Palladium-Catalyzed Direct Cross-Coupling of Carboranyllithium with (Hetero)Aryl Halides

Article abstract of DOI:10.1002/chem.201603967

A palladium-catalyzed direct C-arylation reaction of readily available cage carboranyllithium reagents with aryl halides has been developed for the first time. This method is applicable to a wide range of aryl halide substrates including aryl iodides, aryl bromides, and heteroaromatic halides.

Full text of DOI:10.1002/chem.201603967

DOI: 10.1002/chem.201603967
Communication
&
Cross-Coupling
Palladium-Catalyzed Direct Cross-Coupling of Carboranyllithium
with (Hetero)Aryl Halides
Ju-You Lu,[a] Hong Wan,[a] Jianwei Zhang,[a] Zhixuan Wang,[a] Yang Li,[a] Yongmei Du,[a]
Chunying Li,[a] Zhao-Tie Liu,*[b] Zhong-Wen Liu,[b] and Jian Lu*[a]
Abstract: A palladium-catalyzed direct C-arylation reaction
of readily available cage carboranyllithium reagents with
aryl halides has been developed for the first time. This
method is applicable to a wide range of aryl halide sub-
strates including aryl iodides, aryl bromides, and heteroar-
omatic halides.
Owing to the unique physical and chemical properties, o-car-
boranes are finding many applications in materials science as
building blocks,[1] in medicinal chemistry as boron neutron cap-
ture therapy agents,[2] and in coordination chemistry as li-
gands.[3] Recently, a growing interest has been directed toward
Scheme 1. Direct C-arylation of carboranyl organometallic reagents.
the synthesis of aryl-o-carboranes for their potential applica-
tions in luminescent materials[4] and phosphorescent pro-
and co-workers developed a direct Ni-catalyzed C-arylation by
bes.[2d,5] In general, arylated o-carboranes are prepared through
the condensation reaction of aryl acetylenes with decabor-
ane.[6] However, the hypertoxicity of decaborane complicates
this methodology. It is therefore highly desirable to develop an
efficient synthetic method for the direct C-arylation of o-car-
boranes. Obviously, a direct cross-coupling of carboranyl or-
ganometallic reagents and aryl halides is an attractive strategy
(Scheme 1). This approach has been successfully implemented
in Cu-mediated Ullmann-type coupling reactions in a number
of pioneering examples.[7,8] Wade et al. reported a C-arylation
reaction of carboranylcopper(I) derivatives with aryl iodides.[7]
The strategy of using a C-copper derivative of o-carborane has
also been employed by Endo et al. for the synthesis of 1-(o-car-
boranyl)naphthalene.[8] For these protocols, an additional trans-
formation step must be added to the synthetic sequence for
preparing the carboranylcopper(I) reagents, frequently starting
from the corresponding carboranyllithium reagents. Moreover,
stoichiometric amounts of copper salts and an activating
group (such as a nitro group) are required. Very recently, using
carboranylmagnesium reagents as nucleophilic partners, Xie
Kumada-type coupling of aryl iodides.[9] However, the direct
cross-coupling of carboranyllithium reagents with aryl halides
still represents a very challenging project, despite extensive re-
search on the reactions with alkyl halides.[10] Here, we report
the first transition-metal-catalyzed direct C-arylation of carbora-
nyllithium for the synthesis of aryl-o-carboranes. With palladi-
um complexes as catalyst, the cross-coupling of carboranyllithi-
um and (hetero)aryl halides proceeds readily to provide the
corresponding (hetero)arylated o-carborane derivatives in
good yields.
Carboranyllithium reagents, directly accessible by metalation
of the cage CÀH bonds, have witnessed rapid development in
the past two decades.[11] We chose cross-coupling of carbora-
nyllithium (1-Li-1,2-C2B10H11) with 4-iodotoluene 2a as the
model reaction for optimization. The 1-Li-1,2-C2B10H11 was con-
veniently prepared in situ from an equimolar reaction of o-car-
borane (1,2-C2B10H12, 1) with n-butyllithium (nBuLi) in THF. In-
spired by the transition-metal-catalyzed cross-coupling of orga-
nolithium reagents with aryl halides,[12] we initially used P(tBu)3
as the ligand and toluene as the solvent because these condi-
tions may suppress undesirable side reactions such as lithium–
halogen exchange and homo-coupling reactions. Pd2(dba)3
(dba=dibenzylideneacetone) was used as the catalyst accord-
ing to the previous work.[12a] Unfortunately, the yield of the de-
sired product 3a was very low (Table 1, entry 1). Screening dif-
ferent palladium complexes, we found that the use of
Pd(acac)2 (acac=acetylacetonate) did not significantly improve
the reaction (entry 2), but we were delighted to find that
PdCl2, Pd(OAc)2 and Pd[P(tBu)3]2 provided moderate yields (en-
tries 3–5). To enhance reactivity, we examined in situ prepared
[a] J.-Y. Lu, H. Wan, J. Zhang, Z. Wang, Y. Li, Y. Du, C. Li, Prof. J. Lu
State Key Laboratory of Fluorine & Nitrogen Chemicals
Xi’an Modern Chemistry Research Institute, Xi’an 710065 (P. R. China)
E-mail: lujian204@263.net
[b] Prof. Z.-T. Liu, Prof. Z.-W. Liu
Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Edu-
cation), School of Chemistry & Chemical Engineering, Shaanxi Normal Uni-
versity, Xi’an, 710119 (P. R. China)
E-mail: ztliu@snnu.edu.cn
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201603967.
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was changed from 100 to 808C (entry 15). High temperatures
could facilitate the reaction using m-xylene as the solvent (en-
tries 16–18), and the reaction conditions of entry 18 were iden-
tified as the optimal reaction conditions. An aryl bromide was
also a good substrate (entry 19), but the present conditions
were not effective for the coupling of an aryl chloride, tosylate,
or triflate (entries 20–22). Finally, the reaction did not occur in
the absence of catalyst (entry 23).
Table 1. Optimization of reaction conditions.[a,b]
Under optimal conditions, we next examined the scope of
the direct C-arylation reaction (Table 2). The cross-coupling of
carboranyllithium reagent 1a proceeded with a wide range of
aryl iodides in good yields. The reaction can accommodate var-
ious functional groups, including halides (F and Cl), ethers, thi-
oethers, trifluoromethyl, trifluoromethoxyl, and even benzyl-
protected phenol groups. Both electron-donating (3a–e and
3j–l) and electron-withdrawing (3g–i and 3m–o) substituents
were well-tolerated at either the para or meta positions of the
Entry
X
Catalyst (5 mol%) Ligand (10 mol%) Temp. [8C] Yield [%]
1
2
3
4
5
6
7
8
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
Pd2(dba)3
Pd(acac)2
PdCl2
Pd(OAc)2
P(tBu)3
P(tBu)3
P(tBu)3
P(tBu)3
P(tBu)3
PCy3
JohnPhos
XPhos
DavePhos
BrettPhos
PPh3
(R)-BINAP
XantPhos
–
PCy3
PCy3
100
100
100
100
100
100
100
100
100
100
100
100
100
100
80
110
120
130
130
130
130
130
130
29
24
49
56
63
77
44
62
63
68
55
52
67
61
50
81
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
Pd[P(tBu)3]2
9
10
11
12
13
14
15
16[c]
17[c]
18[c]
19[c]
20[c]
21[c]
22[c]
23[c]
Table 2. Palladium-catalyzed cross-coupling of carboranyllithium with
aryl iodides.[a,b]
I
I
Br
Cl
PCy3
PCy3
PCy3
PCy3
83
91
71
15
OTs Pd[P(tBu)3]2
OTf Pd[P(tBu)3]2
I
PCy3
PCy3
PCy3
Trace
Trace
Trace
–
[a] Reaction conditions: 1,2-C2B10H12 (0.25 mmol), nBuLi (0.3 mmol), THF
(1 mL), at 08C for 1 h; 4-MeC6H4X (0.3 mmol), catalyst (0.0125 mmol),
ligand (0.025 mmol), toluene (1 mL); [b] yield of isolated product; [c] m-
xylene (1 mL) as solvent.
Pd catalysts from Pd[P(tBu)3]2 with various phosphine ligands
for this C(cage)ÀC(sp2) bond formation. Because sterically hin-
dered trialkylphosphines are frequently used as attractive li-
gands in cross-coupling to enhance reductive elimination and
avoid beta-hydrogen elimination,[12d] the ligand PCy3 was also
tested. The use of the in situ formed complex from Pd[P(tBu)3]2
and PCy3 led to 3a in 77% yield at 1008C (entry 6). As dialkyl-
biaryl phosphine ligands have proved to be useful in effecting
the cross-coupling with organometallic reagents,[12c] different
dialkylbiaryl phosphines were screened. Utilizing JohnPhos as
the ligand dramatically reduced the yield, implying that the
nature of the phosphine ligand is a crucial parameter (entry 7).
Other dialkylbiaryl phosphines besides JohnPhos, including
XPhos, DavePhos, and BrettPhos, could also promote the reac-
tion but gave lower yields (entries 8–10). Further optimization
could not increase the yields when triaryl phosphine ligands
were used (entries 11–13). When the commercially available
preformed complex Pd[P(tBu)3]2 was used instead of the in situ
formed catalyst, cross-coupled product 3a was obtained only
in modest yield, meaning that the use of ligands is essential
for this reaction (entry 14). On the other hand, the reaction
temperature also played an important role in this reaction. A
dramatic drop in yield was observed when the temperature
[a] Reactions were conducted at 0.25 mmol scale in 1 mL of m-xylene in
a closed flask at 1308C for 3–12 h; [b] yield of isolated product.
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aryl iodides (49–91% yield). The cross-coupling of p-MeO or m-
MeO-substituted substrates, as reluctant coupling partners,
proceeded well to afford the arylated products 3b and 3k in
77 and 53% yields, respectively. A para-thioether substituent
was also compatible with this protocol (3c). As expected, with
p-chloro-iodobenzene 2g or m-chloro-iodobenzene 2m, cou-
pling reactions occurred exclusively at the iodine-substituted
carbon, but with no detectable chloride displacement (3g and
3m). Notably, the presence of MeO or Cl substituents in prod-
ucts (3b, 3g, 3k, 3m, and 3q) allows for further functionaliza-
tion of the aromatic ring. Fluorinated iodides also underwent
clean coupling without any traces of side products (3h and
3n). The electron-deficient 4-iodobenzotrifluoride 2i and 3-io-
dobenzotrifluoride 2o also underwent clean coupling with car-
boranyllithium, and the trifluoromethylated aryl-o-carborane
scaffolds 3i and 3o were isolated in moderate yields. The use
of trifluoromethoxyl-substituted aryl iodides led to reduced
yields (3e and 3l). A challenging problem in cross-coupling
processes is the combination of carboranyllithium with sterical-
ly hindered coupling partners bearing large ortho-substituents.
To our delight, the coupling with 2-iodotoluene 2p proceeded
smoothly, and aryl-substituted product 3p was obtained in
good yield. Remarkably, the highly hindered 2-iodoisopropyl-
benzene 2r could be coupled under these optimal conditions,
affording the corresponding product 3r in 63% yield. It is im-
portant to note that carboranylation of 4-iodo-1,1’-biphenyl to
form 3v was achieved in high yield. The biaryl-o-carborane
compound 3v is a precursor for a variety of carborane-based
biphenyl derivates with application in optoelectronic material-
s.[4a,g–k] More importantly, 4-benzyloxy-iodobenzene 2x could
be carboranylated (3x) using the carboranyllithium reagent,
despite the acidity of the benzylic protons. The reactions em-
ploying other electron-rich aryl iodides also proceeded in good
yields (3s–u, 3w, and 3y). The polyaromatic compound 1-io-
donaphthalene 2z was regioselectively carboranylated at posi-
tion 1 (3z), indicating that the benzyne intermediate through
1,2-elimination was not formed. However, aryl iodides with
electron-withdrawing substituents, such as NO2, CN, COOCH3,
or COOH, are not suitable substrates because competing reac-
tion pathways lead to the decomposition of the starting mate-
rial under current conditions.
entry 1 in the Supporting Information), we found that by using
5 mol% commercially available Pd[P(tBu)3]2 as the catalyst and
phosphine ligand-free conditions, the yield of aryl product 3a
could be substantially improved to 90% (Table S1, entry 6 in
the Supporting Information). However, a variety of dialkylbiaryl
phosphines proved inferior and led to diminished yields
(Table S1, entries 7–10 in the Supporting Information).
We then explored the scope of aryl bromides and carbora-
nyllithium reagent under new conditions. As illustrated in
Table 3, a wide range of aryl bromides with electron-donating,
-neutral, or -withdrawing substituents were well tolerated (3a,
3b, 3 f, and 3h). Remarkably, highly deactivated dimethyla-
Table 3. Palladium-catalyzed cross-coupling of carboranyllithium with
aryl bromides.[a,b]
[a] Reactions were conducted at 0.25 mmol scale in 1 mL of o-xylene in
a closed flask at 1408C for 12–24 h; [b] yield of isolated product.
We next investigated whether the same strategy could be
applied to aryl bromide substrates, which are versatile and
widely used synthetic intermediates, although carboranylation
of aryl bromides has only been studied by using carboranyl-
magnesium as nucleophilic reagent, giving one example in
50% yield.[9] We were aware that direct cross-coupling of car-
boranyllithium with aryl bromides would pose an inevitable
challenge: Aryl bromides are generally less reactive than io-
dides under these C-arylation conditions. The reactivity trend
of organic halides is inversely proportional to their bond-disso-
ciation energy, and CÀBr bonds arguably possess shorter bond
lengths than CÀI bonds. With this consideration in mind, we
further optimized the reaction conditions for the coupling of
aryl bromides. Although an initial investigation with 4-bromo-
toluene (4a) only provided 60% yield of the desired product
3a under the optimal conditions for aryl iodides (Table S1,
mine- or morpholine-substituted aryl bromides 4e and 4 f
were also converted under the optimized reaction conditions
to the desired products in excellent yields (3aa and 3ab). Fur-
thermore, the cross-coupling of the functionalized aryl bro-
mide (4-bromophenyl)trimethylsilane 4e proceeded with good
yield (3ac). Moderate to good yields were achieved after con-
ducting the reaction with polyaromatic compounds (3ad and
3z). The use of sterically hindered ortho-substituted aryl bro-
mides led to a reduced yield (3p, 52%).
Finally, we examined whether this approach for C-arylation
could be adapted to achieve C-heteroarylation, thereby provid-
ing a method for the synthesis of heteroarylated compounds
(Table 4). In remarkable contrast to diheteroarylation of a car-
boranylcopper(I) reagent with 2-bromopyridine 5a’,[7] direct
cross-coupling of carboranyllithium with 2-iodopyridine 5a
proceeded smoothly to afford the monopyridyl product 6a in
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ture with stirring for 1 h, and was allowed to reach room tempera-
ture. Subsequently, Pd[P(tBu)3]2 (5 mol%, 0.0125 mmol, 6.4 mg),
PCy3 (10 mol%, 0.025 mmol, 7.0 mg), m-xylene (1 mL), and the sub-
strate aryl halides (0.3 mmol) were added under an inert nitrogen
atmosphere, and the mixture was heated at 1308C under stirring
in a closed flask. After the reaction was completed, a saturated so-
lution of aqueous NH4Cl was added and the mixture was extracted
three times with diethyl ether. The organic phases were collected,
and solvent evaporation under reduced pressure afforded the
crude product, which was then purified by column chromatogra-
phy to remove the catalyst and ancillary ligand and provide the
product, by using silica gel as stationary phase and n-hexane as
eluent.
Table 4. Palladium-catalyzed cross-coupling of carboranyllithium with
heteroaromatic halides.[a,b]
Acknowledgements
[a] Reactions were conducted at 0.25 mmol scale in 1 mL of THF in
a closed flask at 708C for 12–20 h; [b] yield of isolated product.
We thank the National Natural Science Foundation of China
(21403163, 21327011, 21376146) and the Natural Science Basic
Research Plan in Shaanxi Province of China (2014JQ2062) for fi-
nancial support.
good yield and with excellent selectivity at a decreased tem-
perature (708C). Both electron-donating and electron-with-
drawing substituents of the heterocyclic halide coupling part-
ners were tolerated, and we were able to provide the C-heter-
oarylated products in moderate yields (6b and 6c). Similarly,
with 5-chloro-2-iodopyridine 5b, cross-coupling occurred ex-
clusively at the iodine-substituted carbon, with no detectable
chloride displacement (6b). Remarkably, the sterically hindered
2-iodo-3-methylpyridine 5c could be coupled under the stan-
dard conditions, affording the desired product 6c in 50%
yield. It is noteworthy that the use of less reactive 2-bromopyr-
idine 5a’ led to an enhanced yield (6a, 70%). These experi-
ments suggest that this reaction is compatible with heteroaro-
matic halides as coupling partners, overriding the strong coor-
dination of heteroatoms to the metal catalyst. This feature ren-
ders the reaction particularly useful for the synthesis of biologi-
cally active compounds bearing icosahedral o-carboranes and
heterocycles.
Keywords: C(cage)ÀC(sp2) formation
· carboranyllithium ·
cross-coupling · direct C-arylation · palladium
ˇ
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In conclusion, we have demonstrated the Pd-catalyzed
direct cross-coupling of carboranyllithium with (hetero)aryl hal-
ides for the selective formation of C(cage)ÀC(sp2) bonds, pro-
viding a new route for the preparation of (hetero)aryl-o-carbor-
anes. This method does not involve transmetalation of the car-
boranyllithium reagent. As a consequence, we expect that this
methodology will be rapidly adopted to prepare diverse (het-
ero)aryl-substituted o-carboranes for use in materials science,
medicinal, and coordination chemistry. Additionally, this trans-
formation is a valuable addition to the tool box for making ico-
sahedral functionalized carboranes.
Experimental Section
General procedure for the Pd-catalyzed cross-coupling of
carboranyllithium with aryl halides
In a dry Schlenk flask, nBuLi (1.6m in n-hexane, 0.3 mmol, 0.18 mL)
was added slowly to
a THF solution (1 mL) of 1,2-C2B10H12
(0.25 mmol, 36 mg) at 08C. The solution was kept at low tempera-
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Received: August 20, 2016
Published online on && &&, 0000
Chem. Eur. J. 2016, 22, 1 – 6
www.chemeurj.org
5
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Communication
COMMUNICATION
&
Cross-Coupling
J.-Y. Lu, H. Wan, J. Zhang, Z. Wang, Y. Li,
Y. Du, C. Li, Z.-T. Liu,* Z.-W. Liu, J. Lu*
&& – &&
Palladium-Catalyzed Direct Cross-
Coupling of Carboranyllithium with
(Hetero)Aryl Halides
Palladium-catalyzed direct C-arylation
of readily available cage carboranyllithi-
um reagents with aryl halides has been
developed for the first time. This
method is applicable to a wide range of
aryl halide substrates including aryl io-
dides, aryl bromides, and heteroaromat-
ic halides.
&
&
Chem. Eur. J. 2016, 22, 1 – 6
www.chemeurj.org
6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!