Alternative Strategies with Iodine: Fast Access to Previously Inaccessible Iodine(III) Compounds

Article abstract of DOI:10.1002/anie.201804642

Non-iodinated arenes can be easily and selectively converted into (diacetoxyiodo)arenes in a single step under mild conditions by using iodine triacetates as reagents. The oxidative step is decoupled from the synthesis of hypervalent iodine(III) reagents, which can now be prepared conveniently in a one-pot synthesis for subsequent reactions without prior purification. The chemistry of iodine triacetates was also expanded to heteroatom ligand exchanges to form novel inorganic hypervalent iodine compounds.

Full text of DOI:10.1002/anie.201804642

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Alternative Strategies with Iodine: Fast Access to New Iodine(III)
Compounds
Authors: Tobias Hokamp, Leonardo Mollari, Lewis C. Wilkins, Rebecca
L. Melen, and Thomas Wirth
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: Angew. Chem. Int. Ed. 10.1002/anie.201804642
Angew. Chem. 10.1002/ange.201804642
Link to VoR: http://dx.doi.org/10.1002/anie.201804642
http://dx.doi.org/10.1002/ange.201804642

10.1002/anie.201804642
Angewandte Chemie International Edition
COMMUNICATION
Alternative Strategies with Iodine: Fast Access to New Iodine(III)
Compounds
Tobias Hokamp, Leonardo Mollari, Lewis C. Wilkins, Rebecca L. Melen and Thomas Wirth*
Abstract: Non-iodinated arenes are easily and selectively converted
into (diacetoxyiodo)arenes in a single step under mild conditions
using iodine triacetates as reagents. The oxidative step is decoupled
from the synthesis of hypervalent iodine(III) reagents which can now
be prepared conveniently in a one-pot synthesis for subsequent
reactions without prior purification. The chemistry of iodine
triacetates was also expanded to heteroatom ligand exchanges to
form novel inorganic hypervalent iodine compounds.
linear 3-center 4-electron (3c-4e) bond, the hypervalent bond.[13]
Recent computational results show an alternative assessment of
the bonding situation in such compounds.[14] Conversely, the
iodine(III) reagent IL3 3 with three heteroatom containing ligands
on the iodine has been rarely investigated owing to their relative
15
]
instability.[
Only very few examples of iodine(III)
tris(carboxylates), such as iodine triacetate 4[ 16 ] and iodine
tris(trifluoroacetate) 5[17] have been reported (Figure 1), while
iodotrichloride 6 is commercially available. Compounds 4 and 5
are best prepared by the oxidation of iodine with fuming nitric
acid in the presence of an appropriate carboxylic acid and the
corresponding carboxylic acid anhydride. Alternative oxidants
such as oxone did not lead to the target reagents.[18] However,
structural information of iodine(III) tris(carboxylates) remain
scarce in the literature. Furthermore, the utilization of potential
heteroatom-containing ligands towards ligand exchanges have
been unexplored prior to this work.
Hypervalent iodine compounds have emerged as versatile and
environmentally benign reagents for modern organic chemistry,
where they have contributed to the realization of novel chemical
transformations.[1] Due to their strongly electrophilic character in
combination with the excellent leaving group ability of the
phenyliodonio group, they can react with a broad range of
nucleophiles. Their synthetic applications include oxidation,[2 ]
halogenation,[3] carbon–carbon bond formation,[4] amination[5]
and oxygenation.[6] (Diacetoxyiodo)arenes and similar polyvalent
iodine carboxylates belong to arguably the most important class
of hypervalent iodine compounds. The main route for their
formation is the reaction of iodoarenes with oxidants such as
Oxone®,[7] m-chloroperbenzoic acid,[8] peracetic acid,[9] sodium
perborate[10] or Selectfluor®[11] in the presence of carboxylic acids
to give the corresponding [bis(acyloxy)iodo]arenes. For this
approach, iodoarenes must be prepared by iodinating arenes
before being oxidized in a second step. Furthermore, excess
and side-products of the oxidants must be removed in a
purification step by washing or by recrystallization of the
hypervalent iodine(III) products. Herein, we describe the
development of a one-step synthesis of (diacetoxyiodo)arenes
from non-iodinated arenes through reaction with iodine triacetate
I(OAc)3.[ 12 ] Furthermore, we demonstrate that the iodine(III)
reaction products obtained in such processes can be used in
subsequent reactions without further purification.
Most known hypervalent iodine(III) reagents have structures of
type ArIL2 1 or Ar2IL 2 with Ar being an aryl moiety and L a
heteroatom (O, N, halogen) containing ligand (Figure 1). The
iodine(III) compounds of type 1 have the overall trigonal
bipyramidal geometry with the heteroatom ligands L in the axial
position and the aryl moiety occupying the equatorial positions.
Iodonium salts 2 show a similar geometry with a weakly bonded
heteroatom containing ligand. One aryl moiety is located in the
equatorial position and bound to the central iodine atom by a
covalent bond while the remaining two substituents are located
in the axial positions and, together with the iodine atom, form a
hypervalent 3-center-4-electron bond
I(OAc)3
I(OCOCF3)3
ICl3
4
5
6
L
I
L
I
L
I
Ar
Ar
L
L
1
Ar
2
L
3
Figure 1. Different types of iodine(III) reagents 1 – 6.
In the preparation of 4, two different crystalline polymorphs were
obtained depending on the crystallization temperature, one is in
agreement with the structural information obtained by Birchall
and co-workers.[19] Surprisingly, in the synthesis of 5, crystals of
a new compound 5a were formed. Solid-state X-ray structure
analysis of this compound revealed it to be dimeric in nature with
the iodine atoms connected via a bridging trifluoroacetate ligand
with a nitrosonium ion derived from nitric acid acting as the
counterion (Figure 2).[20] Reaction of 4 with 5a led to a ligand
exchange of the trifluoroacetate and acetate ligands to give
compound
7
I(OCOCF3)2OAc with the more electron-
withdrawing trifluoroacetates occupying the axial positions and
the acetate being located in equatorial position. This was easily
observed in the 1H NMR spectra which showed a clear
downfield shift of the acetate protons in 7 at δ = 2.42 ppm from
that observed for the corresponding protons in 4 (δ = 2.19 ppm).
This reactivity is explained by the molecular orbital description of
the linear three-center-four-electron hypervalent bond in which
the HOMO contains a node at the central iodine atom. This
renders the hypervalent bond highly polarized resulting in the
more electronegative ligands occupying the axial position.[13]
[*]
T. Hokamp, L. Mollari, Dr. L. C. Wilkins, Dr. R. L. Melen, Prof. Dr. T.
Wirth
School of Chemistry, Cardiff University
Main Building, Park Place, Cardiff CF10 3AT (UK)
E-mail: wirth@cf.ac.uk
Homepage: http://blogs.cardiff.ac.uk/wirth/
Supporting information for this article is given via a link at the end of
the document.
1
This article is protected by copyright. All rights reserved.

10.1002/anie.201804642
Angewandte Chemie International Edition
COMMUNICATION
as sodium perborate, Selectfluor®, m-chloroperbenzoic acid or
Oxone® led to complete decomposition of starting material. The
reaction of the arene precursors with I(OAc)3 4 seems to be
currently the only route to the hypervalent compounds 13a and
13b. The reaction of I(OAc)3 4 with 2 equivalents of 12a did not
lead to the corresponding diaryliodonium derivative.
Less electron-rich aromatic systems are almost inert towards
I(OAc)3 4 under these conditions. Anisole 12c reacted very
slowly to 4-methoxy(diacetoxyiodo)benzene 13c (46% conver-
sion after 8 h and 64% conversion after 27 h according to 1H
NMR analysis), while the use of acetic acid as solvent enhanced
the reactivity of 4 dramatically and 13c was obtained in very
good yield after 20 h (87%, entry 3) without formation of the
corresponding ortho-isomer. Chiral arenes can also be used in
this process leading to 13d and 13e (87% and >99%, entries 4
and 5) and even reactions with less reactive arenes such as
mesitylene 12f may be performed at elevated temperatures of
60 ºC forming product 13f in 76% yield (entry 6). Other
substrates such as 3-methoxybenzoic acid 12g or methyl 3,5-
dimethoxybenzoate 12h reacted smoothly to 13g and 13h (72%
and 77% yield, respectively), however, reactivity limits are
touched with meta-xylene 12i leading to product 13i in only 33%
yield. Noteworthy is the incomplete reaction and the formation of
1-iodo-2,4-dimethylbenzene, which can either come from the
thermal instability of 13i or from the thermal instability of 4 as
I(OAc)3 may thermally decompose to IOAc,[13] which is itself
known for its ability to iodinate aromatic compounds.[22] Other
substrates such as 1-methylindole and azulene decomposed in
presence of I(OAc)3 4.
Figure 2. X-ray structures of iodine(III) reagents 5a (left) and 7 (right). Thermal
ellipsoids shown at 50% probability.
We subsequently investigated the behaviour of 4 towards Lewis
acids and bases. In the presence of pyridine, the coordination
compound 8 is obtained, while the addition of the frustrated
Lewis pair (FLP),[21] B(C6F5)3/2,6-lutidine led to further activation
of 4 yielding 9. Here the strong Lewis acid abstracts one acetate
group giving the [(C6F5)3BOAc]– anion with the [(OAc)2I]+ cation
being stabilized by two lutidine Lewis bases which bind in the
axial positions as revealed by solid-state structural analysis.
Here, one acetate moiety remains in the covalent bond and one
coordinates in a bidentate fashion to the iodine (Figure 3).[20] The
iodine atom in iodine tris(trifluoroacetate) 5a is too reactive to
undergo similar ligand exchange with FLPs using the same
conditions. In contrast to 4, compound 5a undergoes single and
double ligand exchange with B(C6F5)3 to form hypervalent iodine
compounds C6F5-I(OCOCF3)2 10 and [(C6F5)2I] [OCOCF3] 11 of
type 1 and 2 that both crystallized from the reaction mixture and
were structurally characterized (see supporting information).[20]
Reaction products of 4 with ligands such as 2,2’-bipyridine, 1,10-
phenanthroline, 2- or 4-dimethylaminopyridine and 4 with FLPs
such as B(C6F3)3/2,6-lutidine, B(C6F5)3/2,4,6-collidine or
B(C6F5)3/tri-tert-butylphosphine could not be obtained.
Table 1. Substrate scope for the one-step synthesis of (diacetoxyiodo)arenes
using I(OAc)3 4.
OAc
I
1 eq. I(OAc)3
4
Ar
H
Ar
OAc
12
13
Time
[h]
Tempera-
ture [ºC]
Yield
[%]
Entry Product
Solvent
CH2Cl2
MeO
OMe
13a
1
1
20
97
I(OAc)2
OMe
MeO
OMe
13b
13c
O
2
3
CH2Cl2
AcOH
1
20
20
95
87
I(OAc)2
Figure 3. X-ray structures of iodine(III) reagents 8 (left) and 9 (right) derived
from 4. Thermal ellipsoids shown at 50% probability.
MeO
20
I(OAc)2
Reagents 4 and 5 were also shown to react as very powerful
electrophiles in electrophilic aromatic substitutions. Due to its
high electron density on the aromatic ring, we started our
investigation by using 1,3,5-trimethoxybenzene 12a as a test
substrate. The reaction of 12a with one equivalent of 4 led to
quantitative formation of 2,4,6-trimethoxy(diacetoxyiodo)-
benzene (13a, 97%) in dichloromethane at room temperature
after 1 hour (Table 1, entry 1), this structure was also confirmed
by X-ray analysis.[20] Similar results were obtained with 1,3-
dimethoxybenzene (12b), which reacted with 4 exclusively to
yield 2,4-dimethoxy(diacetoxyiodo)benzene (13b, 95%, entry 2),
with the selectivity being explained due to the steric hindrance
between the two methoxy-groups. Several attempts to
synthesize 13a and 13b via oxidation of 2-iodo-1,3,5-trimethoxy-
benzene and 1-iodo-2,4-dimethoxybenzene, with oxidants such
O
O
O
MeO
OMe
4
AcOH
5
20
87
I(OAc)2
13d
OMe
O
O
O
O
OMe
5
6
AcOH
AcOH
2
20
60
99
76
I(OAc)2
O
O
13e
MeO
Me
Me
I(OAc)2
13f
20
Me
2
This article is protected by copyright. All rights reserved.

10.1002/anie.201804642
Angewandte Chemie International Edition
COMMUNICATION
obtained in 94% ee, identical to the previously reported reaction
with a hypervalent iodine reagent with two methyl lactate
substituents on either side of the iodine(III) moiety.[25] The one-
step access to chiral hypervalent iodine(III) reagents without the
need for purification will be of large benefit for their synthetic use.
O
MeO
13g
O
7
AcOH
4
60
72
I
OAc
MeO
OMe
13h
8
9
AcOH
AcOH
4
60
60
77
33
I(OAc)2
CO2Me
Ph
OAc
15
.
OAc
BF3 • OEt2, TMSOAc
Ph
Me
Me
CH2Cl2/AcOH (20:1)
(R)-16
13i
41
–78 °C
rt, 12 h
(Method A, 13d: 54%, 52% ee)
(Method B, 13d: 61%, 49% ee)
(Method B, 13e: 57%, 58% ee)
I(OAc)2
MeO
O
O
O
O
O
Less reactive arenes can react with the more reactive iodine
tris(trifluoroacetate) 5/5a. As shown in Scheme 1, benzene,
fluorobenzene or toluene produce the para-substituted
[bis(trifluoroacetoxy)iodo]arenes 14 in high yields.[20,23]
OH
O
O
1 eq.
I(OAc)3
O
4
R
17
CH2Cl2, –78 °C, 5 h
13d/e
AcOH
rt, 2 h
O
O
(S)-18
O
(Method A, 13d: 41%, 59% ee)
(Method B, 13d: 49%, 56% ee)
MeO
Ph
0.5 eq.
12d R = H
12e R = O-(R)-methyl lactate
I(OCOCF3)2
[I(OCOCF3)3]2 (OCOCF3)NO 5a
Ph
O
19
Ph
Ph
TFA/TFFA (3:1)
0 ºC, 3 h
TsOH • H2O, MeOH
CH2Cl2/TFE (10:1)
–78 °C, 2 h
R
R
(R)-20
12
14a R = H, 88%
14b R = F, 80%
14c R = Me, 94%[a]
(Method B, 13e: 58%, 94% ee)
Scheme 3. Stereoselective diacetoxylation, spirolactonization and
rearrangement using isolated 13d/e (Method A) and in situ prepared 13d/e
(Method B).
Scheme 1. Reaction of [I(OCOCF3) 3]2 (OCOCF3)NO 5a with electron-poor
arenes. [a] Reaction in toluene performed at –40 ºC for 12 h.
In conclusion, novel iodine(III) reagents of type IL3 have been
prepared through various readily accessible synthetic processes.
The use of iodine triacylates allowed an alternative strategy for
the rapid synthesis of (diacyliodo)arenes from non-iodinated
arenes. These hypervalent iodine(III) compounds can
conveniently be used in subsequent reactions in a one-pot
synthesis without further purification.
Finally, the isolated [bis(acetoxy)iodo]arenes 13 were applied in
the diacetoxylation of styrene 15 to 16. As no side-product apart
from acetic acid is formed during the atom-economic one-step
synthesis of 13, these reactions were carried out in a one-pot
operation without purification of the iodine(III) reagent 13. Firstly,
styrene 15 was converted within 2 hours using purified 13f and
triflic acid to give 16 in good yield (75%, Scheme 2). Secondly,
13f was prepared in situ from 12f and I(OAc)3 4. Subsequently,
styrene 15 and triflic acid were added to the crude mixture to
afford 16 after 2 hours in comparable yield (78%).
Acknowledgements
We thank the EPSRC National Mass Spectrometry Facility,
Swansea, for mass spectrometric data. We thank Cardiff
University and the Erasmus program (T.M.) for financial support
and the Fonds der Chemischen Industrie for a Kekulé fellowship
(T.H.).
Me
Me
Ph
1 eq. I(OAc)3
4
OAc
15
13f
OAc
AcOH, 60 °C, 20 h
Ph
TfOH, AcOH
rt, 2 h
Me
12f
16 (Method A: 75%)
(Method B: 78%)
Keywords: aromatic substitution • hypervalent iodine • iodine •
Scheme 2. Diacetoxylation of styrene 15 using purified 13f (Method A) and in
situ prepared 13f (Method B).
one-pot reactions • stereoselective synthesis
These results encouraged us to tackle stereoselective reactions
by using the chiral iodine(III) compound 13d in a stereoselective
diacetoxylation of 15 and in the stereoselective spiro-
lactonization of 17 to 18 (Scheme 3). For both reactions, similar
yields and selectivities were obtained with either pre-formed or
in situ generated iodine(III) reagent 13d. Due to the
regioselective iodination, the iodine(III) moiety is not placed in
between the two chiral substituents in 13d. This can be
overcome by treating 12e with 4. Diacetoxylation of styrene 15
with 13e improved the enantiomeric excess of 16 to 58%, which
is slightly less than in a previously described reaction (70% ee)
with a similar hypervalent iodine reagent using the same
conditions.[24] The lower enantiomeric excess presumably results
from a higher electron density in 13e through the third oxygen
substituent. Also, the rearrangement of 19 to 20 was performed
using the reagent 13e generated in situ. Compound 20 was
[1] a) M. Ochiai, Chem. Rec. 2007, 7, 12–23; b) T. Dohi, Y. Kita, Chem.
Commun. 2009, 2073–2085; c) V. V. Zhdankin, Hypervalent Iodine
Chemistry: Preparation, Structure, and Synthetic Applications of
Polyvalent Iodine Compounds, Wiley, New York, 2014; d) T. Kaiho, Iodine
Chemistry And Applications, Wiley, New York, 2015; e) A. Yoshimura, V.
V. Zhdankin, Chem. Rev. 2016, 116, 3328–3435; f) T. Wirth, Hypervalent
Iodine Chemistry, Top. Curr. Chem. 2016, 373, Springer, Berlin.
[2] a) D. G. Ray, G. F. Koser, J. Am. Chem. Soc. 1990, 112, 5672–5673; b)
V. V. Zhdankin, J. T. Smart, P. Zhao, P. Kiprof, Tetrahedron Lett. 2000,
41, 5299–5302; c) H. Tohma, S. Takizawa, T. Maegawa, Y. Kita, Angew.
Chem. Int. Ed. 2000, 39, 1306−1308; Angew. Chem. 2000, 112, 1362–
1364; d) H. Tohma, T. Maegawa, S. Takizawa, Y. Kita, Adv. Synth. Catal.
2002, 344, 328–337; e) S. M. Altermann, S. Schäfer, T. Wirth,
Tetrahedron 2010, 66, 5902–5907.
[3] a) J. Tao, R. Tran, G. K. Murphy, J. Am. Chem. Soc. 2013, 135, 16312–
16315; b) G. C. Geary, E. G. Hope, K. Singh, A. M. Stuart, Chem.
Commun. 2013, 49, 9263–9265; c) N. O. Ilchenko, B. O. A. Tasch, K. J.
Szabó, Angew. Chem. Int. Ed. 2014, 53, 12897–12901; Angew. Chem.
2014, 126, 13111–13115.
[4] a) T. Dohi, Y. Minamitsuji, A. Maruyama, S. Hirose, Y. Kita, Org. Lett.
2008, 10, 3559–3562; b) K. Matcha, R. Narayan, A. P. Antonchick,
3
This article is protected by copyright. All rights reserved.

10.1002/anie.201804642
Angewandte Chemie International Edition
COMMUNICATION
Angew. Chem. Int. Ed. 2013, 52, 7985–7989; Angew. Chem. 2013, 125,
8143–8147; c) M. Shimogaki, M. Fujita, T. Sugimura, Angew. Chem. Int.
Ed. 2016, 55, 15797–15801; Angew. Chem. 2016, 128, 16029–16033.
[5] a) J. A. Souto, P. Becker, A. Iglesias, K. Muñiz, J. Am. Chem. Soc. 2012,
134, 15505–15511; b) P. Mizar, A. Laverny, M. El–Sherbini, U. Farid, M.
Brown, F. Malmedy, T. Wirth, Chem. Eur. J. 2014, 20, 9910–9913; c) K.
Muñiz, L. Barreiro, R. M. Romero, C. Martínez, J. Am. Chem. Soc. 2017,
139, 4354–4357.
[6] a) E. Hatzigrigoriou, A. Varvoglis, M. Bakola–Christianopoulou, J. Org.
Chem. 1990, 55, 315–318; b) U. H. Hirt, M. F. H. Schuster, A. N. French,
O. G. Wiest, T. Wirth, Eur. J. Org. Chem. 2001, 1569–1579; c) M. Fujita,
Y. Ookubo, T. Sugimura, Tetrahedron Lett. 2009, 50, 1298–1300; d) T.
Takesue, M. Fujita, T. Sugimura, H. Akutsu, Org. Lett. 2014, 4634–4637;
e) P. Mizar, T. Wirth, Angew. Chem. Int. Ed. 2014, 53, 5993–5997;
Angew. Chem. 2014, 126, 6103–6107; f) B. Basdevant, C. Y. Legault, J.
Org. Chem. 2015, 80, 6897–6902.
[12]a) R. C. Cambie, D. Chambers, P. S. Rutledge, P. D. Woodgate, J. Chem.
Soc., Perkin Trans. 1 1977, 2231–2235; b) T. Birchall, C. S. Frampton, P.
Kapoor, Inorg. Chem. 1989, 28, 636–639.
[13] a) A. Varvoglis, The Organic Chemistry of Polycoordinated Iodine, VCH,
Weinheim, 1992; b) M. Ochiai in Chemistry of Hypervalent Compounds,
Ed. K. Akiba, Wiley-VCH, New York, 1999.
[14] A. Stirling, Chem. Eur. J. 2018, 24, 1709–1713.
[15] J. W. H. Oldham, A. R. Ubbelohde, J. Chem. Soc. 1941, 368–375.
[16] F. Fichter, S. Stern, Helv. Chim. Acta 1928, 11, 1256–1264.
[17] M. Schmeißer, K. Dahmen, P. Sartori, Chem. Ber. 1967, 100, 1633–1637.
[18]T. Hokamp, A. T. Storm, M. Yusubov, T. Wirth, Synlett 2018, 29, 415–418.
[19] T. Birchall, C. S. Frampton, P. Kapoor, Inorg. Chem. 1989, 28, 636–639.
[20] CCDC-1836715 (4), CCDC-1836708 (5a), CCDC-1836709 (7), CCDC-
1836710 (8), CCDC-1836711 (9), CCDC-1837674 (10), CCDC-1836712
(11), CCDC-1836713 (13a) and CCDC-1836714 (14c) contain the
supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
[7] a) A. A. Zagulyaeva, M. S. Yusubov, V. V. Zhdankin, J. Org. Chem. 2010,
75, 2119–2122; b) M. S. Yusubov, R. Y. Yusubova, V. N. Nemykin, V. V.
Zhdankin, J. Org. Chem. 2013, 78, 3767–3773.
[21] D. W. Stephan, Science 2016, 354, aaf7229.
[8] a) M. Ochiai, Y. Takeuci, T. Katayama, T. Sueda, K. Miyamoto, J. Am.
Chem. Soc. 2005, 127, 12244–12245; b) E. A. Merritt, V. M. T. Carneiro,
L. F. Silva Jr., B. Olofsson, J. Org. Chem. 2010, 75, 7416–7419; c) M.
Iinuma, K. Moriyama, H. Togo, Synlett 2012, 23, 2663–2666.
[22] a) A. L. Henne, W. F. Zimmer, J. Am. Chem. Soc. 1951, 73, 1362–1363;
b) E. M. Chen, R. M. Keefer, L. J. Andrews, J. Am. Chem. Soc. 1967, 89,
428–430.
[23] I. Maletina, V. V. Orda, L. M. Yagupolskii, Zh. Org. Khim. 1974, 10, 294–
[9] J. G. Sharefkin, H. Saltzman, Org. Synth. 1963, 43, 62.
296.
[10] a) A. McKillop, D. Kemp, Tetrahedron 1989, 45, 3299–3306; b) H. Togo,
T. Nabana, K. Yamaguchi, J. Org. Chem. 2000, 65, 8391–8394; c) M. D.
Hossain, T. Kitamura, J. Org. Chem. 2005, 70, 6984–6986.
[24]M. Fujita, M. Wakita, T. Sugimura, Chem. Commun. 2011, 47, 3983–3985.
[25] M. Brown, R. Kumar, J. Rehbein, T. Wirth, Chem. Eur. J. 2016, 22, 4030–
4035.
[11] C. Ye, B. Twamley, J. M. Shreeve, Org. Lett. 2005, 7, 3961–3964.
4
This article is protected by copyright. All rights reserved.

10.1002/anie.201804642
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
Tobias Hokamp, Leonardo Mollari,
Lewis C. Wilkins, Rebecca L. Melen and
Thomas Wirth*
Page No. – Page No.
Alternative Strategies with Iodine:
Fast Access to New Iodine(III)
Compounds
Text for Table of Contents
Fast and efficient access to new iodine(III) reagents and application in synthesis by decoupling the oxidation from the iodination
step.
5
This article is protected by copyright. All rights reserved.