“This is the peer reviewed version of the following article: N-Iodosuccinimide promoted Hofmann-Löffler Reactions of
Sulfonimides under Visible Light, which has been published in final form at DOI: 10.1002/adsc.201600191 . This
article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving “.

An Improved Catalyst for Iodine(I/III)-Catalysed Intermolecular C-H Amination
Nicola Lucchetti,[a] Michelangelo Scalone,[b] Serena Fantasia,[b] Kilian Muñiz,[a,c]*

Abstract: 1,2-Diiodobenzene is presented as an efficient catalyst precursor for the intermolecular amination of arenes under homogeneous
conditions. N-Troc and N-phthalimido-substituted methoxyamines serve as suitable nitrogen sources providing the corresponding aniline
derivatives in up to 99% yield and with up to 66:1 regioselectivity. Key for this successful C-N coupling protocol is the strained µ−oxo-bridged
conformation of the bisiodine(III) catalyst, which induces unparalleled high reactivity.

Introduction
The development of synthetic methodology for the direct amination of arene hydrocarbons has been a long-standing interest in
organic chemistry and life sciences due to the ubiquity of nitrogen-containing molecules in natural products, pharmaceuticals and
agrochemicals.[1,2] It has implication for the defined installment of C-N bonds from ubiquitously available precursors. The particular
attractiveness of the synthetic endeavor of C-H amination[3] lies in the potential to replace the currently most established protocols for
arylamine synthesis (Buchwald-Hartwig or Ullmann coupling), which require the use of pre-fabricated aryl halides and related
substrates under palladium[4] and copper catalysis,[5] respectively. A conceptually alternative approach of direct C-H to C-N
transformation should be of sufficiently broad application and has recently been pursued widely using transition metal catalysis.[3,6]
However, in most of the cases the presence of a directing group was needed to pre-coordinate the metal center and engage it in a
directed regioselectivity control (Figure 1, eq. 1).[3,7]
An alternative entry into C-H amination relies on the use of an iodine(III) promoter (eq. 2).[8] The viability of such a concept was
initially demonstrated by Chang,[9] DeBoef[10] and Antonchick.[11] Several complimentary intra-[12] and intermolecular[13] protocols
followed.[14] Pioneering was the work of Kita to introduce nitrogenated groups in form of an azido moiety into the aromatic ring.[15]
Finally, the iodine(III) promoter could be conceived as a catalyst by identification of suitable terminal oxidants to re-oxidize the
aryliodide(I) after the organic transformation (eq. 3).[16] A particularly effective approach from Antonchick was obtained using Kita
catalyst 1.[17]

[a]

[b]

[c]

N. Lucchetti, Prof. Dr. K. Muñiz
Institute of Chemical Research of Catalonia (ICIQ)
The Barcelona Institute of Science and Technology
16 Avgda. Paisos Catalans, E-43007 Tarragona, Spain
E-mail: kmuniz@iciq.es
Dr. M. Scalone, Dr. S. Fantasia
F. Hoffmann-La Roche Ltd.
Process Research & Development
Grenzacherstrasse 124, 4070 Basel, Switzerland
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.

Intermolecular Directed C-H Amination
cat. [Pd]
oxidant

DG
RNH2

DG
(1)

!

NHR

Intermolecular Metal-Free C-H Amination: Stoichiometric
R
RNH2

R

PhI(OAc)2

(2)

140 oC

NHR

R = electron donating and withdrawing

Intermolecular Metal-Free C-H Amination: Catalytic
R
R2NH

Aryliodine(III)
catalyst

R
(3)

terminal oxidant

NR2

R = electron donating and withdrawing

Kita catalyst (1)
I

I

Figure 1. Representative examples for oxidative amination of arenes.

The current status quo in the field still leaves room for an improved catalytic system that could improve the turnover number of the
intermolecular approach using less harsh conditions, and increasing the scope of the reaction. We here report on an advanced
iodine(III) catalyst for the direct intermolecular amination of arenes using Troc-protected amines as nitrogen sources.

Results and Discussion
We initially investigated the possible amination of arenes using preformed diaryliodonium salts with N-tosyl N-methoxyamine 2a as
the currently most successful nitrogen source (Table 1).[12b,13e,13j] The aim of this investigation was to arrive at detailed knowledge on
the transferability of different aryl groups and thus to identify an optimum aryl monoiodine(I) catalyst. We started testing different
iodonium salts, both commercially available and literature-known ones.[18] The presence of a small counter-ion effect was observed
from these studies. For diphenyliodonium, the chloride anion provided arylation product 3a in 73% yield (entry 1), which could be
increased by using hexafluorophosphate, acetate or nitrate (77-82% yield, entries 3-5). Selective phenylation was also observed with
a mixed iodonium reagent containing phenyl and 4-anisyl as arenes (entry 8). DCE was identified as the optimum solvent, other
solvents such as CH2Cl2, CHCl3 and fluorinated ones were observed to provide lower or no yields (entries 7-10). Exchanging the tosyl
for a benzoyl group (reagent 2b), provided a less efficient process (entry 11). Reactions at higher temperature resulted in decreased
conversions (entries 2,12).
These orientation experiments revealed the general feasibility to employ hypervalent iodine reagents of the general bisaryliodonium
structure for arylamine synthesis. While this work was under investigation, a related investigation by Olofsson became available.[19]

RNHOMe

iodonium salt I(III)
K2CO3
solvent, 25 ºC

2a,b

RN(Ph)OMe
3a,b

Table 1. Stoichiometric amination using preformed diaryliodonium salts.
Entry

R

Iodine(III)

Solvent

1

Ts (2a)

[Ph2I]Cl

DCE

Yield [%]
73

[a]

2

[b]

Ts (2a)

[Ph2I]Cl

DCE

-

3

Ts (2a)

[Ph2I]PF6

DCE

82

4

Ts (2a)

[Ph2I]OAc

DCE

79

5

Ts (2a)

[Ph2I]NO3

DCE

77

6

Ts (2a)

[PhIAn]OTs

DCE

63

7

Ts (2a)

[PhIAn]OTs

DCM

73

8

Ts (2a)

[PhIAn]OTs

CHCl3

75

9

Ts (2a)

[PhIAn]OTs

TFE

10

Ts (2a)

[PhIAn]OTs

HFIP

nr

11

Bz (2b)

[Ph2I]Cl

DCE

38

Bz (2b)

[Ph2I]Cl

DCE

20

12

[b]

[]c

nr

[d]

[a] Isolated yield after purification. [b] Reaction at 40 ºC. [c] An = 4-anisyl. [d]
nr = no reaction.

In the subsequent investigation, we centered on the possibility to arrive at appropriate catalytic conditions for the corresponding
iodine(III)-promoted arylamine formation. We started screening oxidants, additives, solvents and temperature using the Nmethoxysulfonamide as nitrogen source and iodobenzene as catalyst precursor. The reaction for synthesis of 3a could be transferred
to a catalytic reaction of direct C-H amination of benzene (Table 2) employing peracetic acid as oxidant. With an equimolar amount,
the reaction with 10 equivalents of benzene provided 22% yield of 3a (entry 1). Increasing to 1.5 equivalents improved the yield to
55% (entry 2). Similar values were obtained in the absence of DCE and with 20 equivalents of benzene (entries 3,4). Addition of
HFIP improved the yield to 70% (entry 5), while lowering the temperature had little effect (entry 6).

TsNHOMe

PhI 4a (10 mol%),
C6H6
CH3CO3H, TFA (5 equiv)

TsN(Ph)OMe

solvent, 25 ºC
2a

3a

Table 2. Catalytic amination of benzene using iodobenzene as catalyst.
Entry

CH3CO3H
(equiv.)

C6H6 (equiv)

Solvent

Time
[h]

Yield [%]

1

1.0

10

DCE

22

22

2

1.5

10

DCE

3

55

3

1.5

10

-

2

52

4

1.5

20

DCE

2

57

5

1.5

20

DCE/HFIP

2

70

6

1.5

20

DCE/HFIP

16

[a]

73

[a] Isolated yield after purification. [b] Reaction at 0 ºC.

Following the outcome from Table 1, different sterically demanding iodine derivatives were investigated as catalysts in this
transformation under these conditions, in view to improve future C-H amination reactions with substituted arenes. Iodoarenes bearing
methyl-substitution led to unexpectedly low performances (Figure 2). While iodobenzene as standard gave yields of 3a of 57% and
70% depending on the solvent, dimethylated derivatives 4b and 4c performed less efficient in DCE and did not provide any product in
the presence of HFIP. Iodomesitylene 4d was found to be entirely non-reactive. In contrast, halogenated iodoarenes 4e and 4f led to

yields comparable to 4a, although required significantly prolonged reaction times. Finally, the 1,2-diiodobenzene 4g proofed
surprisingly efficient even at a reduced catalyst loading of 3 mol% and provided the highest yield of 89% within 2 h reaction time.

ArI (10 mol%),
C6H6 (12 equiv)
CH3CO3H (1.3 equiv),
TFA (5 equiv)
TsN(Ph)OMe

TsNHOMe
solvent, 25 ºC

2a

I

3a

I

I

4a

4b

DCE, 2 h, 57%
DCE/HFIP, 2 h, 70%

4c
DCE, 24 h, 25%
DCE/HFIP, 24 h, NR

DCE, 2 h, 36%
DCE/HFIP, 2 h, NR
I

I

I

Cl
4d

Br
4e

DCE, 24 h, NR
DCE/HFIP, 24 h, NR

4f

DCE/HFIP, 24 h, 73%

DCE/HFIP, 24 h, 69%

I
I
4g
DCE/HFIP, 2 h, 89%[a]
Figure 2. Evaluation of aryl iodines for the catalytic amination of benzene with 2a. [a] With 3 mol% catalyst loading.

This compound was explored in a rapid screening of several different nitrogen sources (Figure 3). While due to solubility
problems the mesyl derivative 2c gave a low yield of 19%, the corresponding Cbz and Troc derivatives 2d,e formed the
corresponding products 3d,e in 65% each. Although 3a formed in comparably high yield, further attempts on substituted arenes failed
to give substantial regio- and chemoselectivity for this nitrogen source. Due to the interesting deprotecting properties of the Troc
group,[20,21] this group was subsequently investigated further for several arenes (Figure 4). In the presence of 4 mol% of 4g as
catalyst, 2e underwent several arylation reactions with different arene components, which include hydrocarbons such as toluene,
ethyl benzene, tert-butyl benzene and cyclohexyl benzene. The corresponding products 3f-i are formed in good yields and with
acceptable regioselectivities. Halogenated arenes chlorobenzene, bromobenzene and fluorobenzene are also tolerated and yield
products with good selectivities. For the chloro and bromo derivatives 3j,k the regioisomers could be separated, and for 3l two
isomers are formed in large excess. Disubstituted arenes underwent clean amination as well as deduced from dimethyl derivative 3m
and derivative 3n. In order to demonstrate that other nitrogen sources can be employed equally, Cbz derivative 2d was arylated with
toluene giving regioisomeric derivatives 3o in an outcome comparable to 3f.
C6H4I2 4g (4 mol%),
CH3CO3H (1.3 equiv)
C6H6 (10 - 12 equiv),
TFA (5 equiv)

H

N
R1

OMe
DCE/HFIP (1/1), 25 ºC

2a,c-e

Ts

N

3a:

OMe

89%[a]

Ph
N
R1

OMe

3a,c-e

Ms
3c:

N

OMe

19%[a]

Cbz

N

OMe

3d: 65%

Troc

N

OMe

3e: 65%

Figure 3. Variation of nitrogen sources in the amination of benzene catalysed by 4g. [a] With 3 mol% catalyst loading.

R

N
H

C6H4I2 4g (4 mol%),
CH3CO3H (1.3 equiv),
TFA (5.0 equiv), arene (15.0 equiv),

OMe

DCE/HFIP (1/1), 25 ºC

2d,e

R

OMe
N
Ar
3e-o
Et

Me
Cl3C

O

N

OMe

Cl3C

O

N

OMe

Cl3C

O

3f: 72%
(1/2.7/2.9)[a]

3e: 65%

OMe

O

O

O

N

3g: 78%
(1/2.9/2.9)[a]

Cl
Cl3C

O

N

OMe

Cl3C

O

O

N

3h: 65%
(1/2.2)[b]

O

Cl3C

O

N

3i: 65%
(1/3/1.6)[a]

OMe

3k: 34%[c,d]
(1.7/1)

OMe

3j: 35%[c,d]
(1/1)
F

Cl3C

O

N

OMe

O

O

N
O

Br
Cl3C

OMe

O

3l: 39%[a,d]
(1/17/14)

Cl3C

O

N

OMe

O
3m: 59%

Br
Me
Cl3C

O

N

OMe

Cbz

N

OMe

O
3n: 32%[e]

3o: 66%
(1/3/3.7)[a]

Figure 4. Scope of the amine arylation catalysed by 4g. [a] ratio of o,m,p-regioisomers (unseparated and undetermined regarding the position); regioisomeric
1
1
ratios were calculated on the H-NMR spectra. [b] Ratio of m,p-isomers (unseparated); regioisomeric ratios were calculated on the H-NMR spectra. [c] the
o
ortho/para-regioisomers were fully separated by column chromatography. [d] reaction temperature of 40 C. [e] 2.0 equivalents of arene were used.

In order to compare the efficiency of 4g against the benchmark in the area,[13e] N-acetyl aminophthalimide 5 was employed as
nitrogen source (Figure 5). Excellent chemical yields were obtained for the four C-N coupling products 6a-d from the arenes benzene,
toluene, chlorobenzene and bromobenzene, respectively. In addition, excellent regioselectivities were obtained for the cases of 6c
and 6d, in which the 1,4-derivatives were by far the predominating constitutions. These values surpass previous results and
demonstrate the potential of 4g as catalyst in the oxidative amination of arenes.

PhthN

N
H

C6H4I2 4g (3 mol%),
CH3CO3H (1.3 equiv),
TFA (5.0 equiv)
arene (12.0 equiv),

Ac

PhthN

DCE/HFIP (1/1), 25 ºC

5

N
Ar

Ac

6a-d
O

O

O

O

N N

N N

O

O

Me
6b: 91% (9/4/1)[a]

6a: 99%
O

O

O

N N

O

N N

O

O
Cl

6c: 99% (1/3/79)

Br

6d: 99% (1/66)[b]

Figure 5. Catalytic arylation of N-acetyl aminophthalimide with 4g as catalyst. [a] values in brackets refer to regioisomers
(ortho/meta/para). [b] values in brackets refer to regioisomers (ortho/para).
To gain mechanistic understanding, the reaction of precatalyst 4g with peracetic acid was investigated (Scheme 1). Upon
oxidation,[22] 1,2-diiodobenzene provides the expected µ−oxo-bridged bisiodine(III) derivative 7, which due to its high reactivity could
only be isolated in pure form in 26% yield. Crystals suitable for X-ray analytical studies were grown from a solution of 7 in CH2Cl2/nhexane. The molecular structure of 7 (Figure 6) shows significant deviation from linearity for the central I-O-I group.[23] We reason that
the observed high reactivity in catalysis with 4g results from the marked fragility of the five-membered µ−oxo-arrangement. Indeed,
as demonstrated above, the performance of the 4g/7 catalytic system is essentially better than for comparable diiodine derivatives
such as 1.[13e,24,25]

I
I

OAc
I
O
I
OAc

CH3CO3H
glacial CH3CO2H, 25 ºC,
26%

4g
Scheme 1. Synthesis of µ−oxo-bridged bisiodine(III) derivative 7.

7

[23]

Figure 6. Solid state structure of catalyst 7. Five-membered µ−oxo-arrangement (top) and deviation from linearity of the I-O-I arrangement (bottom). Selected
bond lengths (Å) and angles (º): I1-O1 2.035(7), I2-O1 2.028(7), I1-O2 2.214(7), I2-O4 2.260(8), I2-O1-I1 110.7(3), O1-I1-C1 83.8(3), O1-I2-C2 82.9(4).

OAc
I
O
I
OAc

Troc
Troc

N
H

C6H6 (12.0 equiv)
DCE/HFIP (1/1)
25 ºC

2e

7

OAc
I
O
I
OAc

TFA (5.0 equiv)

OMe

3e (99%)

N
H
2e

7

TFA (5.0 equiv)

OMe

C6H6 (12.0 equiv)
DCE/HFIP (1/1)
25 ºC

OMe
(1)

Troc
Troc

N

N

OMe
(2)

3e (99%)

(2.0 equiv)

Troc

N
H

OMe

2e
(1.0 equiv)

C6H4I2 4g (4 mol%)
CH3CO3H (1.3 equiv)
TFA (5.0 equiv)
C6H6 (6.0 equiv)
C6D6 (6.0 equiv)
DCE/HFIP (1/1)
25 ºC, 65%

Troc

N

OMe

Troc

N

OMe
(3)
D5

3e

3e-d5
kH/kD = 1.18

Scheme 2. Control experiments regarding the reactivity of 4g/7.

To further study this context, three control reactions were carried out (Scheme 2). First, a control reaction was carried out
employing preformed 7 as reagent in the phenylation of 2e under conditions comparable to the catalysis (Scheme 1, eq. 1). In this
case, formation of 3e as the only product was encountered. Importantly, raising the ratio between 2e and 7 to 2:1, an overall yield of
99% (based on 2e) confirms that, in an apparent contrast to earlier systems, both iodine(III) centers in 7 are capable of promoting
arylation (eq. 2). This is a marked contrast to earlier mechanistic suggestions.[13e]
The opening of the five-membered I-O-I ring in 7 and therefore the arylation at the electrophilic iodine(III) centers is indeed not
rate-limiting as a control experiment with C6H6 3e and C6D6 3e-d5 suggests (eq. 3). A low kinetic isotope effect of 1.18 was observed
suggesting that the arylation is rapid for 7. This implies other events as the slow step of the overall catalysis, which may rest with the
introduction of the nitrogen partner into the coordination sphere of the iodine(III) or with the final C-N bond forming reaction.

Conclusions
In summary, we have developed a new catalyst system for the direct C-H amination of arenes. This compound is derived from
oxidation of 1,2-diiodobenzene with peracetic acid as convenient oxidant. The reactions proceed with unprecedented low catalyst
loading of 3-4 mol% and provide the amination of substituted arenes with up to 66:1 regioisomeric control. We expect this catalyst to
be of successful applicability in related oxidative transformations as well.

Experimental Section
Representative synthesis of protected anilines using preformed diaryliodonium salts: The respective nitrogen source (0.15 mmol, 1.0 equiv.)
was dissolved in 1,2-dichloroethane (0.5 mL) and K2CO3 (1.0 equiv.) and diphenyliodonium hexafluorophosphate (1.0 equiv.) were added. The mixture
was stirred at rt for 24 h and then washed with water, extracted with CH2Cl2 (10 mL x 3), dried over Na2SO4 and concentrated under reduced pressure.
The crude product was purified by flash chromatography (n-hexane/EtOAc, 95/5, v/v).
Synthesis of 1,3-diacetoxy-1,3-dihydro-1,3,2-benzooiodooxole (7): In a Schlenk tube under argon atmosphere, 1,2-diiodobenzene (40 µL, 0.3
mmol) was dissolved in glacial acetic acid (2.0 mL) and the mixture was warmed to 30 oC. Peracetic acid (0.23 mL, 35 wt% in acetic acid, 1.2 mmol)
was added dropwise. After all the peracetic acid had been added, the mixture was stirred for 20 min. Distilled water was added leading to formation of
a white precipitate. The white solid was filtered, washed with water and diethyl ether and afforded the desired title compound in pure form (37 mg, 26%
yield); m.p.: 172-175 oC. 1H-NMR (CDCl3, 500 MHz): δ = 2.09 (s, 6H), 7.61-7.65 (m, 2H), 8.01-8.05 (m, 2H). 13C-NMR (CDCl3, 125 MHz): δ = 21.6,
120.1, 131.9, 135.3, 178.4. IR (cm-1): 1629, 1364, 1301, 740, 666, 550, 471. HRMS (MALDI+): calc. for [C8H7I2O3]+: 404.8479; found: 404.8443 [MOAc].

Catalytic synthesis of protected anilines using catalyst 4g: The respective nitrogen source (0.15 mmol, 1.0 equiv.) was dissolved in a mixture of
1,2-dichloroethane and 1,1,1,3,3,3-hexafluoro-2-isopropanol (1/1, v/v) (0.5 mL). 1,2-Diiodobenzene (3 mol%), benzene (12.0 equiv.), peracetic acid
35% wt (1.3 equiv.) and trifluoroacetic acid (5.0 equiv.) were added in the order. The mixture was stirred at rt for the time indicated and then washed
with water, extracted with CH2Cl2 (10 mL x 3), dried over Na2SO4 and concentrated under reduced pressure. The crude was purified by flash
chromatography (n-hexane/EtOAc, 95/5, v/v).
Full product characetrization and additional experimental details are given in the Supporting Information.

Acknowledgements
We thank F. Hoffmann-La Roche Ltd., the Spanish Ministry for Economy and Competitiveness and FEDER (CTQ2014-56474R grant
to K. M., Severo Ochoa Excellence Accreditation 2014-2018 to ICIQ, SEV-2013-0319) for financial support and Dr. E. EscuderoAdán for the X-ray analysis.
Keywords: Amination • Arenes • C-H Functionalization • Catalysis • Hypervalent Iodine
[1]

[2]
[3]

[4]

[5]

[6]

[7]

[8]

[9]
[10]
[11]
[12]

[13]

[14]
[15]

a) A. Ricci, Modern Amination Methods, Wiley-VCH, Weinheim, 2000; b) A. Ricci, Amino Group Chemistry: From Synthesis to the Life Sciences, WileyVCH, Weinheim, 2008; c) R. Hili, A. K. Yudin, Nature Chem. Biol. 2006, 2, 284; d) Chiral Amine Synthesis: Methods, Developments and Applications; T. C.
Nugent (Ed.) Wiley-VCH, Weinheim, 2010.
The Chemistry of Anilines, Z. Rappoport (Ed.), Vol. 1,2, J. Wiley Sons, New York 2007.
2
a) J. Jiao, K. Murakami, K. Itami, ACS Catal. 2016, 6, 610; b) Amination and Formation of sp C-N Bonds, M. Taillefer, D. Ma (Eds.), Topics in Organomet.
Chem. 46, Springer, Berlin Heidelberg, 2012; c) F. Collet, R. H. Dodd, P. Dauban, Chem. Commun. 2009, 5061; d) S. H. Cho, J. Y. Kim, J. Kwak, S.
Chang, Chem. Soc. Rev. 2011, 40, 5068; e) M.-L. Louillat, F. W. Patureau, Chem. Soc. Rev. 2014, 43, 901; f) C. Liu, H. Zhang, W. Lei, Chem. Rev. 2011,
111, 1780.
a) J. F. Hartwig, In Handbook of Organopalladium Chemistry for Organic Synthesis; E. Negishi, Ed.; Wiley-Interscience: New-York, 2002; p 1051; b) L.
nd
Jiang, S. L. Buchwald, Metal-Catalyzed Cross-Coupling Reactions, 2 Ed.; Wiley-VCH: Weinheim, Germany, 2004; Vol. 2, p 699; c) A. R. Muci, S. L.
Buchwald, Top. Curr. Chem. 2002, 219, 131; d) J. F. Hartwig, Synlett 2006, 9, 1283; e) J. F. Hartwig, Acc. Chem. Res. 2008, 41, 1534; f) D. S. Surry, S. L.
Buchwald, Chem. Science 2011, 2, 27; g) J. Kim, H. J. Kim, S. Chang, Eur. J. Org. Chem. 2013, 3201.
a) F. Ullmann, J,. Bielecki, Ber. Dtsch. Chem. Ges. 1901, 34, 2174; b) F. Ullmann Justus Liebigs Ann. Chem. 1904, 332, 38; c) G. Evano, N. Blanchard, M.
Toumi, Chem. Rev. 2008, 108, 3054; d) R. Giri, J. F. Hartwig, J. Am. Chem. Soc. 2010, 132, 15860; e) D. S. Surry, S. L. Buchwald, Chem Science 2010, 1,
13; f) S. H. Cho, J. Y. Kim, J. Kwak, S. Chang, Chem. Soc. Rev. 2011, 40, 5068.
a) K. Shin, H. Kim, S. Chang, Acc. Chem. Res. 2015, 48, 1040; b) A. R. Dick, M. S. Remy, J. W. Kampf, M. S. Sanford, Organometallics 2007, 26, 1365; c)
R. Shrestha, P. Mukherjee, Y. Tan, Z. C. Litman, J. F. Hartwig, J. Am. Chem. Soc. 2013, 135, 8480; d) L. Wang, D. L. Priebbenow, W. Dong, C. Bolm, Org.
Lett. 2014, 16, 1650; e) H. Xu, X. Quiao, S. Yang, Z. Shen, J. Org. Chem. 2014, 79, 4414.
Selected recent work: a) G. B. Boursalian, M.-Y. Ngai, K. N. Hojczyk, T. Ritter, J. Am. Chem. Soc. 2013, 135, 13278; b) A. M. Martínez, N. Rodriguez, R. G.
Arrayás, J. C. Carretero, Chem. Commun. 2014, 50, 2801; c) A. A. Kantak, L. Marchetti, B. DeBoef, Chem. Commun. 2015, 51, 3574; d) D. Zhu, G. Yang,
J. He, L. Chu, G. Chen, W. Gong, K. Chen, M. D. Eastgate, M. J.-Q. Yu, Angew. Chem. Int. Ed. 2015, 54, 2497; e) C. J. Park, S. Chang, Angew. Chem. Int.
Ed., 2015, 54, 14103; f) Y. Park, S. Jee, J. G. Kim, S. Chang, Org. Process Res. Dev. 2015, 19, 1024; g) Y. Park, K. T. Park, J. G. Kim, S. Chang, J. Am.
Chem. Soc., 2015, 137, 4534; h) K. Shin, H. Kim, S. Chang, Acc. Chem. Res., 2015, 48, 1040.
For pertinent reviews on iodine(III)-reagents: a) V. V. Zhdankin, Hypervalent Iodine Chemistry Preparation, Structure and Synthetic Applications of
Polyvalent Iodine Compounds, Wiley, Chichester 2013; b) M. S. Yusubov, V. V. Zhdankin, Reef. Tech. 2015, 1, 49; c) V. V. Zhdankin, J. Org. Chem. 2011,
76, 1185; d) A. Duschek, S. F. Kirsch, Angew. Chem. 2011, 123, 1562; Angew. Chem. Int. Ed. 2011, 50, 1524; e) S. Schäfer, T. Wirth, Angew. Chem.
2010, 122, 2846; Angew. Chem. Int. Ed. 2010, 49, 2786; f) M. Ngatimin, D. W. Lupton, Aust. J. Chem. 2010, 63, 653; g) M. S. Yusubov, D. V. Maskaev, V.
V. Zhdankin, Arkivoc 2009, 1, 370; h) V. V. Zhdankin, P. J. Stang, Chem. Rev. 2008, 108, 5299; i) M. A. Ciufolini, N. A. Braun, S. Canesi, M. Ousmer, J.
Chang, D. Chai, Synthesis 2007, 3759; j) Top. Curr. Chem. 2003, Vol. 224 (Ed.: T. Wirth), Springer, Berlin; k) V. V. Zhdankin, P. J. Stang, Chem. Rev.
2002, 102, 2523; l) P. J. Stang, V. V. Zhdankin, Chem. Rev. 1996, 96, 1123.
a) H. C. Seung, J. Yoon, S. Chang, J. Am. Chem. Soc. 2011, 133, 5996; b) H. J. Kim, J. Kim, S. H. Cho, S. Chang, J. Am. Chem. Soc. 2011, 133, 16382.
A. A. Kantak, S. Potavathri, R. A. Barham, K. M. Romano, B. DeBoef, J. Am. Chem. Soc. 2011, 133, 19960.
R. Samanta, I. Lategahn, A. P. Antonchick, Chem. Commun. 2012, 48, 3194.
Intramolecular reactions: see ref. 9a and a) A. P. Antonchick, R. Samanta, K. Kulikov, J. Lategahn, Angew. Chem. 2011, 123, 8764; Angew. Chem. Int. Ed.
2011, 50, 8605; b) X. Ban, Y. Pan, Y. Lin, S. Wang, Y. Du, K. Zhao, Org. Biomol. Chem. 2010, 10, 3606; c) E. Malamidou-Xenikaki, S. Spyroudis, M.
Tsanakopoulou, D. Hadjipavlou-Litina, J. Org. Chem. 2009, 74, 7315; d) Y. Du, R. Liu, G. Linn, K. Zhao, Org. Lett. 2006, 8, 5919; e) Y. Du, R. Liu, G. Linn,
K. Zhao, Org. Lett. 2006, 8, 5919; f) J. Huang, Y. He, Y. Wang, Q. Zhu, Chem. Eur. J. 2012, 18, 13964; g) X. Ban, Y. Pan, Y. Lin, S. Wang, Y. Du, K. Zhao,
Org. Biomol. Chem. 2012, 10, 3606; h) S. K. Alla, R. K. Kumar, P. Sadhu, T. Punniyamurthy, Org. Lett. 2013, 15, 1334; i) Y. Chi, W.-X. Zhang, Z. Xi, Org.
Lett. 2014, 16, 6274; j) S. Maiti, P. Mal, Adv. Synth. Catal. 2015, 357, 1416; k) He, Y.; Huang, J.; Liang, D.; Liu, L.; Zhu, Q. Chem. Commun. 2013, 49,
7352; l) Y. Chi, W.-X. Zhang, Z. Xi, Org. Lett. 2014, 16, 6274.
Intermolecular reactions:see refs. 9b, 10, 11 and a) N. Itoh, T. Sakamoto, E. Miyazawa, Y. Kikugawa, J. Org. Chem. 2002, 67, 7424; b) R. Samantha, J.
Lategahn, A. P. Antonchick, Chem. Commun. 2012, 48, 3194; c) S. Manna, P. O. Serebrennikova, I. A. Utepova, A. P. Antonchick, Org. Lett. 2015, 17,
4588; d) J. A. Souto, C. Martínez, I. Velilla, K. Muñiz, Angew. Chem. 2012, 125, 1363; Angew. Chem. Int. Ed. 2013, 52, 1324; e) L. Fra, A. Millán, J. A.
Souto, K. Muñiz, Angew. Chem. 2014, 126, 7477; Angew. Chem. Int. Ed. 2014, 53, 7349; f) A. Pialat, J. Bergès, A. Sabourin, R. Vinck, B. Liégault, M.
Taillefer, Chem. Eur. J. 2015, 21, 10014; g) Y. Yang, X. Wu, J. Han, S. Mao, X. Quian, L. Wang, Eur. J. Org. Chem. 2014, 31, 6854.
Reviews: a) R. Narayan, S. Manna, A. P. Antonchick, Synlett 2015, 26, 1785; b) R. Samanta, K. Matcha, A. P. Antonchick, Eur. J. Org. Chem. 2013, 5769.
a) Y. Kita, H. Tohma, K. Hatanaka, T. Takada, S. Fujita, S. Mitoh, H. Sakurai, S. Oka, J. Am. Chem. Soc. 1994, 116, 3684; b) Y. Kita, T. Takada, H. Tohma,
Pure Appl. Chem. 1996, 68, 627.

[16]

[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]

For general reviews on iodine(I/III) catalysis in homogeneous oxidation: a) R. D. Richardson, T. Wirth, Angew. Chem. 2006, 118, 4510; Angew. Chem. Int.
Ed. 2006, 45, 4402; b) M. Ochiai, K. Miyamoto, Eur. J. Org. Chem. 2008, 4229; c) M. Ochiai, Chem. Rec. 2007, 7, 12; d) T. Dohi, Y. Kita, Chem. Commun.
2009, 2073; e) M. Uyanik, K. Ishihara, Chem. Commun. 2009, 2086; f) F. V. Singh, T. Wirth, Chem. Asian J. 2014, 9, 950; g) M. Romero, T. H. Wöste, K.
Muñiz, Chem. Asian J. 2014, 9, 972.
T. Dohi, A. Maruyama, Y. Minamitsuji, T. Takenaga, Y. Kita, Chem. Commun. 2007, 43, 1224.
a) F. M. Beringer, S. A. Galton, S. J. Huang, J. Am. Chem. Soc. 1962, 84, 2819; b) P. Kazmierczak, L. Skulski, Synthesis 1995, 8, 1027; c) T. Dohi, N.
Yamaoka, I. Itani, Y. Kita, Aust. J. Chem. 2011, 64, 529.
F. Tinnis, E. Stridfeldt, H. Lundberg, H. Adolfsson, B. Olofsson, Org. Lett. 2015, 17, 2688.
See Supporting Information for details.
For a previous report on copper-catalysed C-H amination with Troc-amides: A. John, J. Buyn, K. M. Nicholas, Chem. Commun. 2013, 49, 10965.
a) W. Wolf, E. Chalekson, J. Org. Chem. 1967, 32, 3239; b) For the bis-tosylate analogue see: G. F. Koser, R. C. Wettach, J. Org. Chem. 1980, 45, 1542.
X-ray crystallographic data for compound 7 have been deposited with the Cambridge Crystallographic Data Centre database (http://www.ccdc.cam.ac.uk/)
under code CCDC 1451743.
T. Dohi, N. Takenaga, K. Fukushima, T. Uchiyama, D. Kato, M. Shiro, H. Fujioka, Y. Kita, Chem. Commun. 2010, 46, 7697.
For general reports on reactivity and catalyst structure relationship: a) M. Uyanik, K. Ishihara, J. Synth. Org. Chem. Jpn. 2012, 70, 1116; b) M. Uyanik, T.
Yasui, K. Ishihara, Angew. Chem. 2013, 125, 9385; Angew. Chem. Int. Ed. 2013, 52, 9215; c) S. Haubenreisser, T. H. Wöste, C. Martínez, K. Ishihara, K.
Muñiz, Angew. Chem. 2016, 128, 422; Angew. Chem. Int. Ed. 2016, 55, 413.

Entry for the Table of Contents (Please choose one layout)

FULL PAPER
Nicola Lucchetti, Michelangelo Scalone,
Serena Fantasia, Kilian Muñiz *
Page No. – Page No.

Text for Table of Contents

An Improved Catalyst for Iodine(I/III)Catalysed Intermolecular C-H
Amination

Additional Author information for the electronic version of the article.
Kilian Muñiz: 0000-0002-8109-1762
Author:
Author:

ORCID identifier
ORCID identifier