Nickel-Catalyzed Cross-Coupling of Organolithium Reagents with (Hetero)Aryl Electrophiles

Article abstract of DOI:10.1002/chem.201505106

Nickel-catalyzed selective cross-coupling of aromatic electrophiles (bromides, chlorides, fluorides and methyl ethers) with organolithium reagents is presented. The use of a commercially available nickel N-heterocyclic carbene (NHC) complex allows the reaction with a variety of (hetero)aryllithium compounds, including those prepared via metal-halogen exchange or direct metallation, whereas a commercially available electron-rich nickel-bisphosphine complex smoothly converts alkyllithium species into the corresponding coupled product. These reactions proceed rapidly (1 h) under mild conditions (room temperature) while avoiding the undesired formation of reduced or homocoupled products. Nickel-catalyzed cross-coupling of aromatic electrophiles with organolithium reagents is presented. The use of a commercially available nickel N-heterocyclic carbene complex allows reaction with a variety of (hetero)aryllithium compounds, whereas a commercially available electron-rich nickel bisphosphine complex smoothly converts alkyllithium species into the corresponding coupled product.

Full text of DOI:10.1002/chem.201505106

DOI: 10.1002/chem.201505106
Communication
&
Homogeneous Catalysis
Nickel-Catalyzed Cross-Coupling of Organolithium Reagents with
(Hetero)Aryl Electrophiles
Dorus Heijnen, Jean-Baptiste Gualtierotti, Valentín Hornillos,* and Ben L. Feringa*[a]
Abstract: Nickel-catalyzed selective cross-coupling of aro-
matic electrophiles (bromides, chlorides, fluorides and
methyl ethers) with organolithium reagents is presented.
The use of a commercially available nickel N-heterocyclic
carbene (NHC) complex allows the reaction with a variety
of (hetero)aryllithium compounds, including those pre-
pared via metal-halogen exchange or direct metallation,
whereas a commercially available electron-rich nickel-bis-
phosphine complex smoothly converts alkyllithium spe-
cies into the corresponding coupled product. These reac-
tions proceed rapidly (1 h) under mild conditions (room
temperature) while avoiding the undesired formation of
reduced or homocoupled products.
In the ongoing search for more efficient, environmentally
Scheme 1. Nickel-catalyzed cross-coupling methodologies.
benign and economically sustainable processes, current re-
search in cross-coupling methodologies has shown a growing
interest in the use of earth-abundant metal-based catalysts.[1]
Although palladium is applied in the majority of these process-
es, catalytic systems based on iron, nickel, or cobalt have
proven suitable alternatives in several cases. In particular, the
use of nickel has witnessed a rapid growth owing to its low
cost and unique properties.[2] Nickel undergoes oxidative addi-
tion more readily than palladium although reductive elimina-
tion is correspondingly more difficult.[2b,c] Ni0/NiII catalytic
cycles are well known,[2c] but NiI and NiIII oxidation states[2d] can
be also accessed, allowing for different modes of reactivity and
for radical mechanisms to operate.
the less reactive aromatic ethers.[6a–c] Various groups have fur-
ther developed the use of Grignard reagents and other nucleo-
philes, including organozinc and organoboron compounds, in
nickel-catalyzed cross-coupling with aryl[6d–f] and benzyl
ethers[6g] (Scheme 1a). Additionally, nickel has also been found
to activate very strong CÀF bonds.[7] Thus, the coupling of aro-
matic fluorides with organometallic compounds has been re-
ported, although activated fluoroarenes or polyfluorinated aro-
matic substrates are usually employed.[7c] Some of these reac-
tions suffer from competing isomerization of the alkyl coupling
partners.[7d]
Nickel has been extensively used in cross-coupling of orga-
noboron and organozinc reagents with organic halides
(Scheme 1a).[3] For example, a highly efficient nickel-catalyzed
method for the synthesis of heterobiaryls at low temperature
described by the group of Hartwig highlights the potential of
nickel in Suzuki–Miyaura reactions.[4] Since the early reports by
Kumada and co-workers in 1972, Grignard reagents in combi-
nation with nickel are known to be effective in the cross-cou-
pling with aryl halides,[5] and these organometallic reagents
were also the first to be efficiently employed in reactions with
In sharp contrast, the direct use of organolithium reagents,
among the most versatile and widely used reagents in organic
synthesis,[8] in nickel-catalyzed cross-couplings reactions has
been limited to the polymerization of lithiated (hetero)-
arenes,[9a,b] the coupling of (trimethylsilyl)methyllithium with ar-
omatic ethers (Scheme 1b),[9c,d] and the homo-coupling of aryl-
bromides although the scope of the latter is limited so far.[9e]
Despite these important advances, a general method for the
nickel-catalyzed cross-coupling of alkyl and (hetero)aryllithium
reagents with aryl(pseudo)halides remains elusive.
Organolithium compounds[8] are commercially available or
readily accessible by lithium–halogen exchange and they are
often employed as precursors for other organometallic com-
pounds (Mg, B, Zn, Sn) used in cross-coupling reactions. Their
direct use drastically reduces the amount of byproducts with
the light lithium halide being the only stoichiometric reaction
waste. Our group recently described the direct use of these re-
[a] D. Heijnen, Dr. J.-B. Gualtierotti, Dr. V. Hornillos, Prof. Dr. B. L. Feringa
Stratingh Institute for Chemistry, University of Groningen
Nijenborgh 4, 9747 AG, Groningen (The Netherlands)
E-mail: v.hornillos.gomez.recuero@rug.nl
b.l.feringa@rug.nl
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201505106.
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Table 1. different ligands.
agents in palladium-catalyzed cross-coupling under mild condi-
tions of a wide variety of organic bromides,[10] chlorides,[11] and
triflates,[12]
providing
high
yields
and
selectivities
(Scheme 1c).[13] Considering the advantages associated with
the use of nickel-based catalytic systems, the development of
a general nickel-catalyzed cross-coupling with easily accessible
organolithium reagents will provide a highly desirable alterna-
tive to existing methodologies. Moreover, since the palladium-
catalyzed methods with these reagents are based on the use
of aryl bromides, chlorides, and triflates, we were interested in
exploring the coupling of less reactive fluorides and aromatic
ethers, the latter being obtained from a pool of materials en-
tirely distinct from aryl halides.
Herein, we report that the use of a commercially available
nickel N-heterocyclic carbene (NHC) or bisphosphine complex
allows for the selective cross-coupling of organolithium com-
pounds with aryl bromides, chlorides, fluorides, and methyl
ethers in high selectivity under mild conditions (RT) and within
short reaction times (1 h; Scheme 1d).
In preliminary studies, we focused on reactions between
either nBuLi or PhLi and 1-chloronaphthalene (1a) in toluene
at RT (Table 1). Surprisingly, the use of [Ni(cod)2] (cod=1,5-cy-
clooctadiene), which has previously been shown to be effec-
tive for the cross-coupling of (trimethylsilyl)methyllithium with
aryl ethers,[9c,d] gave no conversion into the desired products
2a or 3a. (Table 1, entries 1a,b). Adding a phosphine ligand
such as 1,2-bis(diphenylphosphino)ethane (dppe) to the nickel
catalyst gave the same disappointing result for nBuLi (Table 1,
entry 2a) and 51% conversion, along with dehalogenated side
product 4a, for PhLi (entry 2b). Considering these results and
the fact that [Ni(cod)2] requires rigorous air-free conditions,
hampering both large-scale applications and optimization ef-
forts, we turned our attention to nickel(II) catalysts. Low to
moderate conversions and selectivities were observed when
[NiCl2(dme)] (dme=dimethoxyethane) or [NiCl2(PPh3)2] were
used (Table 1, entries 3a–4b). Using more electron rich and
Entry[a]
R
Catalyst
[Ni(cod)2]
Conv. [%][b]
2a/3a:4a:5a[b]
1a
1b
nBu
Ph
2
0
–
–
2a
2b
nBu
Ph
3
51
–
[Ni(cod)2]/dppe
[NiCl2(dme)]
[NiCl2(PPh3)2]
[NiCl2(PCy3)2]
[NiCl2(dme)]/Xphos
[NiCl2(dppe)]
[NiCl2(dppf)]
C1
53:47:0
3a
3b
nBu
Ph
5
39
–
85:15:0
4a
4b
nBu
Ph
40
30
42:40:18
90:10:0
5a
5b
nBu
Ph
68
>99
25:60:15
68:30:2
6a
6b
nBu
Ph
69
33
15:46:23
67:33:0
7a
7b
nBu
Ph
>99
86
93::7:0
73:25:2
[14]
bulky phosphines (PCy3 or XPhos[15]) resulted in higher con-
version, but the selectivity for 2a or 3a remained unsatisfacto-
ry (Table 1, entries 5a–6b). Subsequently, we investigated the
effect of common bidentate phosphines, which have been re-
ported to impart high activity in related nickel-catalyzed cross-
coupling reactions with other organometallics. The use of
[NiCl2(dppe)][16] and [NiCl2(dppf)] (dppf=1,1’-bis(diphenylphos-
phino)ferrocene)[4] resulted in even higher conversions but de-
halogenation remained substantial (Table 1, entries 7a–8b). En-
couraged by these results, we studied variations in the ligand
structure and we found that the use of commercial nickel com-
plex [NiCl2(depe)] (C1; depe=bis(diethylphosphino)ethane)[17]
bearing a bidentate alkylphosphine, led to full conversion in
the reaction with both nBuLi and PhLi with excellent selectivity
toward the cross-coupled products 2a or 3a (Table 1, entrie-
s 9a,b). The nitrogen-based tridentate ligand C2 (Table 1, en-
tries 10a,b)[18] was not efficient for this transformation. Remark-
ably, the use of Pd-PEPPSI-IPent (Table 1, entry 12), as well as
other palladium-based catalysts (not shown) in the reaction of
nBuLi gave rise to lower selectivity than that observed with
the nickel catalyst C1.
8a
8b
nBu
Ph
85
92
52:35:8
79:15:6
9a
9b
nBu
Ph
>99
>99
94:6:0
95:1:4
10a
10b
nBu
Ph
36
98
11:89:0
58:42:0
C2
11 a
nBu
Ph
Ph
72
>99
>99
>99
57:43:0
>99:0:0
>99:0:0
>99:0:0
(98% yield)
>99:0:0
11 b
11 c[c]
11 d[d]
C3
Ph
11 e[e]
12
Ph
30
nBu
Pd-PEPPSI-Ipent
>99
86:14:0
[a] Conditions: n-Butyllithium (0.45 mmol, 1,6m in hexanes diluted with
toluene to a final concentration of 0.45m) or phenyllithium (0.45 mmol,
1.8m solution in dibutyl ether diluted with toluene to a final concentra-
tion of 0.5m) was added to a solution of 2-chloronaphthalene (0.3 mmol)
in toluene (1,5 mL) over 1 h. [b] Conversion and 2a/3a:4:5 ratios deter-
mined by GC analysis. [c] Using 0.5 mol% of catalyst. [d] 10 mmol (1.63 g)
scale reaction using 1.5 mol% of catalyst. [e] Using 0.25 mol% of catalyst.
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We then explored the effectiveness of catalyst C1 with re-
spect to a less reactive, non-p-extended aryl chloride, such as
1-butyl-4-chlorobenzene 1b (Scheme 2), but incomplete con-
version was observed in the case of PhLi, alongside a large
amount of n-butylbenzene 4b (Scheme 2). As neither elevated
nor lower temperatures improved this result, further screening
of nickel catalysts was carried out. We found that the use of
commercially available nickel(II) complex C3,[9a] bearing a N-
heterocyclic carbene, was key to restoring the conversion
(87% yield of isolated product) and selectivity (98:2) toward
2b (Scheme 2). Catalyst C3 also gave full conversion with high
selectivity in the reaction of 1a with PhLi (Table 1, entry 11 b),
allowing a decrease in the catalyst loading to 0.5 mol%
(entry 11c). Moreover, when this reaction was performed on
a larger scale (10 mmol, 1.63 g) in the presence of 1.5 mol% of
catalyst C3, 2a was still obtained as the exclusive product in
excellent yield (98% isolated product). The use of C3 in the re-
action of 1a with nBuLi afforded the desired compound 3a,
albeit with decreased conversion and selectivity compared to
C1 ((Table 1, entry 11 a).
(2a, 2c–e). Substrates containing two aromatic groups can
also be transformed selectively (2 f, X=Br, and 2g, X=Br, F). It
is important to note that high reactivity was also found for
simple phenyl halides or methyl ethers, regardless of the elec-
tronic nature or the leaving group employed (2i–o). As shown
for 2g, 2j, and 2k, the presence of an ortho substituent did
not significantly hamper the cross-coupling. A substrate con-
taining an olefin (1h) was also readily converted into the corre-
sponding product 2h with high selectivity (Scheme 2). Trifluor-
omethylated compounds, which are very important in the
agrochemical and pharmaceutical industries,[19] were also suita-
ble substrates, furnishing the corresponding products 2l and
2m in moderate to good yield. As expected, CÀBr and CÀCl
bonds are more reactive than a CÀO bond, allowing the selec-
tive coupling of 4-bromo- or 4-chloroanisole at 08C, leaving
the methoxy group untouched (2n). Only dehalogenation was
observed in the reaction of 3-bromo-N,N-dimethylaniline 1o
with PhLi. However, the corresponding chloride provided biaryl
2o in 45% yield. A sulfur-containing heterocycle was also cou-
pled, affording compound 2p with high selectivity.
With two optimized catalyst systems (C3 for (hetero)aryllith-
ium and C1 for alkyllithium, respectively) we examined the
generality of this reaction. A broad range of aryl bromides,
chlorides, fluorides, and methoxyarenes could be coupled with
PhLi, using C3 as catalyst (Scheme 2). Polyaromatic compounds
showed high reactivity and could be transformed into the cou-
pled products in good to high yields with excellent selectivity
We next examined the compatibility of our catalytic system
with the most efficient procedures to access (hetero)aryllithium
species, which include direct metalation[20] and halogen–lithi-
um exchange[8] (Scheme 3). Hindered bis-ortho-substituted
(2,6-dimethoxyphenyl)lithium, prepared by directed lithiation,
undergoes cross-coupling with 1-chloronaphthalene and elec-
tron-rich 4-bromoanisole providing biaryls 2q and 2r, without
the need to increase the temperature or reaction time. More-
Scheme 2. Nickel-catalyzed cross-coupling of phenyllithium with (hetero)aryl
(pseudo)halides. [a] Conditions: Phenyllithium (0.75 mmol, 1.8m solution in
dibutyl ether diluted with toluene to a final concentration of 0.6m) was
added to a solution of organic (pseudo)halide (0.5 mmol) in toluene (1.5 mL)
over 1 h; yields refer to product isolated by column chromatography; [b] re-
action performed at 08C.
Scheme 3. Nickel-catalyzed cross-coupling of (hetero)aryllithium reagents
with aryl halides. Conditions: Aryllithium (0.75 mmol, diluted with toluene to
a final concentration of 0.45m) was added to a solution of organic halide
(0.5 mmol) in toluene (1.5 mL) over 1 h; >90% selectivity to 2 vs. dehalo-
genated + homocoupled products; yields refer to product isolated by
column chromatography.
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Communication
over a methoxymethyl (MOM) protecting group could be toler-
ated at the ortho position of the organolithium reagent, allow-
ing for an easy ortho-lithiation/cross-coupling sequence to
afford the corresponding MOM-protected phenol (2s, 2t). Fur-
yllithium, obtained by direct lithiation of furan, smoothly cou-
ples to provide compounds 2u–w with good yields and high
selectivities. Organolithium compounds, obtained through hal-
ogen–lithium exchange, could also be used as exemplified in
the preparation of 2x and 2z. Importantly, commercially avail-
able 2-thienyllithium, which, according to our previous
study,[10a] requires the addition of stoichiometric amounts of
tetramethylethylenediamine (TMEDA) as activating agent and
elevated temperatures, reacted with 1-chloro- and 1-bromo-
naphthalene at room temperature without the use of any addi-
tive (2y).
With an efficient procedure for aryl–aryl cross-coupling in
hand, we turned our attention to the use of alkyllithium com-
pounds (Table 2).[21] A range of polyaromatic chlorides and flu-
orides were regioselectively alkylated at position 1 or 2, indi-
cating that benzyne intermediates, formed through 1,2-elimi-
nation, are not involved. No isomerization of the alkyl moiety
and less than 5% of reduced product were observed when pri-
mary alkyllithium reagents were employed, demonstrating that
competing b-hydride elimination/dissociation was almost com-
pletely inhibited. Importantly, the use of EtLi, which was un-
reactive in our previous palladium-based systems, afforded the
corresponding products (3a, 3e, 3g) in good yields and nearly
perfect selectivities. These results highlight how alternative
metals such as nickel, besides being inexpensive, can also dis-
play complementary reactivity to palladium. The reaction using
iPrLi, which contains an increased number of b-hydrogen
atoms, proceeds without isomerization, although a minor
amount of the reduced product was formed (Table 2, entries 4
and 14).[22] Cyclopropyllithium,[23] prepared from cyclopropyl
bromide and lithium metal, also provided the coupled product
with high selectivity without any ring-opened side products
(Table 2, entry 11).[24]
In summary, we have described for the first time how
a range of (hetero)aryl and alkyllithium compounds can be em-
ployed in cross-coupling reactions with aryl bromides, chlor-
ides, fluorides, and aromatic ethers, by using nickel as catalyst.
The reaction takes place under mild conditions (RT) with
a broad scope of organolithium compounds and substrates,
enabling transformations that were proven difficult with palla-
dium catalysts, such as the cross-coupling of alkyllithium re-
agents bearing b-hydrogen with aryl chlorides and the use of
EtLi as a coupling partner. The low cost and availability of both
organolithium reagents and nickel catalysts, together with the
selectivity of the novel method presented herein, make it a val-
uable alternative with lower environmental impact for atom-
economic formation of CÀC bonds.
Acknowledgements
The Netherlands Organization for Scientific Research (NWO-
CW), the National Research School Catalysis (NRSC-C), the Euro-
pean Research Council (ERC advanced grant 227897 to B.L.F.),
the Royal Netherlands Academy of Arts and Sciences (KNAW),
the Ministry of Education Culture and Science (Gravitation pro-
gram 024.601035) and the Swiss National Science Foundation
(SNSF) are acknowledged for financial support.
Table 2. catalyzed cross-coupling of alkyllithium compounds
Keywords: biaryl synthesis · cross-coupling · homogeneous
catalysis · nickel · organolithium compounds
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Entry[a]
Aryl halide
Alkyllithium
Yield [%][b]
1 (3a)
2 (3b)
3 (3c)
4 (3d)
EtLi
nBuLi
n-HexLi
iPrLic
65
78
87
63
1-chloronaphthalene
5 (3e)
6 (3 f)
EtLi
n-HexLi
67
39
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1-chloroanthracene
7 (3g)
8 (3h)
9 (3i)
10 (3j)
11 (3k)
EtLi
nBuLi
n-HexLi
iPrLi[c]
94
84
85
44
66
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12 (3b)
13 (3a)
14 (3d)
nBuLi
EtLi
iPrLi
76
66
63
1-fluoronaphthalene
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Received: December 21, 2016
Published online on February 4, 2016
Chem. Eur. J. 2016, 22, 3991 – 3995
www.chemeurj.org
3995
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim