Intramolecular Aryl Migration of Diaryliodonium Salts: Access to ortho-Iodo Diaryl Ethers

Article abstract of DOI:10.1002/anie.201806405

By using vicinal trifluoromethanesulfonate-substituted diaryliodonium salts, a novel approach was developed for the synthesis of ortho-iodo diaryl ethers by intramolecular aryl migration. The reaction conditions are mild with a broad substrate scope. Mechanistic insight suggests a sulfonyl-directed nucleophilic aromatic substitution pathway. Additionally, the product ortho-iodo diaryl ethers serve as versatile synthons as demonstrated with several coupling reactions. Furthermore, a useful thyroxine analogue of the 3-iodo-l-thyronine (3-T₁) derivative was synthesized by this aryl migration procedure.

Full text of DOI:10.1002/anie.201806405

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International Edition: DOI: 10.1002/anie.201806405
German Edition: DOI: 10.1002/ange.201806405
Hypervalent Compounds
Intramolecular Aryl Migration of Diaryliodonium Salts: Access to
ortho-Iodo Diaryl Ethers
Huangguan Chen, Jianwei Han,* and Limin Wang*
Abstract: By using vicinal trifluoromethanesulfonate-substi-
tuted diaryliodonium salts, a novel approach was developed for
the synthesis of ortho-iodo diaryl ethers by intramolecular aryl
migration. The reaction conditions are mild with a broad
substrate scope. Mechanistic insight suggests a sulfonyl-
directed nucleophilic aromatic substitution pathway. Addition-
ally, the product ortho-iodo diaryl ethers serve as versatile
synthons as demonstrated with several coupling reactions.
Furthermore, a useful thyroxine analogue of the 3-iodo-l-
thyronine (3-T1) derivative was synthesized by this aryl
migration procedure.
By exploiting their intrinsic reactivity, diaryliodonium salts
are frequently employed as aromatic electrophiles in aryl-
transfer processes.[1] Over the past decades, the reactivity
resulted in a growing number of useful carbon–carbon or
carbon–heteroatom bond-formation reactions with either
metal catalysts or strong bases as promoters,[1,2] in which the
hyper nucleofuge of the aryliodo moiety facilitates the
reaction efficiency and excellent selectivity (Scheme 1a).[3]
In a search for the synthetic potential of aryliodine(III)
reagents, ortho-substituted iodonium salts are tremendously
attractive for discovering novel reaction pathways.[4] Cyclic
iodonium salts, in which the two aryl groups ortho to the
iodine atom are bridged (A, Scheme 1b), have been widely
used to form tricyclic aromatics.[5] Apart from cyclic iodonium
salts, it is a fact that the coordinating substituents in the
ortho position of acylic diaryliodonium salts have beneficial
effects on reactive properties.[6] In this regard, many pseudo-
cyclic iodonium derivatives were prepared by the group of
Zhdankin and others, and were employed as oxidants for
synthetic applications.[7] Notably, the structures of B and C in
Scheme 1b, including a trimethylsilyl and boronic acid group,
respectively, were used as efficient benzyne precursors.[8]
Recently, the group of Legault reported new trifluoroborate
Scheme 1. Background work on the activation of diaryliodonium salts
in arylations and this work. TMS=trimethylsilyl.
zwitterions, bearing a neighboring trifluoroborate moiety, in
the arylation of phenolates (D, Scheme 1b).[9] Given our
À
interest in exploring the activation of vicinal C H bonds of
diaryliodonium salts for efficient synthesis of aromatic com-
pounds (Scheme 1c),[10] we hypothesized that iodonium salts
that incorporate a heteroatom in the ortho position might
have a neighboring effect, thereby leading to unprecedented
reactivity. Guided by this consideration, a trifluoromethane-
sulfonate group (OTf) was introduced to the ortho position of
acyclic diaryliodonium salts (E, Scheme 1d), and the struc-
ture of its derivative was elucidated by X-ray crystallographic
analysis.[11]
[*] H. Chen, Prof. Dr. J. Han, Prof. Dr. L. Wang
Key Laboratory for Advanced Materials, Institute of Fine Chemicals
School of Chemistry & Molecular Engineering
East China University of Science and Technology
130 Meilong Road, Shanghai 200237 (China)
E-mail: jianweihan@ecust.edu.cn
In nearly all iodonium arylation reactions to date, the
reactivity pattern is centered on intermolecular arylations
with a liberated aryl iodide as a byproduct (Schemes 1a and
c).[1] Interestingly, the iodonium salts of E could undergo
intramolecular aryl migration to generate ortho-iodo diaryl
ethers under basic conditions without wasting the aryl
residues (Scheme 1d).[12] Herein, we describe the detailed
results. It is worth mentioning that ortho-iodo diaryl ethers
wanglimin@ecust.edu.cn
Prof. Dr. J. Han
Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis
Shanghai Institute of Organic Chemistry
The Chinese Academy of Sciences
À
were sterically hindered and the C I bond was fragile under
345 Lingling Road, Shanghai 200032 (China)
the classical Ullman reaction conditions.[13]
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201806405.
To begin our studies, we chose mesityl(2-((trifluorome-
thylsulfonyl)oxy)phenyl)iodonium tosylate (1a) as the model
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substrate and the reaction was performed in the presence of
2.0 equivalents of a base, with acetonitrile as the solvent, at
258C (Table 1). To our delight, the aryl migration product 2aa
was obtained in 76% yield after 12 hours when potassium
carbonates were employed (entry 1). Subsequently, various
ment revealed that the reaction did not occur without Cs2CO3
(entry 20). Pleasingly, the yield was improved to 91% when
the base loading was decreased to 1.1 equivalents (entry 21).
We also examined the counter anion effect, and the diaryl-
iodonium salt with ÀOTf gave the best yield of 94%
(entry 22).
With the optimized reaction conditions in hand, we
subsequently examined the structural diversity of various
diaryliodonium salts by assessing the substitution effect on
the aryl motif. Substrates with a broad range of substitutions
on the benzene ring (Ar2) were first examined. As shown in
Table 2, electron-neutral, electron-donating, and electron-
withdrawing substituents were generally well-tolerated,
affording the desired products 2ab–at bearing hydrogen
(2ab), methyl (2ac–e), dimethyl (2ah–ai), tert-butyl (2af),
methoxy (2ag), halogen (2aj–an), CF3 (2ao–ap), cyano (2aq),
phenyl (2ar), NO2 (2as), and ester (2at) functionalities, in
good to excellent yields, albeit an elevated temperature of
508C was needed for the complete conversion of the starting
materials in some cases. Notably, in the cases of the formation
Table 1: Screening of reaction conditions for the intramolecular aryl
migration of acyclic diaryliodonium salts.[a]
Entry
Base
X
Solvent
T [8C]
Yield [%][b]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21[c]
22
23
24
25
K2CO3
K3PO4
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTf
BF4
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
DCM
PhMe
DMF
THF
DCE
H2O
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
25
25
25
25
25
25
25
25
25
15
10
50
80
25
25
25
25
25
25
25
25
25
25
25
25
76
45
67
20
trace
80
90
trace
51
61
43
89
88
69
74
90
41
74
tBuOK
Na2CO3
NaOAc
NaOH
Cs2CO3
DMAP
DBU
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
–
Table 2: Scope of diverse acyclic diaryliodonium salts for the synthesis of
ortho-iodo diaryl ethers.[a]
n.d.
n.r.
91
94
84
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
PF6
Br
86
84
[a] Reaction conditions: 1a (0.3 mmol), base (0.6 mmol, 2 equiv) in
5 mL solvent, temperature (see table). [b] Yield of isolated product.
[c] 1.1 equiv of base was used. n.d.=not determined, n.r.=no reaction,
Ts =4-toluenesulfonyl.
bases including K3PO4, tBuOK, Na2CO3, NaOAc, NaOH, and
Cs2CO3 were screened, and Cs2CO3 proved to be the best
choice, affording 2aa in 90% yield (entries 2–7). Additionally,
organic bases such as DMAP (4-dimethylaminopyridine) and
DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) were also evalu-
ated in the reaction. As a result, DMAP was inefficient and
DBU gave a moderate yield of 51% (entries 8 and 9).
Elevating the reaction temperature gave comparable yields of
2aa, whereas the yields were significantly decreased at low
temperatures (entries 10–13). Further solvent screening,
including DCM, toluene, DMF, THF, DCE, and water,
showed that DMF also afforded 2aa in 90% yield. Of note,
when the reaction was conducted in water, 2aa was not
detected because of the insolubility of 1a, as well as its
decomposition in aqueous alkaline solution. However, an
intermediate was isolated in this case by a filtration, which
could transform into 2aa in CH3CN. Next, a control experi-
[a] Reaction conditions: 1 (0.3 mmol), Cs2CO3 (0.33 mmol) in 5 mL
MeCN, 258C, 12 hours. Yield is that of product isolated after column
chromatography. [b] Reaction temperature was 508C.
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of 2as and 2at, the byproducts 4-nitrophenyl trifluorometha-
trifluoromethanesulfonyl group has a cationic character was
nesulfonate (3; 26%) and methyl 4-(((trifluoromethyl)sulfo-
nyl)oxy)benzoate (4; 7%), respectively, were isolated,
together with 2-iodophenyl trifluoromethanesulfonate (5; 29
and 5% yield, respectively). To account for the formation of 3
and 4, electron-deficient diaryliodonium salts probably pro-
ceeded through two competing reaction pathways by either
direct substitution with the anion or intramolecular rear-
rangement.[14] Gratifyingly, when the symmetric diaryliodo-
nium salts 1au was employed in the reaction, one of the OTf
substituents was retained and the product 2au was isolated in
84% yield. The reaction is also compatible with diaryliodo-
nium salts containing naphthalene moieties (2av–aw). The
substrate 1ax, bearing a bulky aryl group with 2,4,6-triiso-
propyl substituents, furnished the diaryl ether 2ax in 83%
yield, and the structure of 2ax was verified by the X-ray
crystallographic analysis.[15] We next turned our attention to
the other aryl moiety (Ar1) of the diaryliodonium salts. The
reactions all went smoothly to afford the desired products
2ba–ga in nearly quantitative yields when either the methyl,
tert-butyl, or halogen substituents were positioned at either
the meta or para position to the iodine. The trifluoromethyl-
substituted 2ha was obtained in a good yield of 91%.
Interestingly, substrates bearing electron-withdrawing
groups, such as NO2 or an ester group, furnished the products
of 2ia, 2ka, and 2la in 72–85% yields without the detection of
byproducts, which was not the case in the formation of 2as
and 2at. Importantly, the reaction also led to the polyhalo-
genated ortho-iodo diaryl ethers 2ma–qa in excellent yields,
ethers which are useful as fine chemicals.
suggested by 1H and 19F NMR analyses and ESI-TOF spectra
of an isolated mixture of 1a upon treatment under basic
conditions.[17] An extremely unstable compound was observed
in polar form by thin-layer chromatography when the
reaction was conducted in either MeCN at À308C or in
water at 258C, and it was converted into 2aa immediately. The
base was essential to the reaction for trapping the anion and
accelerating dissociation of the sulfonyl group. The reaction in
Scheme 2c demonstrates that the p-toluenesulfonyl cation is
the leaving group in the reaction, and tosylmorpholine (6) was
obtained in 73% yield, which is the same as that of 2aa.
Next, ortho-iodo diaryl ether products as a family of
synthetically versatile synthons were readily converted into
important aromatic building blocks. Taking advantage of
À
highly reactive C I bond of 2ab, we performed a series of
subsequent synthetic manipulations to transform 2ab into
functional molecules (Scheme 3).[13b,18] For example, treat-
ment of 2ab with nBuLi and B(OMe)3 led to the correspond-
ing boric acid 7. A Sonogashira cross-coupling reaction
provided the diarylalkyne product 8. Ullmann reaction of
2ab with either indole or phenol as nucleophiles, in the
presence of copper catalysts, gave the N-aryl indole 9 and
diaryl ether 14, respectively. Suzuki coupling of 2ab with 4-
tolylboronic acid generated the biaryl 10. Intramolecular
À
C H activation for coupling reaction was attempted to
furnish dibenzofuran (11). Additionally, copper-catalyzed
arylation of diethyl malonate with 2ab formed 12 in good
yield of 88%. Palladium-catalyzed Buchwald–Hartwig cross-
coupling in the synthesis of the diaryl amine 13 was
accomplished with aniline.
Mechanistic studies on possible intermediates in aryla-
tions involving hypervalent iodine reagents have been
recently documented.[14,16] A crossover experiment of the
reaction between 1ah and 1ka revealed the intramolecular
manner of the reaction (Scheme 2a). The aryl migration
products are proposed to be generated through a sulfonyl-
directed nucleophilic aromatic substitution pathway. As
shown in Scheme 2b, the transition state wherein the
Scheme 3. Versatility of 2ab in further transformations. a) 1. nBuLi,
THF, À788C; 2. B(OMe)3; 3. HCl, RT. b) Phenylacetylene, Pd(PPh3)4/
CuI, Et3N, reflux. c) Indole, CuI, K2CO3, DMF, 1208C. d) 4-Tolylboronic
acid, Pd(PPh3)4, K2CO3, DMF, 1008C. e) Pd(OAc)2/PCy3-HBF4, K2CO3,
DMA, 1308C; f) Diethyl malonate, CuI/2-pincolinic acid, Cs2CO3, 1,4-
dioxane, 258C. g) PhNH2, Pd(OAc)2/(tBu)3P, NaOtBu, tol., 1008C.
h) Phenol, CuI/2-picolinic acid, K3PO4, DMSO, 958C. DMA=N,N-
dimethylacetamide, DMF=N,N-dimethylformamide, DMSO=dimethyl
sulfoxide, THF=tetrahydrofuran.
Scheme 2. a) Crossover experiment. b) Proposed mechanism for
migration. c) Investigations on the mechanism.
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To highlight the potential utility of the novel aryl
Conflict of interest
migration reaction, an illustrative case is shown in
Scheme 4. We attempted this transformation for the synthesis
of thyroxine analogues. l-thyroxine (T4) and its deiodination
derivative (T3) are essential hormones for maintaining good
The authors declare no conflict of interest.
Keywords: arylation · ethers · hypervalent compounds ·
reaction mechanisms · synthetic methods
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Acknowledgements
The work was supported by the National Nature Science
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National Key Research and Development Program
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Manuscript received: June 4, 2018
Revised manuscript received: June 28, 2018
Version of record online: && &&, &&&&
Angew. Chem. Int. Ed. 2018, 57, 1 – 6
ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Hypervalent Compounds
H. Chen, J. Han,*
L. Wang*
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Intramolecular Aryl Migration of
Diaryliodonium Salts: Access to ortho-
Iodo Diaryl Ethers
Nothing goes to waste: A novel approach
was developed for the synthesis of ortho-
iodo diaryl ethers by intramolecular aryl
migration. Mechanistic insights sug-
gested a sulfonyl-directed nucleophilic
aromatic substitution pathway. One
advantage of this protocol is that neither
of the aryl residues is lost or wasted in the
process. Tf=trifluoromethanesulfonyl.
6
www.angewandte.org
ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2018, 57, 1 – 6
These are not the final page numbers!