One-Pot Process to Carborano-Coumarin via Catalytic CascadeDehydrogenative Cross-Coupling

Article abstract of DOI:10.1002/cjoc.201900475

Ir-catalyzed cascade dehydrogenative CH/BH and BH/OH cross-coupling of carboranyl carboxylic acid with readily available benzoic acid has been achieved, leading to the facile synthesis of previously unavailable carborano-coumarin in a simple one-pot process. Two cage B—H, one aryl C—H and one O—H bonds are activated to construct efficiently new B—C and B—O bonds. The cascade cyclization can stop at the first B—H/C—H cross-coupling step by tuning the reaction conditions, resulting in a series of α-carboranyl benzoic acid and aryl carborane derivatives. Control experiments indicate that B—H/C—H dehydrocoupling proceeds preferentially over B—H/O—H dehydrocoupling, and both directing groups and oxidants are crucial for this reaction. An iridium(V) intermediate is proposed to be involved in the catalytic cycle.

Full text of DOI:10.1002/cjoc.201900475

Chinese Journal
of Chemistry
CJC 中 国 化 学 - An International Journal
Accepted Article
Title: One-pot process to carborano-coumarin via catalytic cascade
dehydrogenative cross-coupling
Authors: Yik Ki Au, Hairong Lyu, Yangjian Quan,* and Zuowei Xie*
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This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.201900475.
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Keyword 1, Keyword 2, Keyword 3, Keyword 4, Keyword 5, Keyword 6
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One-pot process to carborano-coumarin via catalytic cascade
dehydrogenative cross-coupling
Yik Ki Au, Hairong Lyu, Yangjian Quan,* and Zuowei Xie*a
a
Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong (China)
Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
Summary of main observation and conclusion Ir-catalyzed cascade dehydrogenative CH/BH and BH/OH cross-coupling of carboranyl carboxylic acid with
readily available benzoic acid has been achieved, leading to the facile synthesis of previously unavailable carborano-coumarin in a simple one-pot process.
Two cage B-H, one aryl C-H and one O-H bonds are activated to construct efficiently new B-C and B-O bonds. The cascade cyclization can stop at the first B-
H/C-H cross-coupling step by tuning the reaction conditions, resulting in a series of α-carboranyl benzoic acid and aryl carborane derivatives. Control
experiments indicate that B-H/C-H dehydrocoupling proceeds preferentially over B-H/O-H dehydrocoupling, and both directing groups and oxidants are
crucial for this reaction. An iridium(V) intermediate is proposed to be involved in the catalytic cycle.
Background and Originality Content
catalytic cascade dehydrocoupling of carborane with benzoic acid.
Benzoic acids, occurring naturally in plenty of plants, are
Carboranes, a class of polyhedral boron-carbon molecular
clusters, possess unique properties including icosahedral geometry,
three-dimensional aromaticity conjugated by σ-bonds, and
inherent robustness. These advantages endow carboranes
valuable applications in medicine as boron neutron capture
important precursors in plasticizers, preservations and organic
[13]
synthesis.
To achieve our goal of cascade dehydrocoupling
between carborane and benzoic acid, several issues ought to be
concerned. In spite of the established catalytic systems for carboxyl
[9,10]
[14]
group guided cage B-H
or aryl C-H functionalization, the ideal
[1]
therapy agents, in coordination/organometallic chemistry as
catalytic system for such a two-fold cross-coupling is required not
only to be versatile to activate both B-H and C-H in a one-pot
process, but also to be discriminatory regarding to B-H and C-H
bonds so as to facilitate B-C cross-coupling rather than B-B or C-C
[
2]
versatile ligands, in supramolecular design/nanomaterials as
[3]
useful building blocks and in optoelectronic functional materials
[
4]
as unique electron sinks. Recently, replacing phenyl ring in
bioactive molecules and/or medicines by carborane moiety has
contributed a carborane version of these molecules with
extraordinary properties or enhanced potencies.[ In spite of this,
the limited methods for the functionalization of carboranes restrict
[10]
homo-couplings. On the other hand, the B-O coupling would
definitely undergo a different pathway from the previously
5]
[9]
reported metal-nitrene mediated B-N coupling. After many
attempts, we have developed an efficient and straightforward
methodology for the preparation of carborano-coumarin
derivatives via the cascade dehydrocoupling strategy. By tuning
reaction conditions, the two-fold cross-coupling could be stopped
at the first B-H/C-H cross-coupling step, leading to a series of α-
carboranyl benzoic acids or arylcarboranes, respectively. The detail
is reported in this article (Scheme 1).
[6]
their applications. Hitherto no reported methods are available to
prepare carborano-coumarin derivatives, though their organic
analogues, dibenzopyranone, are widely present in drug molecules
[7]
and natural products. To this end, the development of efficient
and straightforward methodologies for the facile synthesis of
complex carborane-based functional molecules is eagerly
[
8]
desired.
Very recently, our group reported a cascade dehydrocoupling
strategy to prepare carborano-isoquinolinones from readily
[
9]
available carborane and benzamide. Such a protocol possesses
considerable advantages including better atom/step economy,
functional group tolerance and practicability, in comparison with
conventional transition-metal-catalyzed B-H functionalization
10-12
reactions of carboranes,
which require pre-functionalized
coupling partners. Inspired by this, we initiated an investigation of
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First author et al.
Scheme 1 Carboranyl alternatives of benzocoumarin
AgNTf (10)
2
5d
6e
Li
Li
CO
CO
(2.0)
(2.0)
160
160
160
140
140
80
25/-/-
77/-/-
2
3
O
O
AgOAc (10)
2
O
O
AgNTf (15)
2
2
3
AgOAc (15)
AgNTf
AgOAc (10)
AgNTf (10) Li
2
(10) Li
CO
3
(1.0)
(1.0)
(1.0)
(1.0)
(1.0)
(1.0)
(1.0)
(1.0)
(1.0)
(1.0)
7f,g
8 f,g
9 f,g
-/58/20
-/57/18
-/-/86
K
2
CO
3
Our design:
2
2
CO
3
O
O
H
O
H
O
AgOAc (10)
AgOAc (20)
K CO
2
3
+
H
Li
2
CO
CO
CO
CO
CO
CO
3
H
K
2
3
CR
B
other BH
two-fold dehydrocoupling
Li
2
3
1
0 f,g
AgOAc (20)
-
-/75/trace
-/76/trace
K
2
3
Results and Discussion
Synthesis of Carborano-coumarin. To evaluate the the
feasibility of the catalytic cascade dehydrocoupling reaction,
Li
2
3
1
1 f,g
80
K
2
3
a
Reaction conditions: 1a (0.10 mmol) and 2a (0.40 mmol) in 8.0 mL of
toluene in a closed flask; AgNTf
2
= silver bis(trifluoromethanesulfonyl)imide.
carboranyl carboxylic acid 1-COOH-2-CH
benzoic acid (2a) were employed as model coupling partners. With
the employment of 5 mol% [Cp*IrCl , 20 mol% AgOAc, 2.0 equiv
, heating 1a with 4.0 equiv of
3 2 10
-o-C B H10 (1a) and
b
c
d
Isolated yield. o-Xylene was used as solvent. Mesitylene was used as
e
f
g
2
solvent. 7.5 mol% [Cp*IrCl ] was used. Reaction time was 12 h. 2 equiv
of Cu(OPiv) was used
2
2 2
]
2
2
of Li
2
2
CO
3
and 5.0 equiv of Cu(OPiv)
o
a in toluene at 140 C for 15 h offered carborano-coumarin (3a)
We then examined the substrates scope under the optimized
reaction conditions (entry 3, Table 1). Such cascade
dehydrogenative cyclization was tolerant of a variety of functional
and B(4)-phenylated carborane (5a) in 30% and 10% yields
respectively (entry 1, Table 1). The use of 10 mol% AgOAc and 10
mol% AgNTf as united additives offered an improved yield of 39%
2
3 2 2
groups including –CF , –NO , –CO Me, –OMe, –F, –Cl, –Br and –I,
for 3a (entry 2, Table 1). Increasing the reaction temperature to
affording the desired products 3 in 49-99% isolated yields (Table 2).
Electron withdrawing groups on phenyl ring generally offered
higher yields with faster reaction rates, whereas substrates bearing
electron donating groups required higher catalyst loading to afford
comparable results (3a-i, 3m vs 3j-l, 3n-p). Steric effects were
observed when the methyl group on phenyl ring was changed from
para- to meta- to ortho-position, leading to the isolated yields of 3
from 76% to 57% to 46%. Naphthoic acid generated the cyclic
product 3q in 57% isolated yield.
o
1
60 C improved the yield of 3a to 69% (entry 3, Table 1). Screening
of other solvents did not give better results (entry 4 and 5, Table
). Finally, increasing the catalyst loading to 7.5 mol% afforded 3a
in 77% isolated yield (entry 6, Table 1). Surprisingly, the addition of
CO as a co-base was found to suppress efficiently the second B-
1
K
2
3
H/O-H coupling step (entries 7 and 8, Table 1), such that the
reaction was stopped at the B-H/C-H dehydrocoupling stage. Using
2
0 mol% AgOAc as the sole additive gave 5a in 86% isolate yield
(
entey 9, Table 1). On the other hand, α-carboranyl benzoic acid
(
4a) was isolated in 76% yield by decreasing the reaction
Table 2 Synthesis of carborano-coumarinsa
o
temperature to 80 C (entries 10 and 11, Table 1).
Ar
H
O
OH
(5
mol%)
Table 1 Optimization of reaction conditions using benzoic acida
[Cp*IrCl
2
]
2
AgNTf (10 mol%)
AgOAc (10 mol%)
Li CO3 (2.0 equiv)
O
+
COOH
H
Ar
O
H
2
H
O
OH
COOH
]2,
O
Cu(OPiv)
PhMe, 15h, 160 C
2
(5.0 equiv)
5
mol% [Cp*IrCl
additive, base
.0 equiv Cu(OPiv)
Toluene, temp., 15 h
2
o
+
H
O
+
+
1
2
3
H
COOH
H
H
H
5
2
R
=
H, 69%, 77%b 3a Br, 97% 3g
F
R
(
)
(
(
)
1a
2a
3a
4a
5a
CF , 79% 3b
77% 3h
3
(
)
I,
)
F
COOMe, 91% (3c) Ph, 97% (3i)
Me, 76%b 3j
NO , 49% (3d)
O
2
(
)
O
6
3% (3e)
tBu, 91%b 3k
O
O
H
F,
( )
H
OMe, 50%b (3l)
Cl, 62% (3f)
3a/4a/5ab
Additive
mol %)
AgOAc (20) Li
Temp.
(oC)
3
h
3m, 99%
Entry
Base
(
(%)
O
1
2
2
CO
3
3
(2.0)
(2.0)
140
30/-/10
O
AgNTf
AgOAc (10)
AgNTf (10)
AgOAc (10)
AgNTf (10)
AgOAc (10)
2
(10)
O
O
O
O
O
Li
Li
Li
2
CO
140
39/-/-
O
H
H
O
H
O
H
2
3
2
CO
3
3
(2.0)
(2.0)
160
160
69/-/-
28/-/-
3n, 57%
b
3o, 46%b
3p, 93%b
3q, 57%
2
4c
CO
2
a
Reactions were conducted at 0.10 mmol scale in 8 mL of toluene in a closed
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Running title
Chin. J. Chem.
flask, 4 equiv. of benzoic acid was added, and the yields were those of the
isolated products. Reactions were carried out under the conditions shown
in entry 6, Table 1.
Table 3 Synthesis of B(4)–arylated o-carboranesa
b
Ar
mol%)
equiv)
H
O
OH [Cp*IrCl
AgOAc (20 mol%)
2
]
2
(5 mol%)
Ar
[
Cp*IrCl
2
]
2
(5
COOH Li CO
2
3
(1.0
Li
2
CO
CO
Cu(OPiv)
3
(1.0 equiv)
K
2
CO
3
(1.0 equiv)
(2.0 equiv)
COOH +
Ar
K
2
3
(1.0 equiv)
(2.0 equiv)
o
H
Cu(OPiv)
2
H
Synthesis of B(4)-arylated o-Carboranes. As shown in Table 3,
a series of substituted benzoic acids were examined for the
preparation of B(4)-arylated o-carboranes 4 and 5. Compound 5
was generated from in-situ decarboxylation of 4. Under the
reaction conditions shown in entry 11, Table 1, treatment of 1a
with different benzoic acids afforded the B-H/C-H dehydrocoupling
products 4 in 71-79% isolated yields (4a-e, Table 3). No obvious
electronic effects were observed. On the other hand, increasing the
o
PhMe, 12h, 80 C
2
PhMe, 12h, 140 C
4
1
2
5
F
Cl
R
R
R
R = CO
H (4a), 76%
2
R = CO
H (4b), 72% R = CO
H (4c), 79%
2
2
= H (5b), 78%
=
H
5a 86%
5a
(
),
= H (5c), 90%
Br
I
o
reaction temperature to 140 C with the addition of 20 mol%
R
H
HO
2
C
AgOAc as the additive, allowed the facile synthesis of 5 in good to
excellent yields. Both electron-withdrawing and -donating groups
on phenyl ring worked well (5a-i, Table 3). Naphthalenyl carborane
R = CO
H (4d), 71%
5d 82%
2
=
H
4e, 71%
5e, 87%
4c
(
),
5
j was also obtained in 80% yield. It was noteworthy that such B-
OMe
H
OEt
H/C-H dehydrocoupling was tolerant of halo groups (4b-d & 5b-e),
which could be used for further functionalization.
H
H
H
H
Compounds 3, 4, and 5 were fully characterized by H, 13C, and
1
5f, 76%
5g, 82%
5h, 89%
5i, 72%
5j, 80%
11B
NMR spectroscopy as well as high-resolution mass
spectrometry (see the Supporting Information for detail). The
molecular structures of 3h, 4c, and 5a were further confirmed by
single-crystal X-ray analyses.
a
[15]
Reactions were conducted at 0.10 mmol scale in 4 mL of toluene in a
closed flask, 4 equiv of benzoic acid was added, and the yields were those
of the isolated products.
Mechanistic Study. The above experimental results indicated
that: (1) B-H/C-H dehydrocoupling occured preferentially over B-
H/O-H dehydrocoupling; (2) decarboxylation of carboranyl
carboxylic acid proceeded before that of benzoic acid. To gain
more mechanistic insight into the dehydrogenative cross-couplings,
several control experiments were carried out. Addition of 1 equiv
of ethyl acrylate to the reaction mixture illustrated in entry 3, Table
deuterium-labeling experiments, which indicated that aryl C-H
activation might be involved in the rate-determining step (Scheme
2
iridacycle, 2-CH
2 6 4
Cp*Ir(DMSO)(O CC H ) (B’’),
b). Two possible intermediates featuring a five-membered
[
10a]
3
-1,4-[C(O)OCp*Ir(DMSO)]-o-C
2
B
10
H
9
(B’)
and
[
17]
were prepared according to
literature methods. Both of them could catalyze the cascade
dehydrogenative cyclization (Scheme 2c). Treatment of B’ with 4
equiv of benzoic acid under the standard cyclization conditions
gave 3a in 81% GC yield, whereas no coupling product was
1
6
afforded cage B-H and phenyl C-H functionalized products 6a and
b in 82% and 18% GC yields,[16] without the formation of 3a
(
Scheme 2a), suggesting that carboranyl B-H activation might
proceed faster than that of phenyl C-H bond under the reaction
conditions. A KIE value of k /k = 3.1 was measured from
observed in the absence of Cu(OPiv)
2 2
. The importance of Cu(OPiv)
H
D
was further proved by the experimental results shown in Scheme
[18]
2d.
2
Employing Cu(OPiv) as the sole additive resulted in the
formation of 3a and 5a in 51% and 14% yields, whereas Cu(OAc)
2
or AgOPiv could only give 5a as the coupling product. On the other
hand, heating 4a under the standard cyclization conditions led to
3
3
a and 5a in 8% and 92% GC yields. However, 4a-COOH produced
a quantitatively under the same conditions, which illustrated the
crucial role of –COOH at cage C(1) in the cascade cyclization with
benzoic acid (Scheme 2e). In other words, the second-step cage B-
O coupling was also induced by carboxyl group guided B-H
metalation, which is different from the reported B-N coupling
reaction.
On the basis of the aforementioned experimental results and
[9]
[8d,9,18]
literature reports,
a plausible reaction pathway is proposed
in Scheme 3. Acid-base reaction, followed by regioselective
[
10a]
electrophilic metalation of B(4)-H gives an intermediate B.
[9]
Oxidation of B by copper salts offers an Ir(V)-intermediate C,
which undergoes ligand exchange to afford D. Subsequent
electrophilic C-H metalation produces intermediate E. A sequence
Chin. J. Chem. 2019, 37, XXX－XXX
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First author et al.
Scheme 2 Control experiments for dehydrocoupling of o-carborane with benzoic acid
O
O
H
Et
2 2
]
(5
mol%)
Et
O
[
Cp*IrCl
AgNTf
O
H
O
OH
(10 mol%)
mol%)
2
O
O
D
H
O
AgOAc (10
+
(a)
H
COOH
+
+
Et
Li CO3 (2.0 equiv)
2
O
Cu(OPiv)
2
(5.0 equiv)
1
4.0 equiv 2a 1.0 equiv
o
PhMe, 15h, 160 C
6
a, 82%
6b, 18%
Standard Condition
D
(
60/40)
O
OH
H/D
D
H
O
OH
+
D
D
D
O
O
H +
(
b)
c)
Standard Condition
0 min
k /k =3.1
+
COOH
H
2
O
O
O
H
D
H
D
1
D
3
a/3a-d, 20%
2
.0 equiv 2a 2.0 equiv 2a-d5
B'
mol%)
Standard Condition
B''
(10
mol%)
Standard Condition
(10
1
+ 2a
+
O
(
O
H
Cp*
O
H
Cp*
O
H
OSMD
Ir
O
OSMD
Ir
3a, 75%
O
O
3a, 65%
5a, 11%
B'
B''
Cp*
OSMD
O
OH
Standard Condition
Standard Condition
Ir
O
3a
(d)
(81%)
O
+
H
Without Cu(OPiv)
No
3a
3a
3a
was detected
2
coupling product
(51%)
(trace)
5
5
5
.0 equiv Cu(OPiv)
+ 5a
+ 5a
+ 5a
2
(14%)
(50%)
(30%)
.0 equiv Cu(OAc)
.0 equiv AgOPiv
B'
2a
2
(trace)
COOH
Standard Condition
R=COOH
Standard Condition
R=H
(e) 3a
3a
+ 5a
(92%)
(100%)
(8%)
R
4
a or 4a-COOH
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Running title
Chin. J. Chem.
Scheme 3 Proposed reaction mechanism
Cp*
HY
*
Cp OPiv
IrIII
O
Y
H
Cp*
IrIII
Ar
IrIII
O
III
Ir Cl ]
2 2
O
Cu(OPiv)
PivO
2
[
Cp*
O
PivO Cp*
O
O
O
R
IrV
AgY
O
O
O
R
3+CO2
O
R
B
A
CuOPiv
Cp*
O
J
HY
1
Ar
O
PivO IrV
HY
R
III
I
Cp*
HY
Ir Y
2
O
R
PivOH
4
or 5 + CO2
C
OPiv
O
PivO
Cp*
PivOH
IrV
2
COOH
O
O
Cp*
IrIII
Ar
O
O
O
PivO Cp*
*
Cp
Ar
CuOPiv
O
IrV
IrIII
O
IrV
O
R
COOH
Cp*
Ar
O
O
O
Ar
H
R
O
F
O
Ar
O
R
R
O
Cu(OPiv)
2
D
R
PivOH
G
-
-
-
E
Y = OAc or NTf or OPiv
2
of reductive elimination, protonation and decarboxylation occurs
to generate 4 or 5 and reproduce Ir(III) catalyst. Alternatively, in the
presence of carboxyl directing group at C(1), further electrophilic
attack of Ir(III) at B(5)-H gives intermediate G. Similar oxidation and
ligand exchange afford the Ir(V)-intermediate I, which undergoes
reductive elimination, protonation and decarboxylation to
genenrate 3 and reactive Ir(III)-catalyst. It is noted that although an
Ir(V) catalytic cycle is prefered on the basis of previous literature
Experimental
Representative procedure for preparation of carborano-coumarin
derivatives 3
1
-COOH-o-carborane (1) (0.10 mmol), benzoic acid (2) (4.0
equiv, 0.40 mmol), [Cp*IrCl (5 mol%, 0.005 mmol or 7.5 mol%,
.0075 mmol), AgNTf (10 mol%, 0.01 mmol or 15 mol%, 0.015
mmol), AgOAc (10 mol%, 0.01 mmol or 15 mol%, 0.015 mmol),
Li CO (2.0 equiv, 0.20 mmol) and Cu(OPiv) (5.0 equiv, 0.50 mmol)
2 2
]
0
2
[9]
report, the involvement of Ir(IV)-species recently reported by the
[18a]
Chang group cannot be completely excluded.
2
3
2
were mixed in dry toluene (8 mL) in a closable flask. The flask was
closed and heated at 160 C for 15 h under Ar atmosphere. The
resulting reaction mixture was filtered and washed with diethyl
ether. The organic portions were washed with saturated sodium
2 4
carbonate, and dried over Na SO . After removal of the solvent
under vacuum, the residue was then subjected to column
chromatography on silica gel (230-400 mesh) using n-hexane and
ethyl acetate (10/1 in v/v) as eluent to give the products 3.
o
Conclusions
In summary, a regioselective and efficient Ir-catalyzed cascade
B-H/C-H and B-H/O-H dehydrogenative cross-coupling has been
achieved, resulting in the facile synthesis of unprecedented
carborano-coumarin derivatives from readily available carboranyl
carboxylic acid with benzoic acid in a simple one-pot process. By
tuning reaction conditions, a series of B(4)-arylated o-carboranes
were also selectively prepared, indicating that B-H/C-H
dehydrocoupling happened preferentially over B-H/O-H
dehydrocoupling. Moreover, the results of control experiments
proved that both oxidants and the traceless directing group -COOH
were essential for the cascade cyclization. This work not only
provides a tunable platform for the synthesis of a large collection
of functionalized carborane derivatives, which are otherwise
unavailable or quite difficult to be prepared, but also provides
valuable reference on the control of regioselectivity and
chemoselectivity in cascade dehydrogenative cross-coupling
reactions.
Representative procedure for preparation of 4-(2’-benzoic acid)-
o-carboranes 4
1-COOH-o-carborane (1; 0.10 mmol), benzoic acid (2; 4.0 equiv,
0.40 mmol), [Cp*IrCl (1.0 equiv,
2
]
2
(5 mol%, 0.005 mmol), Li
2
CO
3
0.10 mmol), K CO (1.0 equiv. 0.10 mmol) and Cu(OPiv) (2.0 equiv,
2
3
2
0.20 mmol) were mixed in dry toluene (4 mL) in a flask. The flask
was closed and heated at 80 C for 12 h under Ar atmosphere. The
resultant solution was filtered and washed with diethyl ether. The
organic portions were combined and washed with diluted
hydrochloric acid. After removal of the solvents under vacuum, the
residue was then subjected to column chromatography on silica gel
o
(
230-400 mesh) using n-hexane/ethyl acetate (7/1 in v/v) and then
n-hexane/ethyl acetate/acetic acid (60/20/1 in v/v/v) as eluent to
afford the products 4.
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
This article is protected by copyright. All rights reserved.

Report
First author et al.
Lovera, S. O.; Kleinsasser, J. F.; Guo, J.; Asay, M. J.; Nelson, H. M.;
Lavallo, V. Nonclassical Applications of closo-Carborane Anions: From
Main Group Chemistry and Catalysis to Energy Storage. Chem. Rev.
2019, 119, 8262—8290.
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Representative procedure for preparation of 4-aryl-o-carboranes
5
1
-COOH-o-carborane (1; 0.10 mmol), benzoic acid (2; 4.0 equiv,
.40 mmol), [Cp*IrCl (5 mol%, 0.005 mmol), AgOAc (20%, 0.02
(1.0 equiv, 0.10 mmol). K CO (1.0 equiv. 0.10 mmol)
0
2
]
2
mmol), Li
and Cu(OPiv)
2
CO
3
2
2
3
(2.0 equiv, 0.20 mmol) were mixed in dry toluene (4
o
mL) in a closable flask. The flask was closed and heated at 140 C
for 12 h under Ar atmosphere. The resultant solution was filtered
and washed with diethyl ether. The organic portions were
combined and washed with diluted hydrochloric acid. After
removal of the solvents under vacuum, the residue was then
subjected to column chromatography on silica gel (230-400 mesh)
using n-hexane/ethyl acetate (100/1 in v/v) as eluent to give the
products 5.
S. Synthesis and Properties of Carborane-Appended C -Symmetrical
3
Extended π Systems. J. Am. Chem. Soc. 2010, 132, 6578—6587. (d)
Kung, C.-W.; Otake, K.; Buru, C. T.; Goswami, S.; Cui, Y.; Hupp, J. T.;
Spokoyny, A. M.; Farha, O. K. Increased Electrical Conductivity in a
Mesoporous Metal–Organic Framework Featuring Metallacarboranes
Guests. J. Am. Chem. Soc. 2018, 140, 3871—3875. (e) Villagómez, C. J.;
Sasaki, T.; Tour, J. M.; Grill, L. Bottom-up Assembly of Molecular
Wagons on a Surface. J. Am. Chem. Soc. 2010, 132, 16848—16854. (f)
Qian, E. Q.; Wixtrom, A. I.; Axtell, J. C.; Saebi, A.; Rehak, P.; Han, Y.;
Moully, E. H.; Mosallaei, D.; Chow, S.; Messina, M.; Wang, J.-Y.;
Royappa, A. T.; Rheingold, A. L.; Maynard, H. D.; Kral, P.; Spokoyny, A.
M. Atomically Precise Organomimetic Cluster Nanomolecules
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
Acknowledgement
This work was supported by grants from the Research Grants
Council of The Hong Kong Special Administration Region (Project
Nos. 14305017, 14305018 and 14305918) and Direct Grant from
Faculty of Science, CUHK.
Assembled via Perfluoroaryl-thiol S
N
Ar Chemistry. Nat. Chem. 2017, 9,
3
33—340. (g) Saha, A.; Oleshkevich, E.; Viñas, C.; Teixidor, F.
Biomimetic Inspired Core–Canopy Quantum Dots: Ions Trapped in
Voids Induce Kinetic Fluorescence Switching. Adv. Mater. 2017, 29,
Conflict of interest
1
704238. (h) Guo, J.; Liu, D.; Zhang, J.; Zhang, J.; Miao, Q.; Xie, Z. o-
The authors declare no conflict of interest.
Carborane Functionalized Pentacenes: Synthesis, Molecular Packing
and Ambipolar Organic Thin-Film Transistors. Chem. Commun. 2015,
5
1, 12004—12007. (i) Jung, D.; Saleh, L. M. A.; Berkson, Z. J.; El-Kady,
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This article is protected by copyright. All rights reserved.

Running title
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(
The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
(a) Engle, K. M.; Mei, T.-S.; Wasa, M.; Yu, J.-Q. Weak Coordination as a
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Chin. J. Chem. 2019, 37, XXX－XXX
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Entry for the Table of Contents
H
O
H
Ar
Page No.
O
One-pot process to carborano-coumarin via
catalytic cascade dehydrogenative cross-
coupling
cat. [Ir]
oxidant
+
H
O
H
COOH
Ar
O
H
B-C
B-C coupling
coupling
COOH
=
R 1
coupling
Ar
Ar
B-O
O
O
C
B
BH
other
H
H
H
R1
Ir-catalyzed cascade dehydrogenative CH/BH and BH/OH cross-coupling of carboranyl carboxylic
acid with readily available benzoic acid has been achieved, leading to the facile synthesis of
previously unavailable carborano-coumarin in a simple one-pot process, in which two B-H, one C-H
and one O-H bonds are broken, while two new B-C and B-O bonds are formed.
Yik Ki Au, Hairong Lyu, Yangjian Quan,* Zuowei
Xie*
a
c
Department, Institution, Address 1
Department, Institution, Address 3
E-mail:
E-mail:
b
Department, Institution, Address 2
E-mail:
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