. Zapf, M. Beller, J. Chem. Soc. Chem.
Commun. (2000) 2475;
(
i) A. Zapf, A. Ehrentraut, M. Beller, Angew. Chem. 112 (2000)
315; Angew. Chem. Int. Ed. 39 (2000) 4153;
(j) A. Ehrentraut, A. Zapf, M. Beller, Synlett (2000) 1589;
k) M. Beller, T.H. Riermeier, C.-P. Reisinger, W.A. Herrmann,
4
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(
(
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4
020;
(
(
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(
b) S.R. Stauffer, S. Lee, J.P. Stambuli, S.I. Hauck, J.F. Hartwig,
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d) J.F. Hartwig, M. Kawatsura, S.I. Hauck, K.H. Shaughnessy,
(
(c) M. Piber, A.E. Jensen, M. Rottl a¨ nder, P. Knochel, Org. Lett. 1
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1
(
(d) R. Giovannini, T. St u¨ demann, G. Dussin, P. Knochel, Angew.
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[
T. Weskamp, J. Organomet. Chem. 617Á
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(
¨
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(b) M. Beller, M. Eckert, Angew. Chem. 112 (2000) 1026; Angew.
Chem. Int. Ed. 39 (2000) 1010;
(
[
6] (a) Recent examples of Nolan’s group: G.A. Grasa, M.S. Viciu, J.
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(
(
2002) 2866;
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(

A.C. Frisch et al. / Journal of Organometallic Chemistry 687 (2003) 403Á
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409
(
f) M. Beller, M. Eckert, H. Geissler, B. Napierski, H.-P.
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(
(n) E. Peris, J.A. Loch, J. Mata, R.H. Crabtree, J. Chem. Soc.
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[
12] (a) Suzuki coupling of alkyl tosylates: M.R. Netherton, G.C. Fu,
Angew. Chem. 114 (2002) 4066; Angew. Chem. Int. Ed. 41 (2002)
(
(
2000) 1773;
3
910;
b) Suzuki coupling of alkyl chlorides: J.H. Kirchhoff, C. Dai,
G.C. Fu, Angew. Chem. 114 (2002) 2025; Angew. Chem. Int. Ed.
1 (2002) 1945;
c) Suzuki coupling of alkyl bromides: M.R. Netherton, C. Dai,
p) S.R. Stauffer, S. Lee, J.P. Stambuli, S.I. Hauck, J.F. Hartwig,
(
Org. Lett. 2 (2000) 1423;
(
(
q) M.L. Trudell, C. Zhang, Tetrahedron Lett. 41 (2000) 595;
r) V. Cal o´ , R. Del Sole, A. Nacci, E. Schingaro, F. Scondari, Eur.
4
(
J. Org. Chem. (2000) 869;
K. Neusch u¨ tz, G.C. Fu, J. Am. Chem. Soc. 123 (2001) 10099.
13] J. Terao, H. Watanabe, A. Ikumi, H. Kuniyasu, N. Kambe, J.
Am. Chem. Soc. 124 (2002) 4222.
(
(
s) D.S. McGuinness, K.J. Cavell, Organometallics 19 (2000) 741;
t) M.C. Done, T. Ruther, K.J. Cavell, M. Kilner, E.J. Peacock,
[
[
[
N. Braussaud, B.W. Skelton, A. White, J. Organomet. Chem. 607
14] A.C. Frisch, N. Shaikh, A. Zapf, M. Beller, Angew. Chem. 114
(
(
2000) 78;
(2002) 4218; Angew. Chem. Int. Ed. 41 (2002) 4056.
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v) M.G. Gardiner, W.A. Herrmann, C.-P. Reisinger, J. Schwarz,
M. Spiegler, J. Organomet. Chem. 572 (1999) 239;
w) W.A. Herrmann, J. Schwarz, M.G. Gardiner, Organometal-
lics 18 (1999) 4082;
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y) D.S. McGuinness, M.J. Green, K.J. Cavell, B.W. Skelton,
(
(
2002) 1342; Angew. Chem. Int. Ed. 41 (2002) 1290;
b) Original publications: M.S. Viciu, R.A. Kelly, E.D. Stevens, F.
(
Naud, M. Studer, S.P. Nolan, Org. Lett. 5 (2003) 1479;
c) M.S. Viciu, R.F. Germaneau, O. Navarro-Fernandez, E.D.
Stevens, S.P. Nolan, Organometallics 21 (2002) 5470;
(
(
(
(
(
d) M.B. Andrus, C. Song, J. Zhang, Org. Lett. 4 (2002) 2079;
e) C.W.K. Gst o¨ ttmayr, V.P.W. B o¨ hm, E. Herdtweck, M.
(
Grosche, W.A. Herrmann, Angew. Chem. 114 (2002) 1421;
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(
(
f) R.A. Batey, M. Shen, A.J. Lough, Org. Lett. 4 (2002) 1411;
g) J.A. Loch, M. Albrecht, E. Peris, J. Mata, J.W. Faller, R.H.
Crabtree, Organometallics 21 (2002) 700;
h) A.M. Magill, D.S. McGuinness, K.J. Cavell, G.J.P. Britovsek,
4
1 (2002) 986;
b) R. Jackstell, A. Frisch, M. Beller, D. R o¨ ttger, M. Malaun, B.
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(
(
V.C. Gibson, A.J.P. White, D.J. Williams, A.H. White, B.W.
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(
i) W.A. Herrmann, V.P.W. B o¨ hm, C.W.K. Gst o¨ ttmayr, M.
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17-618 (2001) 616;
j) D.S. McGuinness, N. Saendig, B.F. Yates, K.J. Cavell, J. Am.
Chem. Soc. 123 (2001) 4029;
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6
(b) K. Selvakumar, A. Zapf, M. Beller, Org. Lett. 4 (2002) 3031.
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55 (1999) 14523.
(
(
[19] These complexes are commercially available from OMG (Hanau,
Germany).
(