A Practical Aryliodine(I/III) Catalysis for the Vicinal Diamination of Styrenes

Article abstract of DOI:10.1002/cssc.201900360

2,6-Disubstituted iodoarenes bearing amide-functionalized side arms are reported as new structures in redox-active iodine(I/III) catalysis. In combination with bis-sulfonimides as nitrogen sources and 3-chloroperbenzoic acid (mCPBA) as benign terminal oxi

Full text of DOI:10.1002/cssc.201900360

Accepted Article
Title: A Practical Aryliodine(I/III) Catalysis for the Vicinal Diamination of
Styrenes
Authors: Kilian Muniz, Eric Cots, Andrea Flores, and R. Martin Romero
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.201900360
Link to VoR: http://dx.doi.org/10.1002/cssc.201900360
A Journal of
www.chemsuschem.org

10.1002/cssc.201900360
ChemSusChem
COMMUNICATION
A Practical Aryliodine(I/III) Catalysis for the Vicinal Diamination of
Styrenes
Eric Cots,[a] Andrea Flores,[a] R. Martín Romero,[a] and Kilian Muñiz*[a,b]
Dedication ((optional))
Abstract: New 2,6-disubstituted iodoarenes bearing amide-
functionalized side arms are reported as novel structures in redox-
active iodine(I/III) catalysis. In combination with bissulfonimides as
nitrogen sources and mCPBA as benign terminal oxidant, they
catalyze the vicinal diamination of styrenes. The obtained reactivity
and selectivity outperforms other iodoarene catalyst candidates. This
protocol provides a sustainable alternative to previous related
protocols for diamination that are based on stoichiometric iodine(III)
reagents.
aryliodine(I/III) catalysis. In this case, a chiral aryliodine C based
on lactamide units[8a] was identified as the superior catalyst.[11]
Stoichiometric
Ts2N
I
NTs2
A (1.2 equiv)
NTs2
R
R
or
HNTs2
PhI(OAc)2
(1.2 eq)
NTs2
A
Enantioselective stoichiometric
I(OAc)2
NMs2
B (1.2 eq),
HNMs2
MeO2C
R
R
O
O
CO2Me
NMs2
Addressing the quest for the design of environmentally benign
oxidation processes, the class of iodine(III) oxidants has
received major attention in the recent past.[1] Their attractiveness
derives largely from their divers reactivity profile, which often
parallels classical transition metal reactivity. In contrast to the
latter, iodine reagents usually do not pose any toxicity problem.
As an additional important feature, product contamination, which
is often encountered as a serious problem in transition metal
promoted introduction of polar heteroaromatic groups, is not an
issue with iodine reagents.
B
Enantioselective catalytic
I
(iPr)2NOC
O
CON(iPr)2
O
NMs2
C
R
R
NMs2
(10-20 mol%)
HNMs2
mCPBA
C
Figure 1. Development of the intermolecular diamination of styrenes based on
iodine(III) reagents and catalysts.
As to a major addition to the growing field of catalysis with small
organic molecules,[2] iodoarene compounds have emerged as
particularly useful catalyst structures in homogeneous oxidation
reactions. In the vast majority of these cases, aryliodine
compounds bearing common aryl cores such as phenyl, tolyl or
anisyl have served as suitable catalyst sources in the presence
of terminal oxidants.[3]
Iodine reagents have also greatly advanced synthetic
methodology for the direct oxidative transformation of alkenes
into 1,2-diamines.[4] This reaction had long been a domain of
transition metal reactivity,[5] in which reagents based on iodine
have added significant synthetic possibilities.
In view of this successful development of a catalytic reaction, it
appeared of general interest to render the parent transformation
with A catalytic as well. In order to devise conditions for such a
productive homogeneous iodine(I/III) catalysis for the vicinal
diamination of styrenes, we applied findings from our earlier
work, which had demonstrated a significantly reduced rate for
the background reaction of styrene epoxidation with the terminal
oxiant mCPBA (3-chloro perbenzoic acid). Much to our surprise,
submitting standard iodoarenes 1a-c to the diamination reaction
led to styrene degradation without any or only little diamination
product being detected (Table 1, entries 1-6). Throughout all
exploration with these aryl iodines, product formation to 5a was
rarely observed and, when detectable, corresponded only to
minor amounts of product. Instead, styrene decomposition
and/or polymerization appeared to be dominant. Changing the
reaction conditions, in particular, the solvent combination
resulted in the appearance of styrene oxide as the major product.
In order to accomplish a suitable reactivity and reaction rate, the
acetamide derivatives 3a,b were synthesized. Following an
earlier related outline from our group,[10] these compounds are
conveniently prepared from the free 2-iodoresorcinols upon
condensation with known N,N-diisopropyl 2-bromo acetamide.[12]
Using 3a as catalyst resulted in an immediate change in reaction
selectivity providing the desired diamination product 5a in 68%
isolated yield (entry 7). At lower temperature, the reaction did
not reach completion and the isolated yield dropped (entry 8).
The same was observed for a change in solvent to a mixture of
ethyl acetate and HFIP (entry 9). Although the expected
complete chemoselectivity in favor of diamination was still
Important transformations in the area of intermolecular reaction
control have identified bissulfonimides as nitrogen sources in
combination with aryliodine(III) reagents.[6,7] Following the
important insight on the active role of iodine-nitrogen bonds in
the active reagents of the general type ArI[N(SO2R)2]2 (A),[6a] an
enantioselective diamination of styrenes could be accomplished
using a chiral, non-racemic lactate-based reagent B (Figure 1).[8-
10]
This chemistry could be extended to an enantioselective
[a]
[b]
Prof. Dr. K. Muñiz, E. Cots, A. Flores, Dr. R. M. Romero,
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
Prof. Dr. K. Muñiz
ICREA, Pg. Lluís Companys 23, 08010 Barcelona (Spain)
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
This article is protected by copyright. All rights reserved.

10.1002/cssc.201900360
ChemSusChem
COMMUNICATION
obtained, the reaction rate dropped. Finally, a related outcome
was obtained for the 4-methyl derivative 3b, which provided
diamination product 5a in 71% isolated yield (entry 10).
the structure of the related chiral catalyst C,[11] the present
achiral derivative shows a significantly more pronounced spatial
arrangement towards the creation of a pocket around the central
iodine. In contrast, the crystal structure of catalyst 3b[13] shows a
molecular constitution that is widely in agreement with the one
from chiral catalyst C. However, it appears that the orientation of
the side chains in these structures does not predetermine the
subsequent catalysis performance, since both catalysts 3a and
3b give comparable performances.
Table 1. Reaction Optimization.
I
I
O
I
O
H3CO
OCH3
O
O
N
N
R
Following the kinetic courses of the respective reactions of
R
1a (R = H)
1b (R = CH3)
1c (R = OCH3)
2
4a with catalysts 1b, 2 and 3b, respectively, by NMR, the
3a (R = H)
3b (R = CH3)
qualitative outcome from Table
1
was confirmed.[14] For
catalyses with 1b, 2, the main products derive from background
oxidation with mCPBA. Only for 3b, diamine 5a was formed.
This reaction provides a significantly more selective reaction
outcome producing diamine 5a with an initial TOF of 0.4/h.
Catalyst (20 mol%),
NMs2
HNMs2 (2.5 equiv),
NMs2
mCPBA (2.0 equiv)
MTBE/HFIP (3/1, v/v), 0 o
F
F
C
5a
4a
Under the optimized conditions, a number of styrenes were
tested for diamination with bismesylimide and bistosylimide,
respectively, as nitrogen sources (Schemes 1 and 2).
Entry
Catalyst
Deviation from Standard Conditions
Yield 5a [%][a]
n.d. (< 10)[b]
n.d. (< 10)
n.d. (< 10)
n.d. (< 10)
n.d. (< 10)
n.d. (< 10)
68
1
2
3
4
5
6
7
8
9
10
1a
1b
1c
1c
2
none
none
I
(iPr)2NOC
CON(iPr)2
O
O
none
CH2Cl2 as solvent
NMs2
R
R'
R'
3a or 3b (20 mol%)
NMs2
none
mCPBA (2.0 equiv)
HNMs2 (2.5 equiv),
2
-10 ºC
MTBE/HFIP (3/1, v/v), 0 o
C
5a-n
NMs2
4a-n
NMs2
3a
3a
3a
3b
none
NMs2
NMs2
NMs2
NMs2
-5 ºC
48
F
5a: 68% (A)[a]
5b: 66% (A)
5c: 58% (A)
55% (B)
NMs2
EtOAc/HFIP as solvent
none
54
71% (B)[b]
74% (B)
NMs2
NMs2
NMs2
71
NMs2
NMs2
[a] Values from entries 1-6 refer to conversion as determined by 1H NMR of the
crude reaction mixture. Entries 7-10 refer to isolated material after purification.
[b] Substrate decomposition observed.
Ph
Cl
5d: 75% (A)
5e: 69% (A)
5f: 51% (A)
70% (B)
70% (B)
57% (B)
NMs2
NMs2
NMs2
NMs2
NMs2
NMs2
F3C
MeO2C
5g: 65% (A)
5h: 77% (A)
5i: 53% (A)
Ph
72% (B)
81% (B)
47% (B)
NMs2
NMs2
NMs2
NMs2
NMs2
MeO
NMs2
NPhth
CN
5k: 51% (A)
5j: 48% (A)
5l: 56% (A)
53% (B)
50% (B)
63% (B)
NMs2
NMs2
NMs2
F
NMs2
F
5m: 71% (A)
5n: 69% (A)
73% (B)
Figure 2. X-ray structures of catalysts 3a and 3b. Side view (top left) and top
view (top right) for catalyst 3a and side view (bottom) for catalyst 3b.
77% (B)
Scheme 1. Iodine-catalyzed intermolecular diamination of styrenes with
[a]
[b]
bismesylimide as nitrogen source.
Conditions A: with 3a as catalyst.
For catalyst 3a, a crystal structure analysis confirms its
Conditions B: with 3b as catalyst. HNPhth = phthalimide.
expected molecular constitution.[13] Interestingly, in contrast to
This article is protected by copyright. All rights reserved.

10.1002/cssc.201900360
ChemSusChem
COMMUNICATION
H
OR'
The corresponding catalytic diamination with bistosylimide
(Scheme 2) proceeds equally well. This reaction was only
explored for 3b as catalyst and again provided selective
diamination products 6a-i including the expected compatibility
with ortho-, meta- and para-substitution, respectively. As to an
additional substrate scope, (E)-stilbene underwent a moderate
formation of the corresponding diamine 6j, while allylbenzene
generated the corresponding diamine 6k in very good yield.
H
O
OR'
N
N
N
H
H
(iPr)2N
N(iPr)2
I
O
O
O
O
O
I
O
O
N
iPr2N
NiPr2
O
R
R
hydrogen bonding
interactions
n -!* interactions
Figure 4. Possible effect of the ortho-substitution: chelation through n-σ*-
interactions (left), and chelation through hydrogen bonding based on either
water or solvent agglomerates (right). N = N(SO2R)2.
I
(iPr)2NOC
O
CON(iPr)2
O
NTs2
The basic catalytic cycle for the vicinal diamination with
catalysts 3a,b is depicted in Figure 3. The reaction starts with an
oxidation of the iodine(I) 3a,b to an iodine(III), which upon
coordination of the bisimido groups provides the active bisimido
iodine(III) catalyst state D. It is important to note that formation
R
R
3b (20 mol%)
NTs2
mCPBA (2.0 equiv)
HNTs2 (2.5 equiv),
MTBE/HFIP (3/1, v/v), 0 o
6a-j
NTs2
4a-j
C
NTs2
NTs2
of
D should proceed through the corresponding iodoso
NTs2
NTs2
NTs2
NTs2
NTs2
NTs2
NTs2
NTs2
NTs2
intermediate and subsequent reaction with the protic
bissulfonimides. A positive effect of the bulky ortho-substituents
may be the prevention of polymeric derivatives formed at the
iodoso state as insightful designed by Zhdankin.[15,16] However,
this should not be the only factor in the present case due to the
inactivity of the related compound 2. It is therefore more
appropriate to assign an active participation of the two ortho-
substituents throughout the reaction as previously discussed for
the related chiral side chain derivatives.[8a,17] This assignment is
also in agreement with an observation throughout the earlier
diacetoxylation by Fujita.[18] This study demonstrated that 2,6-
dialkoxy-substituted iodoarenes are readily oxidized by mCPBA,
and that the interacting side chains prevent the electron-rich
iodoarene catalyst from decomposing to a diaryliodonium salt.
This interaction should be in form of a chelation with the
catalytically active iodine(III) center and may involve either n-σ*-
interactions or hydrogen bonding within agglomerates of protic
HFIP solvent molecules or water (Figure 4). The observation
that only styrenes and structurally related phenyl-substituted
alkenes are compatible with the present catalysts adds to a
recent theoretic model by Jacobsen, Houk and Xue that invokes
arene π-stacking as an additional stabilizing element within
aryliodine(III) catalysts.[19]
F
Cl
6a: 78%
NTs2
6b: 61%
NTs2
6c: 65%
NTs2
Br
F
Me
F3C
6d: 81%
NTs2
6e: 47%
NTs2
6f: 80%
Me NTs2
PhO
6g: 66%
6h: 76%
6i: 54%
NTs2
NTs2
NTs2
NTs2
6j: 38%
6k: 84%
Scheme 2. Iodine-catalyzed intermolecular diamination of styrenes with
bistosylimide as nitrogen source.
O
I
O
O
O
mCPBA +
2 HN(SO2R')2
iPr2N
NiPr2
R
mCBA
H2O +
3a,b
(R'O2S)2N
Ar
In summary, we have described a new pair of achiral
aryliodine catalysts 3a,b that enable a rapid and productive
vicinal diamination of styrenes under the conditions of
sustainable iodoarene catalysis. These compounds outperform
standard aryliodines as catalysts, which are commonly
employed in iodine(I/III) catalysis.
N(SO2R')2
(R'O2S)2N
O
N(SO2R')2
O
I
5,6
O
O
iPr2N
NiPr2
(R'O2S)2N
R
D
N(SO2R')2
Ar
O
I
O
O
O
iPr2N
NiPr2
Ar
Experimental Section
4
R
Synthesis of Catalyst 3a. To a stirred solution of 2-iodobenzene-1,3-diol
(0.944 g, 4 mmol) in 25 mL of dry dichloromethane at room temperature
were added anhydrous pyridine (5 mL) and 2-bromo-N,N-
diisopropylacetamide (1.11 g, 5 mmol). After 37 hours the reaction was
diluted with CH2Cl2 (50 mL) and washed by careful addition of 6N HCl
aqueous solution (3 x 25 mL). The organic layer was dried over NaSO4,
filtered and concentrated under reduced pressure. The residue was
E
Figure 3. Proposed catalytic cycle. R = H, Me; R’ = Me, Tol.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201900360
ChemSusChem
COMMUNICATION
purified by flash chromatography on silica gel using hexane/AcOEt (5/1,
v/v). The product was isolated as a white solid (1.9 g, 3.67 mmol, 92%).
Colorless crystals for X-ray analysis were grown from methanol solution.
Rf: 0.22 (hexane/AcOEt, 3/1, v/v). 1H-NMR (CDCl3, 300 MHz) δ 1.20 (d, J
= 6.6 Hz, 12H), 1.39 (d, J = 6.7 Hz, 12H), 3.36-3.45 (m, 2H), 4.20-4.27
(m, 2H), 4.69 (s, 4H), 6.61-6.64 (m, 2H), 7.17-7.23 (m, 1H) ppm. 13C-
NMR (CDCl3, 75 MHz) δ 20.3, 21.2, 46.2, 48.8, 70.7, 105.8, 130.8, 158.2,
166.3 ppm. IR: 767, 1094, 1226, 1256, 1335, 1452, 1584, 1627, 2970
cm-1.
[3]
[4]
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) P. Finkbeiner, B. Nachtsheim, Synthesis 2013,
45, 977.
a) K. Muñiz, C. H. Hövelmann, E. Campos-Gómez, J. Barluenga, J. M.
González, J. Streuff, M. Nieger, Chem. Asian J. 2008, 3, 776; b) E. L.
Ingalls, P. A. Sibbald, W. Kaminsky, F. E. Michael, J. Am. Chem. Soc.
2013, 135, 8854; c) U. Farid, T. Wirth, Angew. Chem. 2012, 124, 3518;
Angew. Chem. Int. Ed. 2012, 51, 3462; d) Mizar P.; Laverny A.; El-
Sherbini M.; Farid U.; Brown M.; Malmedy F.; Wirth T. Chem. Eur.
J. 2014, 20, 9910; e) P. V. Balaji, S. Chandrasekaran, Tetrahedron
2016, 72, 1095; f) J. Zhang, X. Zhang, W. Wu, G. Zhang, S. Xu, M. Shi
Tetrahedron Lett. 2015, 56, 1505; g) L. Liu, Q. Sun, Z. Yan, X. Liang, Z.
Zha, Y. Yang, Z. Wang, Green Chem. 2018, 20, 3927.
Synthesis of Catalyst 3b. To
a stirred solution of 2-iodo-5-
methylbenzene-1,3-diol (0.125 g, 0.5 mmol) in 5 mL of dry acetone at
room temperature was added anhydrous K2CO3 (0.173 g, 1.25 mmol)
and stirring was continued for 1 hour. 2-Bromo-N,N-diisopropylacetamide
(0.277 g, 1.25 mmol) was then added to the reaction mixture and the
reaction was heated to reflux. After 36 hours the solvent was evaporated,
water was added and it was extracted using CH2Cl2. The organic layers
were dried over NaSO4, filtered and concentrated under reduced
pressure. The residue was purified by flash chromatography on silica gel
using hexane/AcOEt (8/1 to 3/1, v/v). The product was isolated as a
white solid (75%, 0.2 g, 0.375 mmol). Rf: 0.24 (hexane/AcOEt, 3/1, v/v).
1H-NMR (CDCl3, 500 MHz) δ 1.15 (d, J = 6.7 Hz, 12H), 1.35 (d, J = 6.7
Hz, 12H), 2.24 (s, 3H), 3.36 (m, 2H), 4.20 (m, 2H), 4.62 (s, 4H), 6.41 (s,
2H) ppm. 13C-NMR (CDCl3, 500 MHz) δ 20.3, 21.1, 21.9, 46.2, 48.9,
70.7, 73.6, 106.9, 140.7, 157.9, 166.5 ppm.
[5]
[6]
Reviews diamination a) S. De Jong, D. G. Nosal, D. J. Wardrop, D. J.
Tetrahedron 2012, 68, 4067; b) F. Cardona, A. Goti, Nature Chem.
2009, 1, 269; c) C. Martínez, K. Muñiz, J. Org. Chem. 2013, 78, 2168.
a) J. A. Souto, C. Martínez, I. Velilla, K. Muñiz, Angew. Chem. 2013, 4,
1363; Angew. Chem. Int. Ed. 2013, 52, 1324; b) C. Röben, J. A. Souto,
E. C. Escudero-Adán, K. Muñiz, Org. Lett. 2013, 15, 1008, Chem.
Asian J. 2012, 7, 1103; c) R. M. Romero, J. A. Souto, K. Muñiz J. Org.
Chem. 2016, 81, 6118.
[7]
[8]
K. Muñiz, Acc. Chem. Res. 2018, 57, 1507.
a) M. Uyanik, K. Ishihara, J. Synth. Org. Chem. Jpn. 2012, 70, 1116; a)
M. Uyanik, T. Yasui, K. Ishihara, Tetrahedron 2010, 66, 5841; b) M.
Uyanik, T. Yasui, K. Ishihara, Angew. Chem. 2010, 122, 2221; Angew.
Chem. Int. Ed. 2010, 49, 2175; c) M. Uyanik, T. Yasui, K. Ishihara,
Angew. Chem. 2013, 125, 9385; Angew. Chem. Int. Ed. 2013, 52,
9215; d) S. Haubenreisser, T. H. Wöste, C. Martínez, K. Ishihara, K.
Muñiz, Angew. Chem. 2016, 128, 422; Angew. Chem. Int. Ed. 2016, 55,
413; e) M. Fujita, Tetrahedron Lett. 2017, 58, 4409.
General Protocol for the Vicinal Diamination of Styrenes. In a sealed
pyrex tube, styrene 4b (0.5 mmol) was added to a mixture of HNMs2 (2.5
equiv), catalyst 3a or 3b (0.1 mmol, 20 mol%) and mCPBA (1 equiv) in
HFIP (0.45 mL) and MTBE (1.3 mL) at 0 ºC. After 16 h of reaction,
another portion of mCPBA (1 equiv) was added and the final mixture was
stirred for additional 24 h. After a total of 40 h reacting, the mixture was
quenched with NaHCO3 and extracted with CH2Cl2, dried over Na2SO4
and evaporated under reduced pressure. The final crude product was
purified by chromatography (silica gel, hexane/ AcOEt, 17/3 to 2/1, v/v) to
give the pure diaminated product.
[9]
Reviews: a) F. V. Singh, T. Wirth, Chem. Asian J. 2014, 9, 950; b) M.
Romero, T. H. Wöste, K. Muñiz, Chem. Asian J. 2014, 9, 972; c)
[10] C. Röben, J. A. Souto, Y. González, A. Lishchynskyi, K. Muñiz, Angew.
Chem. 2011, 123, 9478; Angew. Chem. Int. Ed. 2011, 50, 9478.
[11] K. Muñiz, L. Barreiro, R. M. Romero, C. Martínez, J. Am. Chem. Soc.
2017, 139, 4354.
Acknowledgements
[12] a) J. Pospisil, M. Potacek, Tetrahedron 2007, 63, 337; b) R. N. Ram, V.
K. Soni, J. Org. Chem. 2015, 80, 8922.
We thank Dr. Eduardo C. Escudero-Adán (ICIQ) for the X-ray
analysis of compound 3a. Financial support was provided by the
Spanish Ministry for Economy and Competitiveness and FEDER
(CTQ2017-88496R grant to K. M.) and the CERCA Program of
the Government of Catalonia.
[13] X-ray crystallographic data for compounds 3a and 3b have been
deposited with the Cambridge Crystallographic Data Centre database
(http://www.ccdc.cam.ac.uk/) under code CCDC 1895651 and CCDC
1898343, respectively.
[14] See Supporting Information for details.
[15] a) A. Yoshimura, V. N. Nemykin, V. V. Zhdankin, Chem. Eur. J. 2011,
17, 10538; b) Y. S. Masakado, Y. Takemoto, Angew. Chem. 2017, 130,
701; Angew. Chem. Int. Ed. 2017, 57, 693; c) C. Zhu, A. Yoshimura, L.
Ji, Y. Wei, V. N. Nemykin, V. V. Zhdankin, Org. Lett. 2012, 14, 3170.
[16] A. Yoshimura, M. S. Yusubov, V. V. Zhdankin, Org. Biomol. Chem.
2016, 14, 4771.
Keywords: Alkenes • Catalysis • Diamines • Iodine • Oxidation
[1]
Monographs and reviews: a) The Chemistry of Hypervalent Halogen
Compounds (Eds.: I. Marek, B. Olofsson), PATAI’s Chemistry of
Functional Groups, Wiley, New York, 2018; b) V. V. Zhdankin,
Hypervalent Iodine Chemistry: Preparation, Structure, and Synthetic
Applications of Polyvalent Iodine Compounds; Wiley, Chichester, UK,
2014; c) Hypervalent Iodine Chemistry. (Ed.: T. Wirth), Top. Curr.
Chem. 373, Springer, Berlin, 2016; d) A. Yoshimura, V. V. Zhdankin,
Chem. Rev. 2016, 116, 3328; e) V. V. Zhdankin, K. Muñiz, J. Org.
Chem. 2017, 82, 11667.
[17] a) A. Flores, E. Cots, J. Bergès, K. Muñiz Adv. Synth. Catal. 2019, 361,
2; b) A. Claraz, G. Masson, Org. Biomol. Chem. 2018, 16, 5386.
[18] M. Shimogaki, M. Fujita, T. Sugimura, Eur. J. Org. Chem. 2013, 7128.
[19] B. Zhou, M. K. Haj, E. N. Jacobsen, K. N. Houk, X.-S. Xue, J. Am.
Chem. Soc. 2018, 140, 15206.
[2]
a) O. A. Wong, Y. Shi, Chem. Rev. 2008, 108, 3958; b) H. Gröger, A.
Berkessel, in Asymmetric Organocatalysis, Wiley-VCH, Weinheim,
2005, c) B. List, Chem. Rev.2007, 107, 5413-5883.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201900360
ChemSusChem
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 2:
COMMUNICATION
Eric Cots, Andrea Flores, R. Martín
Romero, and Kilian Muñiz*
Page No. – Page No.
A Practical Aryliodine(I/III) Catalysis
for the Vicinal Diamination of
Styrenes
Text for Table of Contents
Rapid and productive: A new iodoarene catalyst promotes the vicinal diamination of styrenes and related compounds under mild
reaction conditions with mCPBA as terminal oxidant.
This article is protected by copyright. All rights reserved.