“This is the peer reviewed version of the following article: Towards Uniform Iodine-Catalysis: Intramolecular C-HAmination of Arenes under Visible Light, which has been published in final form at DOI: 10.1002/chem.201602138. This
article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving “.

Towards Uniform Iodine-Catalysis: Intramolecular C-H-Amination of Arenes under Visible Light

Claudio Martínez,[a] Alexandra E. Bosnidou,[a] Simon Allmendinger,[a] and Kilian Muñiz*[a,b]
Abstract: A photochemical catalytic amination of arenes is presented. The reaction proceeds under benign iodine catalysis in the presence of
visible light as the initiator and provides access to a range of differently substituted arylamines. A total of 29 examples demonstrate the broad
applicability of this mild oxidation method. The scope of the reaction could further be expanded to silyl-tethered derivatives, which undergo
intramolecular amination upon formation of seven-membered heterocycles. Cleavage of the silicon tether provides access to the
corresponding 3-substitued anilines.

Approaches toward the direct C-H amination of arenes are of significant interest as they provide a straight-forward and economic
access to anilines and higher-functionalized aryl amine derivatives.[1] Entities of this type are present in a large number of functional
molecules of pharmaceutical and biological interest.[1,2] Common approaches toward C-H amination rely on the use of transition metal
catalysts and an impressive body of recent work has demonstrated the usefulness of palladium, rhodium, iridium and other metals for
the aforementioned transformation.[3]
High oxidation state iodine reagents have been identified as useful alternatives to common transition metals.[4] Their particular appeal
stems from their broad scope in general oxidation chemistry combined with the fact that their use is not hampered by the occurrence
of residual metal contamination. Consequently, iodine(III)-mediated and catalyzed amination of aromatic C-H bonds has recently
been explored.[5-7] In another area of iodine(III)-mediated reactions, several reports on the combined use of stoichiometric amounts of
molecular iodine in combination with excess equivalents of compounds of the general structure ArI(O2CR)2 have become available
for intramolecular C-H amination reactions. Such reactions have previously been addressed under conditions of overstoichiometric
reagent combinations, which in several cases led to undesired side-product formation upon overoxidation.[8] One may anticipate that
catalysis should avoid such problems as it can operate under more defined oxidation conditions. Despite the general interest in the
field, reliable iodine catalyses remain largely unexplored for the intramolecular oxidative synthesis of aniline derivatives.[5,9]
We recently reported on the iodine-catalyzed Hofmann-Löffler reaction, which includes the visible light induced amination of a sp3hybridized carbon as the key step (Scheme 1, eq. 1).[10] Within this context, we became interested in the application of this amination
concept[11] for the related light induced functionalization of arenes (eq. 2).[12] Usually, conditions for either alkyl or aryl C-H amination
are not transferable from one case to the other since the operating reaction mechanisms are profoundly different in nature. From this
perspective, the exploration of nitrogen radical intermediates from iodine catalysis could result in a useful uniform reactivity
comprising both cases.

Catalytic Csp3-H Amination (ref. 10)
NHTs

I2 (5 mol%)
PhI(O2CAr)2
DCE, 25 ºC,

R

visible light

(1)

R
N
Ts

uniform
conditions
O2
S

N
H

R

I2 (5 mol%)
PhI(O2CAr)2

O2
S

N

R

(2)

DCE, 25 ºC,
visible light

R´

R´

Catalytic Csp2-H Amination (this work)
[a]

Dr. C. Martínez, A. E. Bosnidou, Dr. S. Allmendinger, Prof. Dr. K.
Muñiz
Institute of Chemical Research of Catalonia (ICIQ),
The Barcelona Institute of Science and Technology,
Av. Països Catalans 16, 43007 Tarragona, Spain
E-mail: kmuniz@iciq.es

[b]

Prof. Dr. K. Muñiz
Catalan Institution for Research and Advanced Studies (ICREA),
Pg. Lluís Companys 23, 08010 Barcelona, Spain
Supporting information for this article is given via a link at the end of
the document.

Scheme 1. Uniform reaction conditions for light-initiated iodine-catalyzed alkyl
and aryl amination (eq. 1 and eq. 2, respectively). Ar = 3-Cl-C6H4, DCE = 1,2dichloroethane.

We here report that this assumption indeed leads to a feasible
approach toward a new direct catalytic arene amination using
visible light initiation.[13] The reaction was initially developed for
biaryl derivatives, and was explored for the phenyl derivative 1a
(Scheme 2). Suitable conditions were obtained already at the
outset of a short screening and consist of the application of

comparable catalysis from alkyl amination. A catalyst loading of 5 mol% elemental iodine was optimum in combination with a
hypervalent iodine reagent as terminal oxidant.[14] The formation of 2a proceeds in quantitative yield and can be carried out
conveniently at 4.1 mmol scale (1.06 g). The reaction is general for a series of these derivatives and proceeds in high yields and with
complete selectivity. For example, para-substituted arenes of different electronic parameters were all tolerated in the amination
(compounds 2b-2k, 80-99%). The constitution of the products was unambiguously assured from X-ray analysis of the 4-phenoxy
derivative 2f.[15]
O2
S

O2
S

I2 (5 mol%),
PhI(O2CAr)2 (1.1 equiv)

N
H
R

R

DCE, 12 h, 25 ºC
exposure to visible light
2a-q'

1a-q
O2
S

N

O2
S

N

O2
S

N

O2
S

N

N

t-Bu
2a: 99%
(99%)[a]
O2
S
N

2b: 92%
O2
S

OPh
2f: 85%

OMe

O2
S

N

2h: 80%
O2
S

Cl

2i: 99%

F

N

OEt
2g: 90%
O2
S

N

O2
S

N

O2
S

N

2e: 93%
O2
S

Ph
2d: 94%

2c: 93%

O2
S

N

2j: 99%

CF3

N

2k: 99% Br

O 2S N

N

NSO2Ph

S
2l: 60%
O2
S

N

O2
S
+

O2
S

N
O

O
O
O2
S

2n: 80%

2m: 50%

O2
S
+

N

O
2o/2o': 93% (2:1)
O2
S

N
+
F

N

2p/2p': 96% (1.4:1)

N

F
2q/2q': 93% (4.5:1)

Scheme 2. Intramolecular C-H Amination of Biaryls: Scope. Yields refer to isolated yields after purification. [a] Reaction at 4.1 mmol scale.

1,2,3-Trisubstituted compound 2l demonstrates the compatibility of an ortho-disubstituted arene, and the successful aminations of
1m and 1n expand the scope to heteroarenes such as benzothiophene and indole. Higher-substituted arenes also undergo the
intramolecular amination, although they form regioisomeric mixtures (products 2o/2o’ to 2q/2q’, 1.4:1 to 4.5:1 regioisomeric ratio).
A rigid preorganization of the coupling entities within a biaryl scaffold is not a requirement as related alkyl-connectivity also lead to a
protocol with related efficiency (Scheme 3). Representative substrates 3a-l include common arene substitution patterns and were
investigated for different N-alkyl sulfonamides. As in the case of related biaryl derivatives 2, the formation of compounds 4 proceeds
in high isolated yields (51-99%) and with complete selectivity.

O2
S

N
H

R

3a-l

SO2
N
R
4d (R = Me): 97%
4e (R = Bn): 89%

SO2
N
R
4a (R = Me): 95%
4b (R = Bn): 99%
4c (R = Et): 96%

N

Cl

SO2

N

4a-l

Br

SO2

R

N

SO2

4f (R = Me): 98%
4g (R = Bn): 92%

SO2

Ph

N

SO2

4l (R = Me): 51%

4j (R = Me): 96%
4k (R = Bn): 86%

4h (R = Me): 83%
4i (R = Bn): 89%

N

R´

DCE, 12 h, 25 ºC
exposure to visible light

R´

F

I2 (5 mol%),
PhI(O2CAr)2 (1.1 equiv)

Scheme 3. Intramolecqular C-H Amination of Ethylenylarenes: Scope. Yields refer to isolated yields after purification.

O2
S

I2 (10 mol%),
PhI(O2CAr)2 (1.1 equiv)

N
H

Si
R

5a-l

DCE, 12 h, 25 ºC
exposure to visible light

O2
S N
Si

R

6a-l

O2
S N

O2
S N

Si

Si
6a (X-ray)

6a: 70%

6c: 40%

O2
S N

O2
S N

O2
S N
Si

6b: 74%

OMe

F

Si

Cl

Si
6e: 50%

6d: 50%
O2
S N

O2
S N
+

Si

Si
6f/6f': 80% (1:1)

O2
S N
Si
6a (X = H)
6d (X = F)

TBAF
(2 equiv)
X

PhO2S N

THF,
RT, 12 h,

TMSI

HN

[ref 14]
X
7a (99%)
7d (87%)

X
8a (91%)
8d (80%)

Scheme 4. Intramolecular C-H Amination using a Silyl-Tether: Scope. Yields refer to isolated yields after purification.

Deprotection of these heterocycles is readily accomplished through hydrogenolysis of the benzyl derivatives as demonstrated for the
representative case of product 4b (H2, Pd/C, EtOH, 91%).[14]
The reaction scope could be extended to silicon-tethered arenes 5.[16] The subsequent intramolecular C-H amination proceeds upon
seven-membered ring formation. It requires a slightly higher catalyst loading of 10 mol%, but proceeds with the expected complete
selectivity in favor of C-H amination (Scheme 4). For the parent derivative 6a, the product constitution was secured from X-ray
analysis.[15] Arenes 5b-e with electronically different substitution undergo the C-H amination within this protocol (40-78% yield), and a
2-naphthalene derivative 5f forms the two regioisomeric amination products 6f/f’ in combined 80% yield. Advantageously, as
demonstrated for products 6a,d, the silyl tether can be removed upon mild exposure to tetrabutylammonium fluoride to give the
phenylsulfonyl-substituted anilines 7a,d quantitatively. Conversion of these compounds into the free anilines 8a,d is possible
following a modified literature procedure.[17] This sequence starting from 5 thus provides access to the corresponding 3-substituted

anilines with complete selectivity. Such a substitution pattern would be synthetically difficult via a direct C-H amination or not be
accessible from standard electrophilic aromatic substitution.
Control experiments demonstrate that no conversion is obtained either in the absence of molecular iodine or in the dark lab.[12] The
reaction appears to involve the expected N-I bond as in the related catalytic alkane Csp3-amination.[10] The isolated
tetrabutylammonium iodinane 9[10] was employed to demonstrate the nature of an electrophilic iodine(I) catalyst state at the outset of
the reaction. In line with this anticipation, reagent 9 promoted clean aryl amination with standard compound 1a upon acid activation[18]
(Scheme 5, eq. 3). A competition experiment between 1a and its pentadeuterated derivative 1a-d5 revealed no difference regarding
the individual rates (kinetic isotope effect kH/kD = 1, eq. 4). Finally, an internal electronic competition experiment with precursor 3m
showed exclusive amination at the more electron-rich anisole ring forming 4m in 50% yield (eq. 5, 99% based on recovered starting
material). A related outcome was observed for two intermolecular competition experiments between 3a and 3j, and 3a and 3h,
respectively. In both case, a significant preference for amination of the more electron-rich arene was encountered favoring formation
of 4j over 4a, and 4a over 4h, respectively (eq. 6).
The reaction starts from the established I(O2CAr) catalyst 10 that promotes N-iodination of the sulfonamide starting materials to
intermediate A (Figure 1, the structure of 3 is shown arbitrarily). As demonstrated by the control experiment using the isolated
reagent 9 a potential alternative pathway proceeding via aryl radical cations generated from the hypervalent iodine reagent itself can
be ruled out.[19] Photolytically assisted homolysis of the N-I bond in A provides access to N-centered radical B. This electrophilic
nitrogen radical directly adds to the aromatic ring to generate a delocalized cyclohexadienyl radical C. Subsequent oxidation by the
terminal hypervalent iodine leads to the cationic intermediate D and directly regenerates the iodine(I) catalyst 10. Although less
probable, oxidation may occur already at stage B to generate a positively charged nitrogen atom, which engages in electrophilic
aromatic substitution[20] toward D. Both of the two potential C-N bond formation events should be influenced by the electronic
situation of the arene as corroborated by the control experiments from eqs. 5 and 6. From D, the reaction terminates by final proton
loss upon re-aromatization to the C-N coupling product 4. This final step is rapid as demonstrated by the kinetic isotope experiment
from eq. 4.

O2
S

Bu4N[I(O2CAr)2] 9
(1 equiv),
HO2CAr (1 equiv)

N
H

O2
S

DCE, 12 h, 25 ºC
75%

1a
O2
S

1a
+ O2
S

I2 (0.01 mol%)
PhI(O2CAr)2
(0.1 equiv)

D5

N

2a
+ O2
S

DCE, 25 ºC

N
H

(3)

2a
O2
S

N
H

N

(4)
N

KH/KD = 1.0

D4

2a-d4

1a-d5
OMe

I2 (5 mol%)
PhI(O2CAr)2
(1.1 equiv)

BnN

O2
S
(5)

O2
S

DCE, 25 ºC
NHBn
50%

3m

F

MeO
4m

F

O2
S
X

+

N
H

O2
S

X

N

+
N
H

Y
X = Me (3j), Y = H (3a)
X = H (3a), Y = F (3h)

Scheme 5. Control Experiments.

I2 (0.01 mol%)
PhI(O2CAr)2
(0.1 equiv)
DCE, 25 ºC
Y
KMe/KH = 40/1
KH/KF = 19/1

N

SO2
4j + 4a
4a + 4h

SO2
(6)

catalyst formation:
I2 + PhI(O2CAr)2

2 I(O2CAr) (10) + PhI

catalytic cycle:

O2
S

hv

N
I

R
HO2CAr

O2
S

A
3
O2
S

B

N

R

I(O2CAr)
10

I
O2
S

HO2CAr

H[I(O2CAr)2]

- HO2CAr

PhI +
N R

R

N
H

O2
S

N R
ArCO2

PhI(O2CAr)2

I
C

O2
S

D
N R
- HO2CAr
4

Figure 1. Mechanistic context.

In summary, we have developed an iodine catalysis protocol that provides conditions for a mild and selective intramolecular aryl
amination reaction. This chemistry demonstrates that photochemical iodine catalysis can provide general oxidative amination
conditions for the cases of aliphatic and aromatic hydrocarbons alike. This broad scope is unprecedented in the area and should
stimulate the development of additional reactivity.

Acknowledgements
Financial support for this project was provided from the Spanish Ministry for Economy and Competitiveness and FEDER (CTQ201456474R grant to K. M., Severo Ochoa Excellence Accreditation 2014-2018 to ICIQ, SEV-2013-0319 and FPI Fellowship to A. E. B.)
and Cellex-ICIQ Programme (fellowship to C. M.). The authors thank E. Escudero-Adán for the X-ray structural analyses.
Keywords: amination • arenes • catalysis • iodine • visible light
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Claudio Martínez, Alexandra E.
Bosnidou, Simon Allmendinger, Kilian
Muñiz*
Towards Uniform Iodine-Catalysis:
Intramolecular C-H-Amination of
Arenes under Visible Light

Iodine catalysis aminates arenes! Iodine in catalyst loadings of 5-10 mol%
provides access to intramolecular Csp2-N bond formation. Sulfonamides are
employed as nitrogen sources leading to excellent yields. In some cases,
introduction of a traceless linker provides ready access to aniline derivatives.

Text

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