P(NMe2)3-promoted ortho-selective arylation of phenols with diaryliodonium triflates via rhodium catalysis

Article abstract of DOI:10.1016/j.tet.2017.03.055

Rh-catalyzed ortho-selective arylation of free phenol with diaryliodonium triflates to widely existed phenol-containing biaryls have been developed. The use of P(NMe₂)₃, ^tBuOLi and CH₃CN proved to be critical for the ortho-selectivity of this reaction.

Full text of DOI:10.1016/j.tet.2017.03.055

Tetrahedron xxx (2017) 1e5
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P(NMe2)3-promoted ortho-selective arylation of phenols with
diaryliodonium triflates via rhodium catalysis
, b, *
Qi-Sheng Liu a, De-Yin Wang a, Jin-Fei Yang a, Zhong-Yi Ma a, Mengchun Ye a
a State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
b Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Rh-catalyzed ortho-selective arylation of free phenol with diaryliodonium triflates to widely existed
phenol-containing biaryls have been developed. The use of P(NMe2)3, BuOLi and CH3CN proved to be
critical for the ortho-selectivity of this reaction.
© 2017 Elsevier Ltd. All rights reserved.
t
Received 20 January 2017
Received in revised form
17 February 2017
Accepted 21 March 2017
Available online xxx
Keywords:
Arylation
Rhodium
Phenol
Diaryliodonium salts
Biaryls
1. Introduction
Despite this progress, the requirement of para-substituent greatly
restricted the scope of free phenol. And thus, the development of a
Due to wide existence of phenol motif in natural products,
biologically active compounds, and functional materials, the
development of direct functionalization methods of free phenols
has received great attentions over past decades.1 Depending on the
property of reactants and catalysts, these functionalization re-
actions of free phenols generally have four possible site selectiv-
ities, including O-selectivity and C-selectivities (ortho, meta and
para). The development of practical strategies to obtain desired
selectivities is of great interest and also a significant challenge.2
Diaryliodonium salts as powerful electrophilic arylation reagents
have been used in the functionalization reaction of phenol from a
very early stage, while O-arylation was provided at most cases,
especially in the presence of stoichiometric amount of base
(Scheme 1).3 Remarkably, Gaunt and co-workers recently intro-
duced a copper catalyst in this coupling reaction and obtained a
highly para-selective arylation of phenol other than the traditional
O-arylation for the first time.4 Based on the same strategy, Wang
and co-workers subsequently found that ortho-arylation was ach-
ieved exclusively when the para-site was blocked by a substituent.5
more general strategy to obtain ortho-selective arylation in the
reaction of phenol with versatile diaryliodonium salts is still an
elusive challenge.
Inspired by the achievements of Bedford and Inoue on
phosphite-cocatalyst-promoted ortho-arylation of phenol with aryl
halides,6 we envisioned that an appropriate phosphite cocatalyst
could be employed in the reaction of phenol with diaryliodonium
salts to furnish an ortho-selective arylation.7 However, owing to the
instability and reducibility of phosphite compounds and strong
oxidizability of diaryliodonium salts, this attempt is considerably
challenging. First of all, the selection of an appropriate base is a
tricky problem. The base is required for the interaction of phenol
with phosphite cocatalyst, but it could not promote the O-arylation
of phenol; second, the selection of suitable phosphite catalyst is
also difficult because the phosphite compound should be compat-
ible with diaryliodonium salts. The success of this type of coupling
reaction would significantly broaden the scope of coupling partners
of the elegant phosphite-directed CeH functionalization reaction,
which are typically limited with aryl halides and ethylene. Herein
we report the first ortho-selective arylation of phenol with diary-
liodonium salts catalyzed by rhodium-P(NMe2)3 system (Scheme
1).
* Corresponding author. State Key Laboratory and Institute of Elemento-Organic
Chemistry, Nankai University, Tianjin 300071, China.
E-mail address: mcye@nankai.edu.cn (M. Ye).
http://dx.doi.org/10.1016/j.tet.2017.03.055
0040-4020/© 2017 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Liu Q-S, et al., P(NMe2)3-promoted ortho-selective arylation of phenols with diaryliodonium triflates via
rhodium catalysis, Tetrahedron (2017), http://dx.doi.org/10.1016/j.tet.2017.03.055

2
Q.-S. Liu et al. / Tetrahedron xxx (2017) 1e5
85% yield and only trace amount of O-arylated product (entries
1e4). The absence of either rhodium or phosphite catalyst would
result into no desired product. The further investigation of other
reaction parameters, including rhodium species (entries 7 and 8),
temperature (entry 9), base (entries 10e13) and solvent (entries
14e16) still disclosed that the combination of [Rh(COD)Cl]2, tBuOLi
and CH3CN at 130 ꢀC was the best one.
With the above optimized reaction conditions in hand, we first
explored an array of substituted phenols to test the generality of the
reaction. Various ortho-alkylated phenols bearing either less-
hindered Me and Et (Scheme 3, entries 1 and 2), or sterically-
i
t
Scheme 1. ortho-Selective arylation of phenol.
hindered Pr and Bu (entries 3 and 4), were well tolerated in this
reaction, providing the corresponding products in 39e86% yields.
Phenols bearing either ortho electron-donating group (MeO) or
ortho electron-withdrawing group (F) reacted well in the coupling
reaction to deliver the corresponding products in good yields
2. Results and discussion
At the beginning, we selected diphenyliodonium triflate and 2-
tert-butylphenol as model substrates to optimize a wide range of
reaction parameters. Various inorganic bases, from weak base
(KHCO3) to strong base (KOtBu), provided the O-arylated product as
the main product in toluene at 100 ꢀC in the presence of P(NMe2)3
as the cocatalyst. Surprisingly, the use of tBuOLi drastically
improved the ratio of ortho-arylation between O-arylation to 1:1
(see the Supporting Information). Further examination of a series of
solvents revealed that acetonitrile elevated the ratio to about 8:1,
albeit with a moderate total yield (38%). However, further O-ary-
lation of ortho-arylated phenol was observed after a prolonged
period of time, likely owing to the presence of phenyl iodide, a side
product from the consumption of diaryliodonium triflate. And thus,
we next selected 2-ethylphenol and (mesityl) (phenyl) iodonium
triflate as model substrates for further extensive examinations. In
these cases, mesityl iodide as the side product would be inert to the
ortho-arylated products. As shown in Scheme 2, P(NMe2)3 proved
to be the optimal cocatalyst, providing ortho-arylated product in
Scheme 2. Conditions optimization.
Scheme 3. Scope of phenol.
Please cite this article in press as: Liu Q-S, et al., P(NMe2)3-promoted ortho-selective arylation of phenols with diaryliodonium triflates via
rhodium catalysis, Tetrahedron (2017), http://dx.doi.org/10.1016/j.tet.2017.03.055

Q.-S. Liu et al. / Tetrahedron xxx (2017) 1e5
3
(entries 5 and 6). Although 2,3-dimethylated phenol has no big
influence to the yield, the absence to ortho-substituent in 3-
methylated phenol would lead to significant amounts of di ortho-
arylated products. Further increasing the amount of diphenylio-
donium salt to 2.5 equivalents produced diarylated phenol as the
main product in 53% yield (entry 8). Same diaylated reaction was
observed for other phenols without ortho-substituents, like 4-
ethylphenol (entry 9) and simple phenol (entry 10).
Next, the compatibility of a variety of diaryliodonium salts with
this arylation reaction was examined. As shown in Scheme 4,
counter ion proved to be critical for this reaction. Among several
examined counter ions, triflate was the best one (entry 1). Various
substituents on the aryl of (aryl)(mesityl)iodonium salt, including
para-alkyls, ortho-methoxy, and meta-methyl, were all tolerated,
providing the corresponding arylated phenols in 72e83% yields
(entries 2e5). Impressively, the reaction of sterically hindered
arylated iodonium salts, such as 2,6-dimethylphenyl and 2,4,6-
trimethylphenyl, still proceeded smoothly to yield the corre-
sponding products in moderate yields (entries 6 and 7).
Scheme 5. Possible mechanism.
the intermediate B. A subsequent CeH activation and reductive
elimination provided the intermediate D, which exchanged with
free phenol to regenerate the intermediate A along with the for-
mation the desired ortho-aylated product.
According to the reported observations,6 the reaction was pro-
posed to occur as the following procedure (Scheme 5): phenol
bound with P(NMe2)3 and rhodium to produce the intermediate A,
which was then oxidized by (mesityl)(phenyl)iodonium triflate into
3. Conclusion
In summary, we have developed the first example of ortho-se-
lective arylation of free phenol with diaryliodonium triflates. The
use of P(NMe2)3 as the cocatalyst tBuOLi as the base and CH3CN as
the solvent is critical for the high selectivity in the presence of
rhodium catalyst. Current reaction demonstrated that the appro-
priate selection of reaction parameters would be feasible for other
coupling partners beyond traditional aryl halides and ethylene in
the phosphite-promoted CeH functionalization reaction.
4. Experimental section
4.1. General information
Unless otherwise noted, all solvents were received from com-
mercial sources without further purification. Commercially avail-
able reagents were used as received. Non-commercially available
compounds were synthesized following reported protocols. Silica
gel (particle size 40e63 mm) was used for flash column chroma-
tography. GC/MS spectra were recorded on a Thermo Scientific ISQ
Single Quadrupole GC/MS with a flame ionization detector. NMR
spectra were recorded on Bruker AV 400 spectrometer at 400 MHz
(1H NMR), 100 MHz (13C NMR). Proton and carbon chemical shifts
are reported relative to the solvent used as an internal reference.
High resolution mass spectra (HRMS) were recorded on an Agilent
6520 Q-TOF LC/MS with Electron Spray Ionization (ESI) resource.
4.2. ortho-Arylation of phenol
4.2.1. General procedure
t
To a mixture of [Rh(cod)Cl]2 (3.08 mg, 0.00625 mmol), BuOLi
(40.0 mg, 0.5 mmol), diaryliodonium triflate (0.325 mmol, 1.3 eq)
and CH3CN (2.0 mL) in a pressure tube were added phenol
(0.25 mmol) and P(NMe2)3 (8.16 mg, 0.05 mol). The resulting re-
action mixture was stirred at 130 ꢀC for 12 h under N2. After cooling
to room temperature, the mixture was diluted with 10.0 mL ethyl
acetate and 5.0 mL aq. HCl (2 N) and stirred vigorously for 30 min.
Then the solution was extracted by ethyl acetate for three times,
and the combined organic phases were washed with satd. NaCl, and
dried over MgSO4, filtered through a pad of Celite and concentrated
in vacuo. The residue was purified by flash chromatography eluted
Scheme 4. Scope of diaryliodonium salts.
Please cite this article in press as: Liu Q-S, et al., P(NMe2)3-promoted ortho-selective arylation of phenols with diaryliodonium triflates via
rhodium catalysis, Tetrahedron (2017), http://dx.doi.org/10.1016/j.tet.2017.03.055

4
Q.-S. Liu et al. / Tetrahedron xxx (2017) 1e5
with Hexane/AcOEt (30:1).
129.3, 128.8, 128.5, 127.5, 28.0, 15.8.
4.2.2. 3-Ethyl-[1,1'-biphenyl]-2-ol (3a).8a
4.2.11. [1,1':30,100-Terphenyl]-2'-ol (3j).6b
86% yield. Yellow oil. 1H NMR (400 MHz, CDCl3)
d
7.58e7.45 (m,
61% yield. White solid. mp: 100e101 ꢀC. 1H NMR (400 MHz,
4H), 7.43e7.38 (m, 1H), 7.20e7.14 (m, 1H), 7.09 (dd, J ¼ 7.6, 1.6 Hz,
CDCl3) d 7.57e7.52 (m, 4H), 7.50e7.44 (m, 4H), 7.41e7.34 (m, 2H),
1H), 6.94 (t, J ¼ 7.5 Hz, 1H), 5.26 (s, 1H), 2.72 (q, J ¼ 7.5 Hz, 2H), 1.28
7.29e7.22 (m, 2H), 7.05 (dd, J ¼ 7.9, 7.3 Hz, 1H), 5.39 (s, 1H). 13C NMR
(t, J ¼ 7.5 Hz, 3H). 13C NMR (100 MHz, CDCl3)
d
150.1, 137.3, 130.6,
(100 MHz, CDCl3)
120.6.
d 149.3, 137.5, 129.9, 129.3, 128.8, 128.7, 127.6,
129.3, 129.1, 128.7, 127.8, 127.7, 127.6, 120.3, 23.3, 14.0.
4.2.3. 3-Methyl-[1,1'-biphenyl]-2-ol (3b).6b
4.2.12. 3-Ethyl-4'-methyl-[1,1'-biphenyl]-2-ol (4b)
81% yield. Yellow oil. 1H NMR (400 MHz, CDCl3)
d
7.55e7.46 (m,
83% yield. Colorless oil. 1H NMR (400 MHz, CDCl3)
d 7.43e7.29
4H), 7.43 (td, J ¼ 6.7, 1.9 Hz, 1H), 7.20e7.13 (m, 1H), 7.11 (dd, J ¼ 7.7,
(m, 4H), 7.16 (d, J ¼ 7.6 Hz, 1H), 7.08 (d, J ¼ 7.6 Hz, 1H), 6.93 (td,
1.8 Hz, 1H), 6.93 (t, J ¼ 7.5 Hz, 1H), 5.28 (s, 1H), 2.34 (s, 3H). 13C NMR
J ¼ 7.6, 1.5 Hz, 1H), 5.28 (s, 1H), 2.73 (q, J ¼ 7.5 Hz, 2H), 2.43 (s, 3H),
(100 MHz, CDCl3)
d
150.5, 137.3, 130.5, 129.3, 129.2, 129.1, 127.8,
1.28 (td, J ¼ 7.5,1.4 Hz, 3H). 13C NMR (100 MHz, CDCl3)
d 150.2,137.6,
127.7, 124.6, 120.2, 16.2.
134.2, 130.5, 130.0, 129.0, 128.5, 127.6, 127.6, 120.2, 23.3, 21.1, 14.0.
HRMS (ESI) m/z Calcd for C15H16O [MþH]þ 213.1279, Found
213.1271.
4.2.4. 3-(iso-Propyl)-[1,1'-biphenyl]-2-ol (3c).8b
72% yield. Colorless oil. 1H NMR (400 MHz, CDCl3)
d 7.54e7.45
(m, 4H), 7.44e7.37 (m, 1H), 7.24 (dd, J ¼ 7.6, 1.7 Hz, 1H), 7.08 (dd,
J ¼ 7.5, 1.7 Hz, 1H), 6.97 (t, J ¼ 7.6 Hz, 1H), 5.29 (s, 1H), 3.36 (hept,
J ¼ 7.0 Hz, 1H), 1.30 (d, J ¼ 6.9 Hz, 6H). 13C NMR (100 MHz, CDCl3)
4.2.13. 3,40-Diethyl-[1,1'-biphenyl]-2-ol (4c)
70% yield. Yellow oil. 1H NMR (400 MHz, CDCl3)
d 7.46e7.31 (m,
4H), 7.17 (d, J ¼ 7.5 Hz, 1H), 7.09 (d, J ¼ 7.6 Hz, 1H), 6.94 (td, J ¼ 7.6,
d
149.5, 137.4, 134.9, 129.3, 129.2, 127.8, 127.8, 127.4, 125.9, 120.3,
1.5 Hz, 1H), 5.31 (s, 1H), 2.74 (q, J ¼ 7.6 Hz, 4H), 1.30 (td, J ¼ 9.1, 8.4,
27.2, 22.6.
6.8 Hz, 6H). 13C NMR (100 MHz, CDCl3)
d 150.2, 143.9, 134.5, 130.5,
129.1, 128.9, 128.5, 127.7, 127.6, 120.2, 28.5, 23.3, 15.4, 14.04. HRMS
4.2.5. 3-(tert-Butyl)-[1,1'-biphenyl]-2-ol (3d).8b
(ESI) m/z Calcd for C16H18O [MþH]þ 227.1436, Found 227.1422.
39% yield. Colorless oil. 1H NMR (400 MHz, CDCl3)
d 7.56e7.44
(m, 4H), 7.44e7.40 (m, 1H), 7.31 (dd, J ¼ 7.9, 1.7 Hz, 1H), 7.09 (dd,
4.2.14. 3-Ethyl-2'-methoxy-[1,1'-biphenyl]-2-ol (4d)
J ¼ 7.5, 1.7 Hz, 1H), 6.93 (t, J ¼ 7.7 Hz, 1H), 5.45 (s, 1H), 1.45 (s, 9H).
79% yield. Yellow oil. 1H NMR (400 MHz, CDCl3)
d 7.43e7.32 (m,
13C NMR (100 MHz, CDCl3)
d
150.9, 137.2, 136.2, 129.5, 129.43, 128.7,
2H), 7.20 (dd, J ¼ 7.5, 1.7 Hz, 1H), 7.12 (ddd, J ¼ 7.6, 5.9, 1.5 Hz, 2H),
7.06 (dd, J ¼ 8.3, 1.0 Hz, 1H), 6.97 (t, J ¼ 7.5 Hz, 1H), 6.17 (s, 1H), 3.91
(s, 3H), 2.76 (q, J ¼ 7.5 Hz, 2H), 1.28 (t, J ¼ 7.5 Hz, 3H). 13C NMR
127.9, 127.9, 126.6, 119.8, 34.9, 29.6.
4.2.6. 3-Methoxy-[1,1'-biphenyl]-2-ol (3e).8c
(100 MHz, CDCl3) d 155.5, 151.4, 132.6, 132.0, 129.1, 128.8, 128.7,
77% yield. Colorless oil. 1H NMR (400 MHz, CDCl3)
d
7.61 (dd,
127.3, 125.8, 122.0, 120.5, 111.4, 56.0, 23.5, 14.1. HRMS (ESI) m/z
J ¼ 8.2, 1.3 Hz, 2H), 7.43 (t, J ¼ 7.5 Hz, 2H), 7.37e7.30 (m, 1H),
Calcd for C15H16O2 [MþH]þ 229.1229, Found 229.1221.
7.01e6.83 (m, 3H), 5.85 (s, 1H), 3.95 (s, 3H). 13C NMR (100 MHz,
CDCl3)
d
146.8, 142.8, 137.7, 129.2, 128.2, 127.1, 122.7, 119.7, 114.5,
4.2.15. 3-Ethyl-30,5'-dimethyl-[1,1'-biphenyl]-2-ol (4e)
109.6, 56.2.
72% yield. Colorless oil. 1H NMR (400 MHz, CDCl3)
d 7.16 (dd,
J ¼ 7.5, 1.7 Hz, 1H), 7.08 (s, 2H), 7.08e7.05 (m, 2H), 6.93 (t, J ¼ 7.5 Hz,
4.2.7. 3-Fluoro-[1,1'-biphenyl]-2-ol (3f).8d
1H), 5.39 (s, 1H), 2.73 (q, J ¼ 7.6 Hz, 2H), 2.39 (s, 6H), 1.28 (t,
67% yield. Pale yellow solid. mp: 84e86 ꢀC. 1H NMR (400 MHz,
J ¼ 7.5 Hz, 3H). 13C NMR (100 MHz, CDCl3)
d 150.1, 139.0,137.1, 130.4,
129.4, 128.5, 127.8, 127.4, 126.8, 120.1, 23.3, 21.3, 14.0. HRMS (ESI) m/
CDCl3)
7.14e7.05 (m, 2H), 6.92 (td, J ¼ 8.0, 5.3 Hz, 1H), 5.24 (d, J ¼ 4.4 Hz,
1H). 13C NMR (100 MHz, CDCl3)
d
7.58e7.52 (m, 2H), 7.49e7.44 (m, 2H), 7.41e7.35 (m, 1H),
z Calcd for C16H18O [MþH]þ 227.1436, Found 227.1431.
d
151.4 (d, J ¼ 237 Hz), 140.9 (d,
J ¼ 14 Hz), 136.5 (d, J ¼ 3 Hz), 130.4, 129.1, 128.6, 127.8, 125.7 (d,
J ¼ 3 Hz), 120.2 (d, J ¼ 8.0 Hz), 114.6 (d, J ¼ 18 Hz).
4.2.16. 3-Ethyl-20,6'-dimethyl-[1,1'-biphenyl]-2-ol (4f)
39% yield. Colorless oil. 1H NMR (400 MHz, CDCl3)
d 7.33e7.26
(m, 1H), 7.22 (d, J ¼ 8.2 Hz, 3H), 6.98 (t, J ¼ 7.5 Hz, 1H), 6.91 (dd,
4.2.8. 3,4-Dimethyl-[1,1'-biphenyl]-2-ol (3g).8e
J ¼ 7.6, 1.8 Hz, 1H), 4.63 (s, 1H), 2.76 (q, J ¼ 7.5 Hz, 2H), 2.10 (s, 6H),
62% yield. Colorless oil. 1H NMR (400 MHz, CDCl3)
d
7.54e7.41
1.31 (t, J ¼ 7.5 Hz, 3H). 13C NMR (100 MHz, CDCl3)
d 149.9, 138.0,
(m, 4H), 7.39 (t, J ¼ 7.3 Hz, 1H), 6.98 (d, J ¼ 7.6 Hz, 1H), 6.82 (d,
135.0, 130.2, 128.3, 128.2, 127.9, 127.0, 125.9, 120.3, 23.2, 20.3, 14.0.
HRMS (ESI) m/z Calcd for C16H18O [MþH]þ 227.1436, Found
227.1439.
J ¼ 7.7 Hz, 1H), 5.28 (s, 1H), 2.32 (s, 3H), 2.23 (s, 3H). 13C NMR
(100 MHz, CDCl3)
d 150.2, 137.8, 137.6, 129.3, 129.1, 127.6, 126.6,
125.4, 123.0, 121.8, 20.1, 11.8.
4.2.17. 3-Ethyl-20,40,6'-trimethyl-[1,1'-biphenyl]-2-ol (4g)
4.2.9. 4'-methyl-[1,1':30,100-terphenyl]-2'-ol (3h).6b
32% yield. Colorless oil. 1H NMR (400 MHz, CDCl3)
d 7.17 (dd,
53% yield. Colorless oil. 1H NMR (400 MHz, CDCl3)
d
7.60 (dd,
J ¼ 7.5, 1.7 Hz, 1H), 7.02 (s, 2H), 6.94 (t, J ¼ 7.5 Hz, 1H), 6.87 (dd,
J ¼ 7.5, 1.8 Hz, 1H), 4.64 (s, 1H), 2.73 (q, J ¼ 7.5 Hz, 2H), 2.37 (s, 3H),
2.04 (s, 6H), 1.28 (t, J ¼ 7.5 Hz, 3H). 13C NMR (100 MHz, CDCl3)
J ¼ 8.3, 1.4 Hz, 2H), 7.57e7.50 (m, 2H), 7.50e7.43 (m, 3H), 7.40e7.34
(m, 3H), 7.26 (d, J ¼ 7.8 Hz, 1H), 6.97 (d, J ¼ 7.8 Hz, 1H), 5.02 (s, 1H),
2.14 (s, 3H). 13C NMR (100 MHz, CDCl3)
d
149.6, 138.0, 136.8, 135.7,
d 150.1,137.9,137.8,131.9,130.1,128.7,128.2,127.3,125.9,120.2, 23.2,
130.2,129.4,129.3,129.2,128.6,128.5,128.0,127.1,125.7,122.0, 20.4.
21.0, 20.2, 14.0. HRMS (ESI) m/z Calcd for C17H20O [MþH]þ 241.1592,
Found 241.1588.
4.2.10. 50-Ethyl-[1,1':30,100-terphenyl]-2'-ol (3i).8f
65% yield. White solid. mp: 130e131 ꢀC. 1H NMR (400 MHz,
Acknowledgements
CDCl3)
d
7.58 (d, J ¼ 7.6 Hz, 4H), 7.49 (t, J ¼ 7.5 Hz, 4H), 7.39 (t,
J ¼ 7.4 Hz, 2H), 7.14 (s, 2H), 5.29 (s, 1H), 2.68 (q, J ¼ 7.6 Hz, 2H), 1.29
We thank the National Natural Science Foundation of China
(21402096, 21421062 and 21672107), Tianjin Applied Basic
(t, J ¼ 7.6 Hz, 3H). 13C NMR (100 MHz, CDCl3)
d 147.2, 137.8, 136.3,
Please cite this article in press as: Liu Q-S, et al., P(NMe2)3-promoted ortho-selective arylation of phenols with diaryliodonium triflates via
rhodium catalysis, Tetrahedron (2017), http://dx.doi.org/10.1016/j.tet.2017.03.055

Q.-S. Liu et al. / Tetrahedron xxx (2017) 1e5
5
4. Ciana C-L, Phipps RJ, Brandt JR, Meyer F-M, Gaunt MJ. Angew Chem, Int Ed.
2011;50:458.
5. (a) Qian X, Han J, Wang L. Tetrahedron Lett. 2016;57:607 (For a related example
employing electron-rich arene, see);
Research Project and Cutting-edge Technology Research Plan
(14JCYBJC41400).
(b) Wang X, Huang D, Wang X, Zeng X, Wang X, Hu Y. Tetrahedron Lett. 2016;57:
4235.
Appendix A. Supplementary data
6. (a) Bedford RB, Coles SJ, Hursthouse MB, Limmert ME. Angew Chem, Int Ed.
2003;42:112;
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2017.03.055.
(b) Oi S, Watanabe S-I, Fukita S, Inoue Y. Tetrahedron Lett. 2003;44:8665;
(c) Bedford RB, Limmert ME. J Org Chem. 2003;68:8669.
7. For other strategies on ortho-arylation of phenols, see: (a) Wiebe A,
Schollmeyer D, Dyballa KM, Franke R, Waldvogel SR. Angew Chem, Int Ed.
2016;55:11801;
(b) Satoh T, Kawamura Y, Miura M, Nomura M. Angew Chem, Int Ed. 1997;36:
1740;
(c) Truong T, Daugulis O. Chem Sci. 2013;4:531;
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Please cite this article in press as: Liu Q-S, et al., P(NMe2)3-promoted ortho-selective arylation of phenols with diaryliodonium triflates via
rhodium catalysis, Tetrahedron (2017), http://dx.doi.org/10.1016/j.tet.2017.03.055