Light-promoted copper-catalyzed cage C-Arylation of: O-carboranes: facile synthesis of 1-Aryl-o-carboranes and o-carborane-fused cyclics

Article abstract of DOI:10.1039/d0nj02029j

Light-promoted, copper catalyzed cage C-H arylation of o-carboranes with aryl halides has been achieved, leading to the facile synthesis of a variety of 1-Aryl-o-carboranes and o-carborane-fused cyclics. This method has the following features: (1) using o

Full text of DOI:10.1039/d0nj02029j

View Article Online
View Journal
NJC
New Journal of Chemistry
Accepted Manuscript
A journal for new directions in chemistry
This article can be cited before page numbers have been issued, to do this please use: H. Ni, Z. Lu and Z.
Xie, New J. Chem., 2020, DOI: 10.1039/D0NJ02029J.
Volume 42
This is an Accepted Manuscript, which has been through the
Number
6
21 March 2018
Pages 3963-4776
Royal Society of Chemistry peer review process and has been
accepted for publication.
NJC
New Journal of Chemistry
rsc.li/njc
A journal for new directions in chemistry
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1144-2546
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
rsc.li/njc

Please do not adjust margins
New Journal of Chemistry
Page 1 of 6
1
2
3
4
5
6
7
View Article Online
DOI: 10.1039/D0NJ02029J
ARTICLE
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Light-Promoted Copper-Catalyzed Cage C-Arylation of o-
Carboranes: Facile Synthesis of 1-Aryl-o-Carborane and o-
Carborane-Fused Cyclics†
Received 00th January 20xx,
Accepted 00th January 20xx
Hangcheng Ni, Zhenpin Lu and Zuowei Xie*
DOI: 10.1039/x0xx00000x
Light-promoted copper catalyzed cage C-H arylation of o-carboranes with aryl halides has been achieved, leading to the
facile synthesis of a variety of 1-aryl-o-carboranes and o-carborane-fused cyclics. This method has the following features: 1)
using o-carboranes instead of prefunctionized iodocarboranes as starting materials; 2) employing earth abundant copper as
catalyst; and 3) room-temperature reaction. Control experiments suggest that the reaction proceeds via Cu-catalyzed radical
coupling.
induced copper-catalyzed synthetic method for the synthesis of
1-aryl-o-carboranes. This method is developed by merging
photochemistry with base metal catalysis, which has the
following features: 1) using o-carboranes instead of
prefunctionalized iodocarboranes as starting materials; 2)
employing earth abundant copper as catalyst; and 3) room-
temperature reaction (Scheme 1).
Introduction
The study of icosahedral carboranes, boron-carbon molecular
clusters, has been a topic of great interest in recent years.1 The
unique electronic property, thermal/chemical stabilities and
three-dimensional structure of these molecules, have led to a
variety of applications in medicine as boron neuron capture
therapy agents,2 in supramolecular design/materials as
functional building blocks,3 and in organometallic/coordination
chemistry as valuable ligands.4 Among carborane derivatives,
aryl-o-carboranes are particularly attractive, as they exhibit
fascinating photophysical properties, which can be used as
luminescent materials.5 Several synthetic methods of cage C-
arylated o-carboranes have been developed in the past few
years. An early example was demonstrated from the
condensation reaction of hypertoxic decaborane with the
corresponding alkynes.6 Ullmann-type coupling reaction of 1-
Cu-o-carborane complex with nitrophenyl iodides was reported
to give 1-(O2NC6H4)-o-carboranes under refluxing condition in
low yields.7 Unfortunately, this reaction was not compatible
with other aryl iodides. Our group described a nickel-catalyzed
Kumada-type cross-coupling of 1-MgCl-o-carboranes with a
variety of aryl iodides for the preparation of 1-aryl-o-
carboranes.8 Later on, Lu’s group found that 1-aryl-o-
carboranes was also able to be prepared via Pd-catalyzed cross-
coupling of 1-Li-o-carboranes with aryl iodides.9 Very recently,
we disclosed
a UV light promoted photoarylation of
iodocarboranes with arenes for the synthesis of cage C-arylated
o-carboranes (Scheme 1).10 We report herein a new UV light-
Scheme 1. Cage carbon arylation of o-carboranes.
Department of Chemistry and State Key Laboratory of Synthetic Chemistry,
The Chinese University of Hong Kong, Shatin, N. T., Hong Kong (China).
E-mail: zxie@cuhk.edu.hk
† Dedicated to Professor Todd B. Marder for his contributions to chemistry.
Electronic Supplementary Information (ESI) available: experimental procedures,
characterization data and CIF file. See DOI: 10.1039/x0xx00000x
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 2 of 6
ARTICLE
Journal Name
1
2
3
4
5
6
7
8
9
Table 2. Synthesis of 1-aryl-o-carboranes.a,b
Results and discussion
View Article Online
DOI: 10.1039/D0NJ02029J
Direct irradiation of a DME solution of o-carborane (1a) and
iodobenzene (2a) under 8 W UV light (254 nm) at room
temperature in the presence of 15 mol% CuI and 2 equiv of
LiOtBu for 12 h gave the desired product 1-phenyl-o-carborane
(
3a) in 44% yield (entry 1 in Table 1). Screening a variety of
oxidants revealed that Ag2CO3 was the best one, affording 3a in
74% yield (entries 2-6, Table 1). Increasing the amount of
Ag2CO3 to 1.5 equiv improved the yield of 3a to 80% (entry 7 in
Table 1), which was further increased to 90% if 3 equiv of 2a
was employed (entry 8 in Table 1). On the other hand, no
obvious change in the yield of 3a was observed if the amount
of LiOtBu was reduced to 1.5 equiv (entry 9 in Table 1). Lowering
the catalyst loading to 10 mol% led to a considerable decrease
in the yield of 3a (entry 10 in Table 1). No reaction was observed
in the absence of CuI or without UV irradiation (entries 11-12 in
Table 1). It was noted that a longer reaction time (24 h) was
required if the reaction scale was enlarged by 3 times to 0.3
mmol (entry 13 vs 14 in Table 1). In addition, both
bromobenzene and chlorobenzene were compatible with this
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 1. Optimization of reaction conditions.a
additive
[equiv]
-
2a
[equiv ]
2.0
LiOtBu
[equiv]
2.0
yield
(%)b
44
entry
a All reactions were conducted on 0.3 mmol scale of
1 in 3.0 mL
1
2
tBuOOtBu (1.0) 2.0
2.0
40
of DME in a closed flask for 24 h at room temperature under an
irradiation of 8 W UV lamp. b Isolated yields. c Recovered yields
of starting materials.
3
4
5
6
7
8
9
10c
11d
12e
13f
14f,g
O2
2.0
2.0
2.0
2.0
2.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
2.0
2.0
2.0
2.0
2.0
2.0
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
trace
74
46
31
80
90
91
80
trace
trace
73
88(83)
75(62)
69(59)
Ag2CO3 (1.0)
Ag2O (1.0)
AgNO3 (2.0)
Ag2CO3 (1.5)
Ag2CO3 (1.5)
Ag2CO3 (1.5)
Ag2CO3 (1.5)
Ag2CO3 (1.0)
Ag2CO3 (1.5)
Ag2CO3 (1.5)
Ag2CO3 (1.5)
reaction, offering 3a in the reduced yields of 75% and 69%,
respectively (entries 15-16 in Table 1).
Under the optimal reaction conditions (entry 14, Table 1),
the substrate scope was examined, and results were
summarized in Table 2. In general, the reaction proceeded well
to give the desired products in very good yields. It was tolerant
of many functional groups such as OMe, OCF3, SMe, Cl, F, CF3,
and CN. The electronic nature of substituents on the phenyl ring
did not have much effect on the reaction efficiency (3a-3r).
15f,g,h Ag2CO3 (1.5)
16f,g,i Ag2CO3 (1.5)
H o w e v e r , h i g h l y e l e c t r o n - d e f i c i e n t 3 , 5 -
bis(trifluoromethyl)iodobenzene gave the product 3s in 37%
yield. Iodonaphthalene and iodophenanthrene worked well to
a
Reaction conditions: 1a (0.1 mmol), 1,2-dimethoxyethane
afford the corresponding products 3t, 3u and 3v in 40-73%
(DME, 1.0 mL), CuI (0.015 mmol, 15 mol%), 8 W UV (254 nm),
b
12 h. 1H NMR yield using CH2Br2 as an internal standard; in
yields. On the other hand, 2-iodothiophene offered the desired
product 3w in only 15% yield with the recovery of 70% starting
material 1a, due probably to the interaction of Cu with the S
atom. It was noteworthy that this reaction was very sensitive to
the substituents on another cage carbon. For example, 1-
methyl-o-carborane gave the corresponding product 3x in 20%
yield; and no reaction was observed for 1-phenyl-o-
c
d
parentheses isolated yields. 10 mol% CuI used. Reaction
e
f
without CuI.
Reaction without irradiation.
Reaction
conditions: 1a (0.3 mmol), DME (3.0 mL), CuI (0.045 mmol, 15
g
h
mol%), 8 W UV (254 nm), 12 h. Reaction time 24 h.
i
Bromobenzene as the substrate instead of iodobenzene.
Chlorobenzene as the substrate instead of iodobenzene.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
New Journal of Chemistry
Please do not adjust margins
Journal Name
Table 3. Synthesis of o-carborane-fused cyclics.a,b
ARTICLE
1
2
3
4
View Article Online
DOI: 10.1039/D0NJ02029J
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 2. Control experiments.
a All reactions were conducted on 0.3 mmol scale of
1 in 3.0 mL
of DME in a closed flask for 24 h at room temperature under the
irradiation of 8 W UV lamp. b Isolated yields.
carborane.7,11 In contrast, cage boron substituted o-carborane,
9,12-Me2-o-carborane, afforded the desired product 3y in 76%
yield.
Having achieved the intermolecular cage C-monoarylation
of o-carborane with aryl iodides, we then evaluated the
intramolecular arylation/cyclization reaction of
results were compiled in Table 3. It was found that both o-
carborane-fused five- and six-membered ring compounds 4a 4d
could be prepared in low yields (20-57%). The reason why six-
membered ring compounds 4c 4d were isolated in much lower
1, and the
-
,
yields (20-29%) was likely due to the formation of unfavorable
seven-membered Cu intermediate. The aforementioned results
indicated that this Cu-catalyzed arylation reaction is very
sensitive to steric effects.7.11
Scheme 3. Proposed reaction mechanism.
that the SET process ( ) may not be efficient. Thus, Ag2CO3
A
 B
is required to promote such process, driving the reaction to
completion. It is noted that Ag(I) salt serves as an oxidant in the
reaction, not a catalyst (entry 11 in Table 1).
To gain some insight into the reaction mechanism, the
following control experiments were conducted (Scheme 2).
Replacement of CuI with CuCl2 under the standard reaction
conditions afforded 3a in 90% GC yield. In the absence of
Ag2CO3, however, the yield of 3a was dropped to 41%, which
was comparable to that of CuI (entry 1 in Table 1). These results
suggested that both Cu(I) and Cu(II) salts played the same role
in the reaction. On the other hand, addition of the radical
scavenger TEMPO (2,2,6,6-Tetramethylpiperidine 1-oxyl)
resulted in significant inhibition of the reaction, suggesting that
radicals may be involved in the reaction. In fact, it has been
documented that aryl radical can be generated either via single
electron transfer from Cu(I) complex to aryl halide12 or
homolytic C-I bond cleavage under UV light irradiation.10,13
On the basis of the control experiments and literature
reports,12-18 a possible mechanism was proposed in Scheme 3.
Conclusions
In summary, by merging photochemistry with base metal
catalysis, a light-promoted Cu catalyzed cage C-arylation of o-
carboranes with a variety of aryl iodides at room temperature
has been developed, leading to the preparation of a variety of
1-aryl-o-carboranes
and
o-carborane-fused
cyclics.
Employment of earth abundant copper as catalyst, this method
also demonstrates the advantages of using simple o-carboranes
as starting material, not prefunctionalized iodocarboranes, and
mild reaction condition under room temperature. Further
control experiments suggest that the reaction undergoes a
radical pathway facilitated by Cu catalyst. This work offers some
hints for the development of radical-based methods for the
functionalization of carboranes and boron clusters.
Reaction of o-carborane with CuI in the presence of LiOtBu gives
7,11
a Cu(I)-o-carborane complex
(SET) from
complex
A
.
Single-electron-transfer
A
to ArI under UV irradiation generates a Cu(II)
and aryl radical.15 Alternatively, oxidation of
by
, and homolytic C-I
B
A
Ag(I) salt also yields a Cu(II) complex
B
cleavage under UV irradiation produces aryl radicals.18a
Experimental
Coupling between the Cu(II)-o-carborane complex with aryl
radical gives the desired coupling product
3 and releases the
General experimental information
C u ( I ) c a t a l y s t . I t i s a s s u m e d
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 4 of 6
ARTICLE
Journal Name
1
2
3
4
5
6
7
8
9
Schwartz, A. M. Mendoza, N. Wattanatorn, Y. Zhao, V. T.
All reactions were carried out in flame-dried glassware under an
atmosphere of dry argon with the rigid exclusion of air and
moisture using standard Schlenk techniques or in a glovebox.
All chemicals were purchased from commercial corporations
and used as received unless otherwise specified.
View Article Online
Nguyen, A. M. Spokoyny, C. A. Mirkin, T. Baše and P. S. Weiss,
DOI: 10.1039/D0NJ02029J
J. Am. Chem. Soc. 2016, 138, 5957; (h) S. G. McArthur, L. Geng,
J. Guo and V. Lavallo, Inorg. Chem. Front. 2015, 2, 1101; (i) D.
J. Clingerman, W. Morris, J. E. Mondloch, R. D. Kennedy, A. A.
Sarjeant, C. Stern, J. T. Hupp, O. K. Farha and C. A. Mirkin,
Chem. Commun. 2015, 51, 6521.
4
(a) N. S. Hosmane and J. A. Maguire in Comprehensive
Organometallic Chemistry III, Vol. 3 (Eds.: R. H. Crabtree, D. M.
P. Mingos), Elsevier, Oxford, 2007, Chapter 5; (b) Z. Xie, Coord.
General experimental procedure for the synthesis of 1-Aryl-o-
carboranes 3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chem. Rev. 2002, 231, 23; (c) Z. Xie, Acc. Chem. Res. 2003, 36
,
o-Carborane (1; 43.2 mg, 0.30 mmol), aryl iodide (pre-dried with
1; (d) A. M. Spokoyny, C. W. Machan, D. J. Clingerman, M. S.
Rosen, M. J. Wiester, R. D. Kennedy, C. L. Stern, A. A. Sarjeant
molecular sieves, 0.90 mmol), LiOtBu (36.0 mg, 0.45 mmol),
Ag2CO3 (126.0 mg, 0.45 mmol) and CuI (8.4 mg, 0.045 mmol)
were mixed in dry DME (3 mL) in a 10 mL quartz tube equipped
with a magnetic stirring bar. The reaction mixture was
irradiated with 8 W UV lamp (254 nm) and stirred at room
temperature for 24 h. After quenching with aqueous acetyl acid
solution, the mixture was extracted with diethyl ether (15 mL ×
3). The ether solutions were combined and dried over Na2SO4.
After filtration, the clear solution was concentrated to dryness
in vacuo. The residue was subjected to flash column
chromatography on silica gel (230-400 mesh) using n-hexane as
and C. A. Mirkin, Nat. Chem. 2011,
3, 590; (e) C. A. Lugo, C. E.
Moore, A. L. Rheingold and V. Lavallo, Inorg. Chem. 2015, 54
,
2094; (f) L. M. A. Saleh, R. M. Dziedzic, S. I. Khan and A. M.
Spokoyny, Chem. Eur. J. 2016, 22, 8466.
5
(a) K. Kenta and C. Yoshiki, J. Org. Chem., 2011, 76, 316; (b) M.
Tominaga, H. Naito, Y. Morisaki and Y. Chujo, New J. Chem.
2014, 38, 5686; (c) K. R. Wee, W. S. Han, D. W. Cho, S. Kwon,
C. Pac and S. O. Kang, Angew. Chem. Int. Ed. 2012, 51, 2677;
Angew. Chem. 2012, 124, 2731; (d) K. R. Wee, Y. J. Cho, S.
Jeong, S. Kwon, J. D. Lee, I. H. Suh and S. O. Kang, J. Am. Chem.
Soc. 2012, 134, 17982; (e) A. Ferrer–Ugalde, E. J. Juárez–
Pérez, F. Teixidor, C. Vañas, R. Sillanpää, E. Pérez-Inestrosa
and R. Núñez. Chem. Eur. J. 2012, 18, 544; (f) K. R. Wee, Y. J.
eluent to give the desired products 3.
Cho, J. K. Song and S. O. Kang, Angew. Chem. Int. Ed. 2013, 52
,
9682; Angew. Chem. 2013, 125, 9864; (g) C. Shi, H. Sun, X.
Tang, H. Lv, H. Yan, Q. Zhao, J. Wang and W. Huang, Angew.
Conflicts of interest
There are no conflicts to declare.
Chem. Int. Ed. 2013, 52, 13434; Angew. Chem. 2013, 125
,
13676; (h) C. Shi, H. Sun, Q. Jiang, Q. Zhao, J. Wang, W. Huang
and H. Yan, Chem. Commun. 2013, 49, 4746; (i) H. J. Bae, J.
Chung, H. Kim, J. Park, K. M. Lee, T-W. Koh, Y. S. Lee, S. Yoo, Y.
Do and M. H. Lee, Inorg. Chem. 2014, 53, 128; (j) H. Naito, Y.
Morisaki and Y. Chujo, Angew. Chem. Int. Ed. 2015, 54, 5084;
Angew. Chem. 2015, 127, 5173; (k) A. Ferrer–Ugalde, A.
González–Campo, J. Rodríguez–Romero, R. Santillan, N.
Acknowledgements
This work was supported by grants from the Research Grants
Council of HKSAR (Project No. 14306519) and Direct Grant from
the Research Committee, CUHK.
Farfán, R. Sillanpää and F. Teixidor, Chem. Eur. J. 2014, 20
9940; (l) K. O. Kirlikovali, J. C. Axtell, A. Gonzalez, A. C. Phung,
S. I. Khan and A. M. Spokoyny, Chem. Sci. 2016, , 5132; (m)
,
7
X. Wei, M.-J. Zhu, Z. Cheng, M. Lee, H. Yan, C. Lu and J.-J. Xu,
Angew. Chem. Int. Ed. 2019, 58, 3162; Angew. Chem. 2019,
131, 3194.
Notes and references
1
For selected reviews, see: (a) R. N. Grimes, Carboranes, 2nd
ed.; Elsevier: Oxford, 2011; (b) N. S. Hosmane, Boron Science:
6
(a) T. L. Heying, J. W. Ager. Jr., S. L. Clark, D. J. Mangold, H. L.
Goldstein, M. Hillman, R. J. Polak and J. W. Szymanski, Inorg.
Chem. 1963, 2, 1089; (b) U. Kusari, Y. Li, M. G. Bradley and L.
G. Sneddon, J. Am. Chem. Soc. 2004, 126, 8662; (c) Y. Li, P. J.
Carroll and L. G. Sneddon, Inorg. Chem. 2008, 47, 9193; (d) M.
E. El-Zaria, K. Keskar, A. R. Genady, J. A. Ioppolo, J. McNulty
and J. F. Valliant, Angew. Chem. Int. Ed. 2014, 53, 5156;
Angew. Chem. 2014, 126, 5256.
R. Coult, M. A. Fox, W. R. Gill, P. L. Herbertson and K. Wade, J.
Organomet. Chem. 1993, 462, 19.
C. Tang and Z. Xie, Angew. Chem. Int. Ed. 2015, 54, 7662;
Angew. Chem. 2015, 127, 7772.
J.-Y. Lu, H. Wan, J. Zhang, Z. Wang, Y. Li, Y. Du, C. Li, Z.-T. Liu,
Z.-W. Liu and J. Lu, Chem. Eur. J. 2016, 22, 17542.
New Technologies and Applications; Taylor
& Francis
Books/CRC: Boca Raton, FL, 2011; (c) Z. Qiu, Tetrahedron Lett.
2015, 56, 963; (d) D. Olid, R. Núñez, C. Viñas and F. Teixidor,
Chem. Soc. Rev. 2013, 42, 3318; (e) M. Scholz and E. Hey-
Hawkins, Chem. Rev. 2011, 111, 7035.
For selected reviews, see: (a) M. F. Hawthorne, Angew. Chem.
Int. Ed. 1993, 32, 950; Angew. Chem. 1993, 105, 997; (b) A. F.
Armstrong and J. F. Valliant, Dalton Trans. 2007, 4240; (c) F.
2
3
7
8
9
Issa, M. Kassiou and L. M. Rendina, Chem. Rev. 2011, 111
5701.
,
For selected examples, see: (a) H. Jude, H. Disteldorf, S.
Fischer, T. Wedge, A. M. Hawkridge, A. M. Arif, M. F.
Hawthorne, D. C. Muddiman and P. J. Stang, J. Am. Chem. Soc.
2005, 127, 12131; (b) B. P. Dash, R. Satapathy, E. R. Gaillard, J.
10 H. Ni, Z. Qiu and Z. Xie, Angew. Chem. Int. Ed. 2017, 56, 712;
Angew. Chem. 2017, 129, 730.
A. Maguire and N. S. Hosmane, J. Am. Chem. Soc. 2010, 132
,
11 S. Ren and Z. Xie, Organometallics 2008, 27, 5167.
12 M. W. Johnson, K. I. Hannoun, Y. Tan, G. C. Fu and J. C. Peters,
6578; (c) M. Koshino, T. Tanaka, N. Solin, K. Suenaga, H. Isobe
and E. Nakamura, Science 2007, 316, 853; (d) D. Brusselle, P.
Bauduin, L. Girard, A. Zaulet, C. Viꢀas, F. Teixidor, I. Ly and O.
Diat, Angew. Chem. Int. Ed. 2013, 52, 12114; Angew. Chem.
2013, 125, 12336; (e) J. Guo, D. Liu, J. Zhang, J. Zhang, Q. Miao
and Z. Xie, Chem. Commun. 2015, 51, 12004; (f) O. K. Farha, A.
M. Spokoyny, K. L. Mulfort, M. F. Hawthorne, C. A. Mirkin and
J. T. Hupp, J. Am. Chem. Soc. 2007, 129, 12680; (g) J. J.
Chem. Sci. 2016,
13 (a) W. Wolf and N. Kharasch, J. Org. Chem. 1961, 26, 283; (b)
R. K. Sharma and N. Kharach, Angew. Chem. Int. Ed. 1968,
7, 4091.
7,
36; Angew. Chem. 1968, 80, 69; (c) T. Ho, C. Ku and S. H. Liu,
Tetrahedron Lett. 2001, 42, 715; (d) J. M. O’Connell, E.
Moriarty and F. Aldabbagh, Synthesis 2012, 44, 3371; (e) A. M.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
New Journal of Chemistry
Please do not adjust margins
Journal Name
ARTICLE
1
2
3
4
5
6
7
8
9
Linsenmeier, C. M. Williams and S. Bräse, Eur. J. Org. Chem.
View Article Online
DOI: 10.1039/D0NJ02029J
2013, 3847.
14 (a) C. Le, T. Q. Chen, T. Liang, P. Zhang and D. W. C. MacMillan,
Science 2018, 360, 1010; (b) Y. Liang, X. Zhang and D. W. C.
MacMillan, Nature 2018, 559, 83.
15 (a) Y. Tan, J. M. Munoz-Molina, G. C. Fu and J. C. Peters, Chem.
Sci. 2014, 5, 2831; (b) C. Uyeda, Y. Tan, G. C. Fu and J. C. Peters,
J. Am. Chem. Soc. 2013, 135, 9548; (c) D. Ziegler, J. Choi, J.
Muñoz-Molina, A. Bissember, J. C. Peters and G. C. Fu, J. Am.
Chem. Soc. 2013, 135, 13107; (d) S. E. Creutz, K. J. Lotito, G. C.
Fu and J. C. Peters, Science, 2012, 338, 647.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
16 Y. Ye and M. S. Sanford, J. Am. Chem. Soc. 2012, 134, 9034.
17 F. Yang, J. Koeller and L. Ackermann, Angew. Chem. Int. Ed.
2016, 55, 4759; Angew. Chem. 2016, 128, 4837.
18 (a) O. Daugulis, J. Roane and L. D. Tran, Acc. Chem. Res. 2015, 48,
1053; (b) L. D. Tran, J. Roane and O. Daugulis, Angew. Chem. Int.
Ed. 2013, 52, 6043; Angew. Chem. 2013, 125, 6159; (c) W.-H. Rao
and B.-F. Shi, Org. Chem. Front. 2016, 3, 1028.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

New Journal of Chemistry
Page 6 of 6
View Article Online
DOI: 10.1039/D0NJ02029J
1
2
3
4
For Table of Contents
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Ar
H
ArI
, cat. CuI, hv
LiOtBu/Ag2CO3
H
H
Copper
catalysis
29 Examples
Up to 83% yield
Light promoted
Non-functionalized S.M.
R.T. reaction
Light-promoted copper catalyzed cage C-H arylation of o-carboranes with aryl halides has been
achieved, leading to the facile synthesis of a variety of 1-aryl-o-carboranes and o-carborane-
fused cyclics.