Iridium-catalyzed, ligand-controlled directed alkynylation and alkenylation of arenes with terminal alkynes

Article abstract of DOI:10.1039/c9cc08735d

We report iridium-catalyzed C-C formation between benzamides and terminal alkynes. With the choice of a suitable ligand, a C-H alkynylation or alkenylation product could be obtained selectively. The directed C-H alkynylation proceeded without the need for an external oxidant, while the directed C-H alkenylation likely involves an unusual vinylidene mechanism. This divergent reactivity provides access to both alkynylation and alkenylation products from the same set of starting materials.

Full text of DOI:10.1039/c9cc08735d

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Sun, W. Zhao
and B. Li, Chem. Commun., 2020, DOI: 10.1039/C9CC08735D.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
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 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC08735D
COMMUNICATION
Iridium-catalyzed, ligand-controlled directed alkynylation and
alkenylation of arene with terminal alkyne
Xin Sun, a Wei Zhao a and Bi-Jie Li a*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
We report iridium-catalyzed C-C formation between benzamide C-H alkynylation product was obtained. When an electron-
and terminal alkyne. With the choice of a proper ligand, C-H deficient bisphosphine ligand was used, directed C-H
alkynylation or alkenylation product could be obtained selectively. alkenylation product was observed. External oxidant was not
The directed C-H alkynylation proceeded without the need for necessary in either cases. This ligand-controlled reactivity
external oxidant, while the directed C-H alkenylation likely involves enables the access to both alkynylation and alkenylation
an unusual vinylidene mechanism. This divergent reactivity provide products from the same set of starting material.
access to both alkynylation and alkenylation products from the
same set of starting material.
Scheme 1. Initial experiment.
nPr
NH
nPr
NH
nPr
O
Ir(COD)2OTf (10 mol%)
BINAP (12 mol%)
O
Alkynes are important structural units in many bioactive
compounds and material molecules.1 In addition, the alkyne
group can undergo many transformations to afford diverse
functionalized compounds.2 The Pd-catalyzed Sonogashira
coupling of aryl halide with terminal alkyne is one of the most
reliable methods to construct aryl alkynes.3 The recent
development of C-H alkynylation has provided an alternative
strategy to access aryl alkynes directly from arenes.4 For
example, directed C-H alkynylation of arenes containing various
coordinating groups have been developed using alkynyl
halides.5 In comparison, the direct dehydrogenative coupling
between arene and terminal alkyne is more desirable due to the
synthetic practicability and atom economy.6 However, an
external oxidant, usually a metal salt, is necessary in many cases,
thus producing undesired metal salt waste.7
We sought to develop an arene C-H alkynylation with
terminal alkyne where alkyne also functions as a hydrogen
acceptor. If successful, an external oxidant would not be
necessary. However, external-oxidant-free C-H alkynylation
with terminal alkyne is particularly rare.8,9 On the other hand,
the catalytic reaction of arene and alkyne could also afford C-H
alkenylation product.10 Although both aromatic C-H
alkynylation and C-H alkenylation with terminal alkyne have
been developed, a ligand-controlled reaction with switchable
reactivity remains underdeveloped.11
TIPS
O
NH
TIPS
+
CHCl3, 80 oC, 24 h
H
TIPS
Me
not observed
O
10% yield
Table 1. Reaction development.a
O
O
Ir(COD)2OTf (10 mol%)
Ligand (12 mol%)
TIPS
Me
Me
+
N
N
N
H
H
+
H
CHCl3, 80 oC, 24 h
H
H
TIPS
TIPS
1a
2a
3a
4a
MeO
MeO
PPh2
PPh2
MeO
MeO
PiPr2
PiPr2
PPh2
PPh2
L1
4a
L3
L2
4a
b
3a
3a
4a
31%,
<5%
92% (87%) ,
<5%
3a
12%,
<5%
OMe
CF3
OMe
OMe
Me
2
2
MeO
MeO
P
P
CF3
CF3
2
2
MeO
MeO
PPh2 MeO
PPh2 MeO
P
P
Me
Me
OMe
CF3
OMe
OMe
Me
L4
L5
4a
L6
c
3a
4a
3a
3a
4a
<5%, 79% (65%)
49%,
<5%
27%,
<5%
2a
a
1a
Reaction conditions:
(0.05 mmol, 1.0 equiv),
(3.0 equiv), Ir(COD)2OTf (10 mol%),
We report here an iridium-catalyzed reaction between
arene and terminal alkyne with ligand-controlled reactivity. In
the presence of an electron-rich bisphosphine ligand, directed
Ligand (12 mol%), CHCl3 (0.5 mL). Yields were determined by GC using n-dodecane as
an internal standard. Isolated yield in parenthesis. b 0.2 mmol. c 48 h.
During the investigation of catalytic hydroalkynylation of
cyclohexenyl carboxamide,12 we observed dehydrogenative
alkynylation of alkenyl C-H bond with terminal alkyne (Scheme
1). Thus, we further tested the directed C-H alkynylation of
benzamide (Table 1). Evaluation of various biaryl bisphosphine
a. Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua
University, Beijing, 100084, China. E-mail: bijieli@mail.tsinghua.edu.cn
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
Journal Name
ligands (L1-L3) indicated that electron-rich ligand significantly for a variety of substituted benzamides. Substituents located at
View Article Online
improved the yield of alkynylation product. Interestingly, the ortho, meta, and para-positions didDnOoI:t1h0.a10v3e9/aCs9iCgCn0if8i7c3a5nDt
further variation of the substituent on the Garphos ligand impact on the yield and selectivity (1a-1n), except compound 1b
revealed that the reaction pathway could be completely altered. which gave a low yield of alkenylation product. In general, the
In the presence of ligand L6, the C-H alkenylation product was yields of C-H alkenylation were lower than that of C-H
obtained exclusively. Thus, both C-H alkynylation and C-H alkynylation, due to the formation of unidentified side products.
alkenylation products can be selectively prepared by choice of Functional groups such as halide, ester and ketone were well
the ligand.
The substrate scope of the ligand-controlled reactions was
tolerated.
subsequently investigated (Table 2). Both reactions worked well
Table 2. Substrate scope of C-H alkynylation and alkenylation.a
O
O
+ L3
+ L6
Ir / (10 mol%)
O
H
Ir / (10 mol%)
Me
Me
Me
N
N
H
2a
2a
(3.0 equiv)
(3.0 equiv)
N
R
H
R
R
H
CHCl3, 80 oC, 24 h
CHCl3, 80 oC, 48 h
TIPS
TIPS
Alkynylation
Alkenylation
Entry
Substrate
O
Alkynylation
O
Alkenylation
O
Entry
Substrate
Alkynylation
O
Alkenylation
O
O
Me
Me
Me
Me
Me
N
N
H
N
H
Me
N
H
N
H
8
1
N
H
H
AcO
H
AcO
AcO
H
TIPS
TIPS
TIPS
TIPS
, 65%
1a
3a
3b
3c
3d
4a
1h
3h
4h
, 89%
, 90%
O
, 43%
Me
O
Me
O
O
Me
O
O
Me
Me
Me
Me
Me
N
H
N
Me
N
N
2
9
N
H
N
H
H
H
H
H
H
TIPS
OTBS
TIPS
OTBS
TIPS
, 18%
OTBS
TIPS
1b
4b
4c
4d
, 89%
O
1i
1j
3i
3j
4i
, 70%
, 39%
O
O
O
O
H
O
H
Me
Me
Me
Me
Me
Me
Me
Me
N
N
Me
N
N
H
3
N
10
H
N
H
H
H
H
Br
Br
Br
TIPS
TIPS
TIPS
, 93%
TIPS
4j
, 81%
O
, 48%
O
1c
, 93%
O
O
O
H
O
Me
Me
F
Me
F
Me
Me
N
N
H
F
Me
N
N
11
N
H
4
H
N
H
H
H
F3C
F3C
F3C
H
TIPS
TIPS
TIPS
TIPS
, 64%
1k
3k
4k
, 80%
O
, 48%
1d
, 71%
O
O
O
O
O
Me
Me
Cl
Me
Cl
Me
Me
N
H
N
H
Cl
Me
N
N
12
13
N
H
5
N
H
H
H
Ac
Ac
Ac
H
H
TIPS
TIPS
TIPS
TIPS
, 32%
1l
3l
4l
, 92%
O
, 42%
O
1e
3e
4e
, 67%
O
O
O
Me
O
H
Me
Me
N
Br
Me
N
H
Br
Me
N
Br
Me
N
H
N
6
7
N
H
H
H
H
MeO2C
MeO2C
MeO2C
H
TIPS
TIPS
TIPS
TIPS
1m
3m
4m
, 88%
, 47%
1f
3f
4f
, 88%
O
, 46%
O
O
O
O
O
Br
Me
Br
Me
I
Me
I
Me
Br
Me
N
H
N
I
Me
N
N
H
14
N
H
N
H
H
H
H
H
F
TIPS
F
TIPS
F
TIPS
TIPS
1n
3n
4n
, 59%
1g
3g
4g
, 53%
, 90%
, 43%
a
1a
2a
(3.0 equiv.), Ir(COD)2OTf (10 mol%), Ligand (12 mol%), CHCl3 (1.0 mL). Isolated yields were reported.
Reaction conditions:
(0.1 mmol, 1.0 equiv),
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 3 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC08735D
COMMUNICATION
hydrogen acceptor. This hydrogen transfer event was further
corroborated by the reactions of deuterated benzamide with 2
and deuterated 2-D, where mono-deuteration and triple-
deuteration were observed in the vinyl silanes, respectively.
Table 3. Substrate scope of alkyne
The catalytic system also worked well for alkenyl C-H bond
(Scheme 2). For example, under the standard reaction
conditions, alkynylation and alkenylation products were
obtained in good yields and good selectivity from 1o. These
methods provide a facile route for the synthesis of tetra-
substituted conjugated alkenes.
To further demonstrate the synthetic utility, the catalytic
transformations of a benzamide derived from an intermediate
of Rivaroxaban were conducted. Both C-H alkynylation and
alkenylation occurred chemoselectively at the benzamide
moiety despite the potential reaction at the other arene. These
results highlighted the chemoselectivity and the functional
O
O
O
Me
Me
N
or
Me
N
H
H
N
H
+ L3 L6
Ir / or
(10 mol%)
H
1a
R
CHCl3, 80 o
C
R
+
3
L3
4
L6
, with
, with
H
R
Alkynylation
Alkenylation
2
OTBS
H
H
group tolerance of the catalytic system.
2c
Alkynylation 3r
O
2b
Alkynylation 3q
nPr
+ L3
Ir / (10 mol%)
:
, <10%
, <10%
:
, <10%
N
H
2a
Alkenylation 4q
Alkenylation 4r
: , <10%
(3.0 equiv)
:
CHCl3, 80 °C, 24 h
TIPS
nPr
Me
Si t-Bu
Me
Ph
Si t-Bu
Ph
O
H
3o
, 91%
O
nPr
H
H
N
H
+ L6
2e
Ir / (10 mol%)
2d
N
H
2a
(3.0 equiv)
Alkynylation: 3s, 37%
Alkenylation: 4s, 33%
Alkynylation: 3t, 56%
Alkenylation: 4t, 49%
1o
CHCl3, 80 °C, 48 h
TIPS
, 69%
a
1a
2
(0.05 mmol, 1.0 equiv), (3.0 equiv.), Ir(COD)2OTf
Reaction conditions:
4o
(10 mol%), Ligand (12 mol%), CHCl3 (1.0 mL), 24 h for alkynylation and 48 h
for alkenylation. Isolated yields were reported.
TIPS
H
O
+ L3
Substrate
Alkynylation
Alkenylation
O
O
Ir / (10 mol%)
NH
2a
(3.0 equiv)
O
N
H
20% D
CHCl3, 80 °C, 24 h
O
O
O
TIPS
D
N
H
O
Me
3p
N
H
H
, 83%
Me
D2
Me
N
+
N
H
H
TIPS
TIPS
+ L6
20% D
Ir / (10 mol%)
70% D
O
D
TIPS
2a
(3.0 equiv)
N
TIPS
1a
2a
-D
0.96 eq
5
, 84%
6
, 58%
N
CHCl3, 80 °C, 48 h
H
O
88% D
4p
, 58%
1p
D
D
O
D
D
O
D
O
TIPS
D
D
Me
D
D
Me
D
D
Me
D1
N
N
N
H
+
Scheme 2. Reactions of alkenyl C-H substrate and a drug-
derived molecule. Reaction conditions: 1 (0.1 mmol, 1.0 equiv),
2a (3.0 equiv.), Ir(COD)2OTf (10 mol%), ligand (12 mol%), CHCl3
(1.0 mL). Isolated yields were reported.
H
TIPS
H
D
D
H
>95% D
TIPS
D
TIPS
1.2 eq
1a-
2a
D5
7
, 89%
8
, 68%
O
89% D
D
D
D
D
O
D
The scope of the alkyne, however, is relatively limited (Table
3). Catalytic alkynylation or alkenylation did not work for alkyl
and aryl alkynes (2b, 2c). Thus, a silyl group on the alkyne is
important for catalytic reactivity. In particular, the alkynylation
and alkenylation proceeded to give better yields for alkyne
bearing more hindered silyl group (2d vs 2e), likely due to the
suppression of undesired homodimerization of the alkyne.
To gain insight into the reaction mechanism, deuterium
labelling experiments were conducted (Scheme 3). Under the C-
H alkynylation conditions, the reaction of benzamide 1a with 2-
D afforded the alkynylation product where the ortho C-H bond
was partially deuterated. Thus it is likely that the C-H cleavage
TIPS
D
D
O
D
D
Me
D
D
Me
N
H
D
D
N
D
D
Me
+
H
N
H
D
TIPS
>95% D
TIPS
D
D
D
TIPS
1a-
2a
-D
D5
1.2 eq
10
, 65%
9
, 90%
70% D
Scheme 3. Deuterium labelling experiments. Reaction
conditions: 1a or 1a-D5 (0.1 mmol, 1.0 equiv), 2a or 2a-D (3.0
equiv.), Ir(COD)2OTf (10 mol%), ligand (12 mol%), CHCl3 (1.0
mL). 24 h for alkynylation and 48 h for alkenylation. Isolated
yields were reported.
Under the C-H alkenylation conditions, the reaction of
is reversible for C-H alkynylation. In addition, almost equal benzamide 1a with 2-D afforded the alkenylation product with
molecular amount of vinyl silane with two deuterium atoms was
observed, indicating that silyl acetylene functions as the
significant deuteration α to the silicon rather than the expected
benzylic position. Thus, it is likely that a metal vinylidene
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
intermediate was involved.13 The alkenylation product formed
from the reaction of deuterated benzamide with 2 further
supports this mechanism.
2014, 50, 9865-9868; (e) K. D. Collins, F. Lied and F.VGiewlorAirutisc,leCOhnelimne.
Commun., 2014, 50, 4459-4461; (f) F. Xie, Z. Qi, S. Yu and X. Li, J. Am.
DOI: 10.1039/C9CC08735D
Chem. Soc., 2014, 136, 4780-4787; (g) W. Wu and H. Jiang, Acc. Chem.
Res., 2014, 47, 2483-2504; (h) Y. J. Liu, Y. H. Liu, S. Y. Yan and B. F. Shi,
Chem. Commun., 2015, 51, 6388-6391; (i) X. Ye, C. Xu, L. Wojtas, N. G.
Akhmedov, H. Chen and X. Shi, Org. Lett., 2016, 18, 2970-2973; (j) Z.
Ruan, S. Lackner and L. Ackermann, ACS Catal., 2016, 6, 4690-4693; (k) C.
Chen, P. Liu, J. Tang, G. Deng and X. Zeng, Org. Lett., 2017, 19, 2474-2477;
(l) J. Han, N. Wang, Z. B. Huang, Y. Zhao and D. Q. Shi, Org. Biomol. Chem.,
2017, 15, 5112-5116; (m) X. Li, G. Wu, X. Liu, Z. Zhu, Y. Huo and H. Jiang,
J. Org. Chem., 2017, 82, 13003-13011; (n) H. M. Viart, A. Bachmann, W.
Kayitare and R. Sarpong, J. Am. Chem. Soc., 2017, 139, 1325-1329; (o) Z.
Ruan, N. Sauermann, E. Manoni and L. Ackermann, Angew. Chem. Int.
Ed., 2017, 56, 3172-3176; (p) G. Cera, T. Haven and L. Ackermann, Chem.
Eur. J., 2017, 23, 3577-3582; (q) G. Li, P. Liu, J. Zhang, D.-Q. Shi and Y.
Zhao, Org. Chem. Front., 2017, 4, 1931-1934; (r) G. Jiang, W. Hu, J. Li, C.
Zhu, W. Wu and H. Jiang, Chem. Commun., 2018, 54, 1746-1749; (s) W.
Wu, S. Fang, G. Jiang, M. Li and H. Jiang, Org. Chem. Front., 2019, 6, 2200-
2204; (t) Y. Zheng and W. Song, Org. Lett., 2019, 21, 3257-3260.
6. C. Liu, J. Yuan, M. Gao, S. Tang, W. Li, R. Shi and A. Lei, Chem. Rev., 2015,
115, 12138-12204.
Taken together, the following mechanism was proposed
(Scheme 4). Directed C-H cleavage affords an iridacycle 12.
Insertion of an alkyne into the iridium hydride generates a vinyl
iridium species 13, which undergoes reaction with a terminal
alkyne to form an iridium acetylide 14. Finally, reductive
elimination delivers the alkynylation product and regenerates
the catalyst. Alternatively, the iridacycle 12 interacts with
terminal alkyne to form a vinylidene species 15. Migratory
insertion of the vinylidene followed by reductive elimination
generates the alkenylation product.
NHMe
NHMe
O
4a 1a
1a 3a
NHMe
O
O
Ir
P
P
Ir
Ir
P
P
H
H
11
16
P
14
P
TIPS
TIPS
TIPS
7. For leading references: (a) X. Jie, Y. Shang, P. Hu and W. Su, Angew. Chem.
Int. Ed., 2013, 52, 3630-3633; (b) J. Dong, F. Wang and J. You, Org. Lett.,
2014, 16, 2884-2887; (c) M. Shang, H. L. Wang, S. Z. Sun, H. X. Dai and J.
Q. Yu, J. Am. Chem. Soc., 2014, 136, 11590-11593; (d) G. Wu, W. Ouyang,
Q. Chen, Y. Huo and X. Li, Org. Chem. Front., 2019, 6, 284-289.
8. Molecular oxygen as oxidant: (a) N. Matsuyama, M. Kitahara, K. Hirano,
T. Satoh and M. Miura, Org. Lett., 2010, 12, 2358-2361; (b) S. H. Kim, J.
Yoon and S. Chang, Org. Lett., 2011, 13, 1474-1477; (c) Y. H. Liu, Y. J. Liu,
S. Y. Yan and B. F. Shi, Chem Commun., 2015, 51, 11650-11653.
9. Directing group as oxidant: J. Zhou, J. Shi, Z. Qi, X. Li, H. E. Xu and W. Yi,
ACS Catal., 2015, 5, 6999-7003.
10. For a review: (a) V. P. Boyarskiy, D. S. Ryabukhin, N. A. Bokach and A. V.
Vasilyev, Chem. Rev., 2016, 116, 5894-5986; For leading references: (b)
R. Tanaka, H. Ikemoto, M. Kanai, T. Yoshino and S. Matsunaga, Org. Lett.,
2016, 18, 5732-5735; (c) F. Hu and M. Szostak, Chem. Commun., 2016,
52, 9715-9718; (d) S. Wang, J. T. Hou, M. L. Feng, X. Z. Zhang, S. Y. Chen
and X. Q. Yu, Chem. Commun., 2016, 52, 2709-2712; (e) L. Huang, A.
Biafora, G. Zhang, V. Bragoni and L. J. Gooßen, Angew. Chem. Int. Ed.,
2016, 55, 6933-6937; (f) S. S. Bera, S. Debbarma, A. K. Ghosh, S. Chand
and M. S. Maji, J. Org. Chem., 2017, 82, 420-430; (g) M. Nagamoto, J.-i.
Fukuda, M. Hatano, H. Yorimitsu and T. Nishimura, Org. Lett., 2017, 19,
5952-5955; (h) Y.-C. Chang, S. Prakash and C.-H. Cheng, Org. Chem.
Front., 2019, 6, 432-436.
NHMe
2
NHMe
O
NHMe
O
O
P
Ir
H
Ir
Ir
P
P
P
H
P
2
P
2
15
H
TIPS
12
TIPS
13
Scheme 4. Proposed mechanism.
In summary, we have developed an iridium-catalyzed, ligand-
controlled reaction of arenes with terminal alkynes. Both C-H
alkynylation and alkenylation products were obtained in high
selectivity by simple choice of the ligand. The C-H alkynylation
proceeds without any external oxidant, while the C-H alkenylation
occurs through an unusual vinylidene mechanism. Further
improvement of the reaction efficiency and elucidation of the
reaction mechanism are currently ongoing in our laboratory.
This work was supported by the National Natural Science
Foundation of China (Grant No. 21672122 and No. 91856107).
Conflicts of interest
There are no conflicts to declare.
11. J. Kim, S. W. Park, M. H. Baik and S. Chang, J. Am. Chem. Soc., 2015, 137,
13448-13451.
12. (a) Z.-X. Wang, X.-Y. Bai, H.-C. Yao and B.-J. Li, J. Am. Chem. Soc., 2016,
138, 14872-14875; (b) Z.-X. Wang and B.-J. Li, J. Am. Chem. Soc., 2019,
141, 9312-9320.
Notes and references
13. C. Bruneau and P. H. Dixneuf, Angew. Chem. Int. Ed., 2006, 45, 2176-
2203.
1. B. M. Trost and C.-J. Li, Modern Alkyne Chemistry, Wiley-VCH, Verlag
GmbH & Co. KGaA, 2014.
2. (a) I.-T. Trotuş, T. Zimmermann and F. Schüth, Chem. Rev., 2014, 114,
1761-1782; (b) R. Chinchilla and C. Nájera, Chem. Rev., 2014, 114, 1783-
1826; (c) A. K. Mourad and C. Czekelius, Synlett, 2013, 24, 1459-1463.
3. R. Chinchilla and C. Nájera, Chem. Soc. Rev., 2011, 40, 5084-5121.
4. L. D. Caspers and B. J. Nachtsheim, Chem. Asian J., 2018, 13, 1231-1247.
5. For leading references: (a) A. S. Dudnik and V. Gevorgyan, Angew. Chem.
Int. Ed., 2010, 49, 2096-2098; (b) Y. Ano, M. Tobisu and N. Chatani, Org.
Lett., 2012, 14, 354-357; (c) C. Feng and T. P. Loh, Angew. Chem. Int. Ed.,
2014, 53, 2722-2726; (d) C. Feng, D. Feng and T. P. Loh, Chem. Commun.,
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC08735D
COMMUNICATION
TOC
O
Me
+ Ligand 1
Ir /
N
H
R
O
H
Alkynylation
Me
TIPS
O
N
R
H
Me
+ Ligand 2
Ir /
N
H
H
TIPS
R
Alkenylation
TIPS
Please do not adjust margins