Copper-Catalyzed Selective Diphenylation of Carboxylic Acids with Cyclic Diaryliodonium Salts

Article abstract of DOI:10.1021/acs.joc.7b00513

Herein, we describe a novel one-step copper-catalyzed diphenylation of readily available aliphatic or (hetero)aromatic carboxylic acids with cyclic hypervalent diaryliodonium reagents. The selective diphenylation of benzoic acids with high atom economy can be achieved without observation of the arylation at the phenyl hydroxyl/thio/amino position. The valuable biphenyl esters with an additional iodo-substituent were obtained in good to excellent yields, which can be further transformed to diversified building blocks for the synthesis of bioactive natural products, pharmaceuticals, and functional materials. A wide range of different functional groups are compatible under the optimized reaction conditions.

Full text of DOI:10.1021/acs.joc.7b00513

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Article
Copper-Catalyzed Selective Diphenylation of
Carboxylic Acids with Cyclic Diaryliodonium Salts
Hao Xie, Shuai Yang, Chunxia Zhang, Mingruo Ding, Min Liu, Jie Guo, and Fengzhi Zhang
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 26 Apr 2017
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CopperꢀCatalyzed Selective Diphenylation of Carboxylic Acids
with Cyclic Diaryliodonium Salts
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Hao Xie, Shuai Yang, Chunxia Zhang, Mingruo Ding, Min Liu, Jie Guo and Fengzhi
Zhang*
College of Pharmaceutical Science & Green Pharmaceutical Collaborative Innovation Center of
Yangtze River Delta Region, Zhejiang University of Technology, Hangzhou, 310014, P. R. China
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Supporting Information Placeholder
R3
Cu-catalyzed selective diphenylation
O
OH
I
+
R3
R2
O
♦ Simple one-step procedure
♦ High atom economy/eco-friendly
♦ Broad substrate scopes
♦ Gram scale synthesis
O
R1
I
R1
-OTf
R2
simple aliphatic or readily available cyclic
(hetero)aryl acids diaryliodonium salts
valuable biphenyl esters
with iodo-f unctional handle
42 examples; up to 97% yield
ABSTRACT: Herein, we describe a novel oneꢀstep copperꢀcatalyzed diphenylation of readily available
aliphatic or (hetero)aromatic carboxylic acids with cyclic hypervalent diaryliodonium reagents. The selective
diphenylation of benzoic acids with high atomꢀeconomy can be achieved without observation of the
arylation at the phenyl hydroxyl/thio/amino position. The valuable biphenyl esters with an additional
iodoꢀsubstituent were obtained in good to excellent yields, which can be further transformed to diversified
building blocks for the synthesis of bioactive natural products, pharmaceuticals and functional materials. A
wide range of different functional groups are compatible under the optimized reaction conditions.
1. INTRODUCTION
Functionalized biphenyl esters are commonly encountered in the core structures of therapeutic reagents,1
functional materials,2 bioactive natural products3 and ligands (Figure 1).4 Constructing a CꢀO bond of
monoaryl ether5 or aryl ester6 by metal catalysis is a longꢀstanding interest to organic chemists, and a lot of
excellent research works have been reported from different research groups. However, conventional
biphenyl ester syntheses still involve the direct esterfication of carboxylic acids with biphenyl alcohol under
strongly acidic or basic conditions,7 which might cause side reactions and limit scopes of substrates.8
Furthermore, the esterfication reactions generally rely on the preꢀactivation of the carboxylic acids to either
acyl chloride or mixed anhydride by using a stoichiometric amount of coupling reagents, making them
generally expensive and wasteful procedures.
Figure 1. Representative examples of biphenyl esters
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The biphenyl esters also can be accessed by a twoꢀstep procedure either by reacting preformed
monoꢀarylated ester 2 with an aryl coupling component 4 (substituted benzenes,9 arylboronic acids10 or
arylzinc reagents11) or a direct CꢀH functionalization of the preformed ester 3 with linear diaryliodonium salt
5 (Scheme 1a)12. Inspired by Cheng’s work about copper triflate mediated ChanꢀLam reaction of carboxylic
acids with arylboronic acids,13 Kumaran and coꢀworkers developed a metalꢀfree synthesis of biphenyl ester
by coupling arylcarboxylic acids with arylboronic acids.14 Even though the biphenyl ester can be accessed by
this oneꢀstep procedure, there is only one example reported with benzoic acid as the substrate. Besides, these
methodologies still suffered from the inherent drawback of using organometallic reagents and producing
harmful byproducts along with the desired biphenyl esters.
Scheme 1. Approaches for the synthesis of biphenyl esters
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Increasing attention is now being devoted to develop such CꢀO bond formation which is not only
atomꢀeconomical but also low cost and more environmentally friendly. A possible solution lies with oneꢀstep
metal catalysis procedure with hypervalent diaryliodonium salts. Combining the excellent usability, stability,
readily availability and high reactivity, linear hypervalent diaryliodonium salts have been extensively
investigated as electrophilic arylation agents for the formation of CꢀC and Cꢀheteroatom bonds.15ꢀ16 In 2011
Olofsson group reported a nice example about the monoꢀarylation of the carboxylic acids under basic
conditions. 17 However, this metalꢀfree condition doesn’t work for the biarylation of carboxylic acids with
cyclic iodonium salts (entry 1, Table 1). Compared to linear iodonium salts, the employment of cyclic
iodonium salts is advantageous in terms of atom economy because both aryl group will be incorporated in
the arylated products.18 Our interest in arylation chemistry19 led us to question whether the CꢀO bonds of
biphenyl esters could be constructed by coupling of carboxylic acids with cyclic diaryliodonium salts
(Scheme 1b), which are not only highly atom and stepꢀeconomical but also environmentally friendly. More
importantly, this novel reaction will generate the biphenyl esters which may be difficult to obtain by other
methods. Furthermore, these esters with very useful iodoꢀfunctional handles can be further transformed to
valuable diversified building blocks.
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2. RESULTS AND DISCUSSION
We initiated the study by performing the reaction of the commercially available 2ꢀaminoꢀ3ꢀmethylbenzoic
acid 1a with cyclic diaryliodonium salt 7a (Table 1). By choosing a model substrate 1a with both phenyl
acid and amino functional groups, we would like to achieve the selective diphenylation at the benzoic acid
position without arylation at the phenyl amino position. Firstly, We tried the metal free acid arylation
conditions reported by Olofsson and coꢀworkers,17 and we were surprised to observe no desired product at all
in the presence of KOtBu as base and toluene as solvent (entry 1), which might because the cyclic diaryl
iodonium salts are generally less reactive than the linear counterpart.20 We then tried a catalyst system of
Pd(OAc)2/Ag2CO3 and 1,10ꢀphenanthroline in toluene, there was no product detected either (entry 2). With
CuSO4 as catalyst reported by Fuson and Albright for the arylation of acetic acid (entry 3),21 the reaction was
still failed even with the addition of 1,10ꢀphenanthroline (phen) as the ligand (entry 4). To our delight, 10
mol % CuCl as catalyst with Na2CO3 as base at 150 oC in toluene was proved effective, the desired biphenyl
ester 8a was formed selectively in 41% yield without observation of arylation at the phenyl amino position
(entry 5). The yields can be further improved by using either Cu(OAc)2 (49%, entry 6) or CuI (63%, entry 7)
as catalyst. All attempts to improve the reaction by changing the ligands (entries 8ꢀ10) and bases (entries
11ꢀ14) did not give better result. The influence of the solvents was then studied (entries 15ꢀ19). We found
the yield was improved to 70% by using 1, 4ꢀdioxane as the solvent (entry 19). A further jump in yield could
o
o
be attained by reducing the temperature to 120 C (84% yield, entry 20) and 95 C (92% yield, entry 21).
However, the yield was dropped to 70% by decreasing the temperature to 70 oC (entry 22). By increasing the
amount of the base, there is no further improvement for the reaction (entry 23). The yields were dropped
significantly by reducing the amount of either catalyst/ligand (70%, entry 24) or iodonium salts (61%, entry
25). The blank experiments showed that both the catalyst/ligand and base were required for this reaction
(entries 26ꢀ28). Pleasingly, this reaction was equally effective on gram scale; 5.7 g of biphenyl ester 8a was
easily prepared in 88% yield on 15 mmol scale (entry 29).
Table 1. Reaction optimizationa
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entrya
catalyst
ꢀ
ligand
ꢀ
base
solventb
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
temp (oC)
100
yield (%)c
1
2d
3
KOtBu
Na2CO3
NaOAc
NaOAc
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
0
0
Pd(OAc)2
CuSO4
CuSO4
CuCl
Cu(OAc)2
CuI
phen
100
ꢀ
100
0
4
phen
100
0
5
phen
150
41
49
63
trace
trace
53
6
phen
150
7
phen
150
8
CuI
PPh3
150
9
CuI
valine
2,2’ꢀdipyridyl
150
10
CuI
150
11
12
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19
20
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
phen
phen
phen
phen
phen
phen
phen
phen
phen
phen
KOtBu
Cs2CO3
NaHCO3
K2CO3
toluene
toluene
toluene
toluene
DMF
150
150
150
150
150
150
150
150
150
120
0
trace
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60
0
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
DMSO
THF
0
40
45
70
84
DCE
1,4ꢀdioxane
1,4ꢀdioxane
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22
CuI
CuI
CuI
CuI
CuI
ꢀ
phen
phen
phen
phen
phen
phen
ꢀ
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
ꢀ
1,4ꢀdioxane
1,4ꢀdioxane
1,4ꢀdioxane
1,4ꢀdioxane
1,4ꢀdioxane
1,4ꢀdioxane
1,4ꢀdioxane
1,4ꢀdioxane
1,4ꢀdioxane
95
70
95
95
95
95
95
95
95
92
70
90
70
61
0
23e
24f
25g
26
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27
CuI
CuI
CuI
27
11
88
28
phen
phen
29h
Na2CO3
aReaction condtions: benzoic acid (0.25 mmol), iodonium salt (0.5 mmol), catalyst (10 mol %), ligand (10
b
mol %), base (1.5 equiv), 3 Å molecular sieves (0.4 g/mmol), solvent (1.5 mL), heat, 17 h. Anhydrous
c
solvent. Isolated yields. d With the addition of 1 equiv Ag2CO3. eThe amount of Na2CO3 was increased to 3
equiv. fThe yield was decreased to 70% by reducing the loading of both catalyst and ligand to 5 mol %. g The
amount of iodonium salt was decreased to 1.5 equiv. h15 mmol Scale.
With this optimized procedure in hand, we next examined the scope of this new process using a range of
carboxylic acids (Table 2). Yields were generally good to excellent for a variety of simple benzoic acids
(8bꢀ8e). We were pleased to find the orthoꢀhydroxy benzoic acid was effective in the reaction; the desired
biphenyl ester 8f was obtained selectively in 85% yield without arylation at the phenyl hydroxyl position.
Interestingly, the 2ꢀmercaptobenzoic acid led to the dimerized product 8g in 57% yield. For the anthranilic
acid derivatives, both highly electron withdrawing groups (such as NO2, CF3) and electron donating groups
(such as OMe) were tolerated under the reaction conditions (8h, 8i, 8p, and 8k). Gratifyingly, all the
substrates with different halogenated functionalities (F, Cl, Br and I) were effective to give the desired
products in good to excellent yields (8j, 8nꢀo, and 8qꢀr). The benzoic acid with orthoꢀbenzoyl functionality
also reacted well providing the product 8s in 84% yield with multiꢀfunctional handles which allow for
further transformations. Importantly, we found that both aliphatic and heterocyclic carboxylic acids were
equally effective as the benzoic acids (8tꢀy).
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Table 2. Diphenylation of various carboxylic acids
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To fully establish the scopes of the diphenylation reaction, a range of substituted cyclic diaryliodonium
salts were prepared according to Olofsson’s method and subjected to the optimized reaction protocol with
carboxylic acids (Table 3). 22 Good to excellent yields were obtained with alkyl substituted symmetrical
cylic diaryliodonium salts (9aꢀe). The electron rich cyclic diaryliodonium salts only gave the desired
product 9f in poor yield.20 For the electron withdrawing halogenated cyclic diaryliodonium salts, we found
that both the fluoro and chloro groups were tolerated (9gꢀl). The reaction was proved insensitive to the
steric hindrance on both coupling partners (9m and 9n). For the unsymmetrical cyclic diaryliodonium salts,
it was found that 9o was obtained as a single product. However, 9p/9p' and 9q/9q' were obtained as a
mixture of products with a ratio around 1:1 respectively. Overall, various functional groups including free
phenyl amino and hydroxyl groups were compatible under the optimized reaction conditions.
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Table 3. Diphenylation of carboxylic acids with various cyclic diaryliodonium salts
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We already demonstrated the successful diphenylation of aliphatic, aromatic and heteroaromatic
carboxylic acids. Our procedure was equally effective for the arylation of carboxylic acids with linear
iodonium salts (Scheme 2). To investigate the regioselective arylation of the acid in the presence of the other
nucleophile, we especially chose 1a, 6f and 6g as the substrates which contain phenolic amino, hydroxyl and
thiol group respectively. Interestingly, compared to Olofsson’s condition,17 the desired products 10 and 11
were obtained in much better yields under our Cuꢀcatalyzed conditions with the phenolic amino, hydroxyl
group untouched. However, for the 2ꢀthiolbenzoic acid substrate 6g both the acid and thiol groups were
arylated to give the product 12 in poor yield.
Scheme 2. Monoꢀarylation of anthranilic acid derivatives
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To further understand this diphenylation reaction we carried out the following experiments (Scheme 3):
firstly we treated the aniline 13a and phenol 13b with the optimized reaction conditions respectively, and we
found that only the diphenylated aniline 14a was obtained in 53% yield, which means the selective
diphenylation of aniline derivatives also can be achieved in the presence of free phenyl hydroxyl group
under our reaction conditions (Scheme 3a). We then conducted the competition experiment between benzoic
acid 6b and aniline 13a (Scheme 3b), interestingly, biphenyl ester 8b was obtained in 95% yield and only 4%
yield of 14a was obtained. These experiments demonstrated why the selective diphenylation of benzoic
carboxylic acids can be achieved in the presence of phenyl amino or hydroxyl groups. Finally, we performed
the reaction of our model substrate 1a with 2,2’ꢀdiiodoꢀ1,1’ꢀbiphenyl 15 under the optimized conditions
(Scheme 3c), and no reaction was happened, which means the diiodo compound 15 is not the intermediate of
this diphenylation reaction. Therefore, the possible reaction mechanism might involve a Cu(III)ꢀaryl
intermediate I from the cyclic diaryliodonium salt 7a in the presence of CuI, which was then attacked by the
carboxylic acid 6 and generated the intermediate II. Finally, the desired product 8 was produced by reductive
elimination.
Scheme 3. Experiments about selectivity and mechanistic study
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To demonstrate the utility of this new copperꢀcatalyzed diphenylation process, the biphenyl ester 8a was
transformed to various valuable building blocks. Firstly, we carried out some experiments to functionalize
the iodoꢀposition (Scheme 4). Treated ester 8a with trimethylsilylacetylene under the Sonogashira coupling
conditions the desired product 16 was obtained in 73% yield, which could be further modified if necessary.
By reacting with styrene under Heck coupling conditions the alkene product 17 was prepared in 53% yield.
Alkyne 16 and alkene 17 could be cyclized to afford the phenanthrene products via Rutheniumꢀcatalyzed
benzannulation Protocol or photocyclization conditions.23 Under the conditions of metal catalysis the
iodoꢀfunctionalized biphenyl ester 8a can be converted to the cyano ester 1824 or phosphino ester 1925
respectively which potentially could be worked as bidentate ligands for various transformations.
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Scheme 4. Further transformations of iodoꢀfunctional group
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I
R
conditions
O
O
O
O
9
H2N
H3C
H2N
H3C
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8a
1) 2.5 equiv
SiMe3 10 mol % Pd(PPh3)2Cl2
SiMe3
16
17
, 73%, R =
Et3N, THF, rt, 12 h
2) 1.2 equiv styrene, 5 mol % Pd(OAc)2
2.0 eq. AcOH, 110 oC
, 53%, R =
Ph
3) 1.5 equiv CuCN, NMP, reflux, 12 h
18, 50%, R =
CN
4) 2.0 equiv Ph2PH, 10 mol % Pd(OAc)2
KOAc, DMA, 100 oC, 12 h
19
, 54%, R =
PPh2
We then carried out the further transformations based on the aminoꢀfunctionality (Scheme 5). By a 3ꢀstep
oneꢀpot process the amino functionality in biphenyl ester 8a can be removed to give ester 20 in 62% yield.
t
The amino group also can be transformed to azide group in ester 21 by treating ester 8a with BuONO and
TMSN3.26
Scheme 5. Further transformations of aminoꢀfunctional group
Finally we demonstrated the biphenyl ester 8a can be cyclized to give different valuable heterocycles
t
(Scheme 6). By reacting with BuONO the biphenyl ester 8a can be cyclized to give the indazole compund
22.27 By a twoꢀstep procedure the biphenyl ester 8a can be cyclized successfully to give the benzocoumarin
23, an important skeleton for both pharmaceutical molecules and natural products. 28
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Scheme 6. Intramolecular cyclization to form various hetreocycles
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3. CONCLUSIONS
In summary, we have developed a general and efficient scalable procedure for Cuꢀcatalyzed
monoꢀarylation or diphenylation of carboxylic acids with readily available diaryliodonium salts. The
selective diphenylation of benzoic acids with high atomꢀeconomy can be achieved without arylation at the
phenyl hydroxyl/thio/amino positions. The corresponding dipheylated esters with an iodoꢀsubstitutent are
obtained in good to excellent yields with various aliphatic, aromatic or heteroaromatic carboxylic acids. This
transformation is tolerant to a wide range of functional groups (such as halogens, nitro and free phenyl
amino/hydroxyl groups etc.) on both coupling partners. The valuable biphenyl esters can be easily
transformed to diversified products which are prevalent building blocks for bioactive natural products,
pharmaceuticals, organic electronic devices and bidentate ligands.
4. EXPERIMENTAL SECTION
4.1. General Information. All reagents were obtained from commercial suppliers and used without
further purification. Yields for all compounds were determined by the column chromatography which was
generally performed on silica gel (200ꢀ300 mesh) using petroleum ether 40ꢀ60 PE/EtOAc as eluent, and
reactions were monitored by thin layer chromatography (TLC) on a glass pate coated with silica gel with
fluorescent indicator (GF254) using UV light. The H and 13C nuclear magnetic resonance (NMR) spectra
1
were recorded on a Bruker AVANCE III 500 MHz using CDCl3 as solvent with TMS as internal standard.
Chemical shifts are given in ppm (δ) referenced to CDCl3 with 7.26 for H and 77.16 for 13C, and to
1
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DMSOꢀd6 with 2.50 for H and 39.52 for 13C. Signals are abbreviated as follows: s, singlet; d, doublet; t,
triplet; q, quartet; m, multiplet, and coupling constants are expressed in hertz. Melting points were measured
on a SGW® Xꢀ4B apparatus and uncorrected. HRMS were recorded on Agilent 6210TOF LC/MS mass
spectrometer.
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4.2. General procedure for the diphenylation reaction. Synthesis of
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl 2ꢀaminoꢀ3ꢀmethylbenzoate (8a, Table 1). The reaction of cyclic diaryliodonium
salt 7a, 2ꢀAminoꢀ3ꢀmethylbenzoic acid 1a was exemplified here. 2ꢀAminoꢀ3ꢀmethylbenzoic acid 1a (37.25
mg, 0.25 mmol), cyclic diphenyleneiodonium 7a (214 mg, 0.50 mmol), Na2CO3 (39.75 mg, 0.375 mmol),
CuI (4.8 mg, 0.025 mmol) and 1,10ꢀPhenanthroline (4.5 mg, 0.025 mmol) were dissolved in anhydrous
1,4ꢀdioxane (1.5 mL) in a pressure νessel. 3 Å molecular sieves (100 mg) were then added. The reaction
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mixture was stirred at 95 C for 17 h before it was cooled to rt and filtered. The mixture was then extracted
with EtOAc (50 mL) and washed with water (10 mL) and brine (10 mL) before the organic phase was dried
over anhydrous Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography
(PE/EtOAc = 20:1) on silica gel to provide the desired product 8a (98.9 mg, 92% yield). Mp = 97.9ꢀ98.4 oC;
Rf = 0.50 (PE/EtOAc = 10:1); 1H NMR (CDCl3; 500 MHz): δ 7.88 (d, J = 8.3 Hz, 1 H), 7.67 (d, J = 8.2 Hz,
1 H), 7.50 (td, J = 7.6, 0.8 Hz, 1 H), 7.36 (td, J = 7.6, 0.6 Hz, 1 H), 7.28ꢀ7.33 (m, 4 H), 7.17 (d, J = 7.3 Hz, 1
H), 6.96 (td, J = 7.1, 1.6 Hz, 1 H), 6.52 (t, J =7.6 Hz, 1 H), 5.69 (s, 2 H), 2.12 (s, 3 H) ppm; 13C NMR
(CDCl3; 126 MHz): δ 166.8, 149.6, 147.9, 142.8, 139.0, 137.9, 135.4, 131.1, 130.5, 129.7, 129.3, 129.3,
128.0, 125.8, 123.1, 122.9, 115.8, 109.2, 99.7, 17.5 ppm; IR (KBr) ν 3491, 3378, 1709, 1615, 1464, 1244,
1196, 1067, 1002, 468 cmꢀ1; HRMS m/z (ESI): calcd for C20H17INO2 [M + H]+ 430.0298, found 430.0303,
error 1.02 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl benzoate (8b): Following the general experiment procedure, 8b was purified
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by PE/EtOAc (30:1) and obtained as a white solid (97% yield). Mp = 46.4ꢀ47.2 C; Rf = 0.60 (PE/EtOAc =
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15:1); H NMR (CDCl3; 500 MHz): δ 7.90ꢀ7.93 (m, 2 H), 7.88 (d, J = 7.6, 1 H), 7.49ꢀ7.55 (m, 2 H),
7.34ꢀ7.40 (m, 4 H), 7.28ꢀ7.32 (m, 3 H), 6.94ꢀ7.00 (m, 1 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 164.7,
148.0, 142.7, 138.9, 137.4, 133.4, 131.0, 130.5, 130.1, 129.4, 129.3, 129.2, 128.5, 128.0, 126.0, 122.7, 99.7
ppm; IR (KBr) ν 1737, 1600, 1496, 1462, 1262, 1194, 1062, 497 cm ꢀ1; HRMS m/z (ESI): calcd for
C19H13INaO2 [M + Na]+ 422.9852, found: 422.9846, error 1.59 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl 2,5ꢀdimethylbenzoate (8c): Following the general experiment procedure, 8c
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was purified by PE/EtOAc (15:1) and obtained as a white solid (72% yield). Mp = 73.3ꢀ74.2 C; Rf = 0.55
(PE/EtOAc = 6:1); 1H NMR (CDCl3; 500 MHz): δ 7.93 (d, J = 7.6 Hz, 1 H), 7.52 (td, J = 7.8, 0.9 Hz, 1 H),
7.48 (s, 1 H), 7.35ꢀ7.40 (m, 2 H), 7.31ꢀ7.34 (m, 3 H), 7.19 (d, J = 7.8 Hz, 1 H), 7.08 (d, J = 7.8 Hz, 1 H),
7.00ꢀ7.03 (m, 1 H), 2.41 (s, 3 H), 2.28 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 165.6, 148.1, 142.9,
138.8, 137.7, 137.6, 135.2, 133.2, 131.5, 131.5, 130.9, 130.6, 129.4, 129.3, 128.3, 127.9, 125.9, 122.9,
100.0, 21.0, 20.8 ppm; IR (KBr) ν 1745, 1593, 1469, 1244, 1189, 1102, 489 cmꢀ1; HRMS m/z (ESI): calcd
for C21H17INaO2 [M + Na]+ 451.0165, found: 451.0162, error 0.67 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl 4ꢀmethoxybenzoate (8d): Following the general experiment procedure, 8d was
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purified by PE/EtOAc (15:1) and obtained as a yellow liquid (80% yield). Rf = 0.28 (PE/EtOAc = 6:1); H
NMR (CDCl3; 500 MHz): δ 7.87ꢀ7.90 (m, 3 H), 7.50 (dd, J = 7.8, 0.9 Hz, 1 H), 7.34ꢀ7.38 (m, 2 H),
7.27ꢀ7.31 (m, 3 H), 6.94ꢀ6.97 (m, 1 H), 6.86 (d, J = 9.0 Hz, 2 H), 3.83 (s, 3 H) ppm; 13C NMR (CDCl3; 126
MHz): δ 164.4, 163.8, 148.1, 142.8, 138.8, 137.5, 132.2, 130.9, 130.5, 129.4, 129.2, 127.9, 125.8, 122.8,
121.7, 113.8, 99.7, 55.5 ppm; IR (KBr) ν 1733, 1604, 1508, 1263, 1173, 1070, 451 cmꢀ1; HRMS m/z (ESI):
calcd for C20H15INaO3 [M + Na]+452.9958, found: 452.9956, error 0.44 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl 2ꢀchlorobenzoate (8e): Following the general experiment procedure, 8e was
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purified by PE/EtOAc (15:1) and obtained as a white solid (65% yield). Mp = 74.6ꢀ75.2 C; Rf = 0.45
(PE/EtOAc = 6:1); 1H NMR (CDCl3; 500 MHz): δ 7.92 (d, J = 8.0 Hz, 1 H), 7.51 (td, J= 7.8, 0.9 Hz, 1 H),
7.46 (dd, J = 7.6, 0.7 Hz, 1 H), 7.30ꢀ7.41 (m, 7 H), 7.21 (td, J = 7.8, 1.0 Hz, 1 H), 7.02 (td, J = 7.5, 1.0 Hz, 1
H) ppm;13C NMR (CDCl3; 126 MHz): δ 163.5, 147.8, 142.6, 138.9, 137.6, 134.3, 133.0, 131.5, 131.2, 131.1,
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130.6, 129.5, 129.4, 129.2, 128.1, 126.6, 126.3, 122.8, 99.9 ppm; IR (KBr) ν 1744, 1595, 1453, 1244, 1183,
1105, 735, 495 cm ꢀ1; HRMS m/z (ESI): calcd for C19H12ClINaO2 [M + Na]+ 456.9463, found: 456.9460,
error 0.66 ppm.
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2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl 2ꢀhydroxybenzoate (8f): Following the general experiment procedure, 8f was
purified by PE/EtOAc (50:1) and obtained as a white oilꢀliquid (85% yield). Rf = 0.60 (PE/EtOAc = 25:1);
1H NMR (CDCl3; 500 MHz): δ 10.36 (s, 1 H), 7.90 (d, J = 8.1, 0.5 Hz, 1 H), 7.81 (dd, J = 8.1, 0.9 Hz,1 H),
7.54 (td, J = 7.8, 0.9 Hz, 1 H), 7.41 ꢀ7.47 (m, 2 H), 7.30ꢀ7.38 (m, 4 H), 6.95ꢀ7.00 (m, 2 H), 6.88 (t, J = 7.6, 1
H) ppm; 13C NMR (CDCl3; 126 MHz): δ 168.3, 161.9, 147.2, 142.2, 139.0, 137.4, 136.3, 131.2, 130.4, 130.4,
129.5, 129.4, 128.0, 126.5, 122.5, 119.4, 117.6, 111.6, 99.5 ppm; IR (KBr) ν 3230, 1691, 1615, 1582, 1463,
1249, 1188, 1156, 529 cm ꢀ1; HRMS m/z (ESI): calcd for C19H13INaO3 [M + Na]+ 438.9802, found: 438.9802,
error 0 ppm.
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bis(2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl)ꢀ2,2'ꢀdisulfanediyldibenzoate (8g): Following the general experiment
procedure, 8g was purified by PE/EtOAc (30:1) and obtained as a white solid (57% yield). Mp = 84.8ꢀ85.9
oC; Rf = 0.40 (PE/EtOAc = 6:1); 1H NMR (CDCl3; 500 MHz): δ 7.89 (d, J = 7.9 Hz, 2 H), 7.86 (dd, J = 7.8,
0.7 Hz, 2 H), 7.61 (d, J = 8.1 Hz,2 H), 7.52 (td, J = 7.8, 0.8 Hz, 2 H), 7.40ꢀ7.42 (m, 2 H), 7.35ꢀ7.39 (m, 4 H),
7.30ꢀ7.33 (m, 6 H), 7.15 (t, J = 7.6 Hz, 2 H), 6.96ꢀ7.00 (m, 2 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 164.5,
147.8, 142.7, 141.1, 138.9, 137.5, 133.5, 131.9, 131.1, 130.7, 129.5, 129.4, 128.1, 126.6, 126.3, 126.0, 125.7,
122.8, 99.8 ppm; IR (KBr) ν 1719, 1585, 1450, 1244, 1189, 1139, 648, 552, 486 cm ꢀ1; HRMS m/z (ESI):
calcd for C38H24I2NaO4S2 [M + Na]+ 884.9098, found: 884.9096, error 0.05 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀnitrobenzoate (8h): Following the general experiment procedure,
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8h was purified by PE/EtOAc (15:1) and obtained as a yellow solid (70% yield). Mp= 159.5ꢀ160.5 C; Rf =
0.40 (PE/EtOAc = 6:1); 1H NMR (CDCl3; 500 MHz)：δ 8.35 (dd, J = 8.5, 0.8 Hz, 1 H), 8.29 (s, 2 H), 8.11
(dd, J =7.7, 0.8 Hz, 1 H), 7.87 (dd, J = 8.0, 0.5 Hz, 1 H), 7.53 (td, J=7.8, 0.8 Hz, 1H), 7.41 (td, J = 7.5, 0.6
Hz, 2 H), 7.30ꢀ7.33 (m, 2 H), 7.25ꢀ7.27 (m, 1 H), 6.98 (td, J = 7.7, 0.9 Hz, 1 H), 6.59 (t, J = 8.1 Hz, 1 H)
ppm; 13C NMR (CDCl3; 126 MHz)：δ 165.3, 147.6, 147.4, 142.4, 139.9, 139.0, 137.6, 133.4, 132.9, 131.2,
130.5, 129.6, 129.4, 128.1, 126.5, 122.7, 114.3, 113.4, 99.5 ppm; IR (KBr) ν3476, 3353, 1713, 1619, 1574,
1512, 1354, 1255, 1191, 469 cmꢀ1; HRMS m/z (ESI) : calcd for C19 H13 IN2NaO4 [M + Na]+ 482.9812, found:
482.9816, error 0.79 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ4ꢀ(trifluoromethyl) benzoate (8i): Following the general experiment
procedure, 8i was purified by PE/EtOAc (30:1) and obtained as a white solid (87% yield). Mp = 133.7ꢀ134.6
oC; Rf = 0.50 (PE/EtOAc = 15:1); 1H NMR (CDCl3; 500 MHz)：δ 7.89 (dd, J = 8.0, 0.5 Hz, 1 H), 7.82 (d, J =
8.3 Hz, 1 H), 7.52 (td, J = 7.8, 0.9 Hz, 1 H), 7.39 (td, J = 7.5, 0.6 Hz, 1 H), 7.30ꢀ7.35 (m, 3 H), 7.26ꢀ7.28 (m,
1 H), 6.99 (td, J = 7.6, 0.9 Hz, 1 H), 6.84 (s, 1 H), 6.78 (dd, J = 8.4, 0.7 Hz, 1 H), 5.79 (s, 2 H) ppm; 13C
NMR (CDCl3; 126 MHz)：δ 165.5, 150.7, 147.6, 142.6, 139.0, 137.6, 136.1, 135.9, 132.6, 131.1, 130.5,
129.5 (d, J = 6.0 Hz), 128.0, 126.2, 122.8, 113.4(d, J = 4.0 Hz), 112.5 (d, J = 3.7 Hz), 112.0, 99.6 ppm; IR
(KBr) ν 3518, 3393, 1720, 1599, 1444, 1356, 1246, 1192, 1120, 1071, 500 cm ꢀ1; HRMS m/z (ESI): calcd for
C20H14F3INO2 [M + H]+ 484.0016, found: 484.0017, error 0.26 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ4ꢀbromobenzoate (8j): Following the general experiment procedure,
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8j was purified by PE/EtOAc (15:1) and obtained as a yellow solid (80% yield). Mp = 128.2ꢀ129.0 C; Rf =
0.42 (PE/EtOAc = 6:1); 1H NMR (CDCl3; 500 MHz)：δ 7.74 (dd, J = 8.0, 0.5 Hz, 1 H), 7.43 (d, J = 8.6 Hz, 1
H), 7.36 (td, J = 7.8, 0.9 Hz, 1 H), 7.23 (td, J = 7.5, 0.6, 1 H), 7.16ꢀ7.19 (m, 3 H), 7.11ꢀ7.13 (m, 1 H), 6.84
(td, J = 7.6, 0.9 Hz, 1 H), 6.63 (d, J = 1.8 Hz, 1 H), 6.55 (dd, J = 8.6, 0.9 Hz, 1 H), 5.51 (s, 2 H) ppm; 13C
NMR (CDCl3; 126 MHz)：δ 165.4, 149.1, 147.9, 142.7, 139.1, 137.6, 134.4, 132.3, 131.4, 130.9, 129.6,
129.5, 127.9, 126.3, 122.8, 119.5, 114.8, 113.7, 100.1 ppm; IR (KBr) ν 3489, 3373, 1711, 1603, 1461, 1233,
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1190, 1058, 555, 496 cm ꢀ1; HRMS m/z (ESI): calcd for C19H13 BrINNaO2 [M + Na]+ 515.9067, found:
515.9073, error 1.46 ppm.
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2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ4,5ꢀdimethoxybenzoate (8k): Following the general experiment
procedure, 8k was purified by PE/EtOAc (5:1) and obtained as a yellow solid (82% yield). Mp =
188.5ꢀ189.4 oC; Rf = 0.35 (PE/EtOAc = 2:1); 1H NMR (CDCl3; 500 MHz)：δ 7.88 (d, J = 7.9 Hz, 1 H), 7.51
(td, J = 8.2, 0.9 Hz, 1 H), 7.39 (d, J = 8.2 Hz, 1 H), 7.36 (t, J = 7.5 Hz, 1 H), 7.32 (t, J = 7.5 Hz, 1 H),
7.27ꢀ7.29 (m, 2 H), 7.18 (s, 1 H), 6.98 (td, J = 7.4, 1.0 Hz, 1 H), 6.08 (s, 1 H), 5.50 (s, 2 H), 3.85 (s, 3 H),
3.77 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 165.6, 155.3, 147.9, 147.8, 143.2, 140.8, 138.8, 137.6,
130.7, 130.6, 129.3, 129.2, 128.1, 125.7, 123.1, 112.4, 101.0, 99.9, 99.2, 56.4, 55.9 ppm; IR (KBr) ν3494,
3385, 1688, 1599, 1510, 1462, 1163,1042, 499 cm ꢀ1; HRMS m/z (ESI): calcd for C21H19INO4 [M + H]+
476.0353, found: 476.0350, error 0.6 ppm.
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2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl 2ꢀaminobenzoate (8l): Following the general experiment procedure, 8l was
purified by PE/EtOAc (20:1) and obtained as a yellow oilꢀliquid (79% yield). Rf = 0.45 (PE/EtOAc = 10:1);
1H NMR (CDCl3; 500 MHz): δ 7.88 (d, J = 8.3 Hz,1 H), 7.74 (dd, J = 8.1, 0.8 Hz, 1 H), 7.50 (td, J = 7.7, 0.9
Hz, 1 H), 7.36 (td, J = 7.6, 0.6 Hz, 1 H), 7.33 (d, J = 8.2 Hz, 1 H), 7.27ꢀ7.32 (m, 3 H), 7.24 (td, J = 7.7, 0.8
Hz, 1 H), 6.97 (td, J = 7.4, 1.2 Hz, 1 H), 6.56ꢀ6.60 (m, 2 H), 5.56 (s, 2 H) ppm; 13C NMR (CDCl3; 126 MHz):
δ 166.3, 151.1, 147.8, 142.8, 139.0, 137.7, 134.7, 131.7, 131.1, 130.5, 129.4, 129.3, 128.0, 125.9, 123.0,
116.6, 116.5, 109.7, 99.9 ppm; IR (KBr) ν 3488, 3375, 1702, 1616, 1459, 1289, 1239, 1200, 1048, 496 cmꢀ1;
HRMS m/z (ESI): calcd for C19H15INO2 [M + H]+416.0142, found: 416.0145, error 0.72 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ5ꢀmethylbenzoate (8m): Following the general experiment procedure,
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8m was purified by PE/EtOAc (30:1) and obtained as a white solid (74% yield). Mp = 128.4ꢀ129.2 C; Rf =
0.44 (PE/EtOAc = 15:1);1H NMR (CDCl3; 500 MHz): δ 8.40 (d, J = 8.2 Hz, 1 H), 7.99ꢀ8.02 (m, 2 H),
7.84ꢀ7.88 (m, 2 H), 7.79ꢀ7.82 (m, 3 H), 7.57 (dd, J = 8.4, 1.0 Hz, 1 H), 7.48 (td, J = 7.6, 1.1 Hz, 1 H), 7.03
(d, J = 8.4 Hz, 1 H), 5.90 (s, 2 H), 2.68 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 166.2, 148.9, 148.0,
142.8, 138.9, 137.6, 135.9, 131.4, 130.9, 130.5, 129.3, 129.2, 127.9, 125.8, 125.5, 123.0, 116.7, 109.6, 99.8,
20.2 ppm; IR (KBr) ν 3438, 3371, 1693, 1564, 1494, 1292, 1193, 1160, 1051, 497 cm ꢀ1; HRMS m/z (ESI):
calcd for C20H17INO2 [M + H]+ 430.0298, found: 430.0301, error 0.57 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ5ꢀchlorobenzoate (8n): Following the general experiment procedure,
8n was purified by PE/EtOAc (15:1) and obtained as a yellow solid (70% yield). Mp = 121.9ꢀ122.4 oC; Rf =
0.40 (PE/EtOAc = 6:1); 1H NMR (CDCl3; 500 MHz)：δ 7.91 (dd, J = 8.0, 0.6 Hz, 1 H), 7.67 (d, J = 2.6 Hz,
1H), 7.50 (td, J = 7.8, 0.9 Hz, 1 H), 7.31ꢀ7.39 (m, 4 H), 7.26ꢀ7.29 (m, 1 H), 7.17 (dd, J = 8.8, 1.3 Hz, 1 H),
7.00 (td, J = 7.6, 0.9 Hz, 1 H), 6.52 (d, J = 8.8 Hz, 1 H), 5.42 (s, 2 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ
165.3, 149.7, 147.8, 142.6, 139.1, 137.6, 134.8, 134.6, 131.2, 130.8, 130.5, 129.3, 127.9, 126.2, 122.8, 120.6,
118.2, 110.5, 99.5 ppm; IR (KBr) ν 3502, 3381, 1705, 1618, 1460, 1225, 1187, 746, 492 cm ꢀ1; HRMS m/z
(ESI): calcd for C19H14ClINO2 [M + H]+449.9752, found: 449.9750, error 0.06 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ5ꢀiodobenzoate (8o): Following the general experiment procedure,
8o was purified by PE/EtOAc (8:1) and obtained as a brown oilꢀliquid (64% yield). Rf = 0.40 (PE/EtOAc =
3:1); 1H NMR (CDCl3; 500 MHz): δ 7.91 (d, J = 2.2 Hz, 1 H), 7.88 (dd, J = 7.8, 0.5 Hz, 1 H), 7.45 (td, J =
7.8, 0.8 Hz, 1 H), 7.38 (dd, J = 8.7, 1.1 Hz, 1 H), 7.28ꢀ7.34 (m, 4 H), 7.22 (dd, J = 7.9, 0.9 Hz, 1 H), 6.97 (td，
J = 7.7, 0.9 Hz, 1 H), 6.32 (d，J = 8.8 Hz, 1 H), 5.59 (s, 2 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ 164.9,
150.3, 147.7, 142.8, 142.5, 139.9, 139.1, 137.5, 131.0, 130.5, 129.5, 129.4, 128.0, 126.0, 122.7, 118.7, 111.7,
99.7, 76.0 ppm;IR (KBr) ν 3507, 3396, 1707, 1611, 1462, 1259, 1185, 1074, 501 cmꢀ1; HRMS m/z (ESI):
calcd for C19H13I2NNaO2 [M + Na]+ 563.8928, found: 563.8920, error 1.37 ppm.
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2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ5ꢀnitrobenzoate (8p): Following the general experiment procedure,
8p was purified by PE/EtOAc (6:1) and obtained as a yellow solid (77% yield). Mp = 134.6ꢀ135.5 oC; Rf =
0.34 (PE/EtOAc = 3:1); 1H NMR (CDCl3; 500 MHz)：δ 8.67 (d, J = 2.6 Hz, 1 H), 8.09 (dd, J = 9.2, 1.3 Hz, 1
H), 7.89 (dd, J = 8.0, 1.0 Hz, 1 H), 7.52 (td, J = 7.8, 0.9 Hz, 1 H), 7.32ꢀ7.41 (m, 4 H), 7.28ꢀ7.30 (m, 1 H),
6.98 (td, J = 7.7, 0.9 Hz, 1 H), 6.60 (d, J = 9.2 Hz, 1 H), 6.53 (s, 2 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ
165.1, 155.2, 147.7, 142.3, 139.5, 137.4, 131.2, 130.4, 129.9, 129.7, 129.5, 129.5, 129.3, 128.3, 126.5, 122.6,
116.3, 108.5, 99.5 ppm; IR (KBr) ν 3453, 3331, 1714, 1626, 1313, 1248, 1192, 1119, 495 cm ꢀ1; HRMS m/z
(ESI) : calcd for C19H13IN2NaO4 [M + Na]+482.9812, found: 482.9812, error 0 ppm.
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2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ6ꢀfluorobenzoate (8q): Following the general experiment procedure,
8q was purified by PE/EtOAc (15:1) and obtained as a white solid (90% yield). Mp = 90.3ꢀ91.0 oC; Rf = 0.44
(PE/EtOAc = 6:1); 1H NMR (CDCl3; 500 MHz)：δ 7.89 (d, J = 7.9 Hz, 1 H), 7.49 (td, J = 7.7, 0.9 Hz, 1 H),
7.37 (td, J = 7.5, 0.5 Hz, 1 H), 7.29ꢀ7.33 (m, 4 H), 7.09ꢀ7.14 (m, 1 H), 6.97ꢀ7.00 (m, 1 H), 6.35 (d, J = 8.3
Hz, 1 H), 6.28 (t, J = 9.6 Hz, 1 H), 5.48 (s, 2 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ 165.0 (d, J = 3.7 Hz),
164.5, 162.5, 152.0 (d, J = 4.4 Hz), 147.8, 142.4, 139.0, 137.7, 134.4 (d, J = 12.0 Hz), 131.4, 130.5, 129.3 (d,
J = 10.0 Hz), 127.7, 126.0, 122.9, 112.0 (d, J = 3.0 Hz), 104.0, 103.7, 100.6 (d, J = 14.4 Hz), 99.7 ppm; IR
(KBr) ν 3491, 3377, 1700, 1625, 1465, 1275, 1191, 1077, 482 cm ꢀ1; HRMS m/z (ESI): calcd for
C19H14FINO2 [M + H]+ 434.0048, found: 434.0048, error 0 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ6ꢀchlorobenzoate (8r): Following the general experiment procedure,
o
8r was purified by PE/EtOAc (15:1) and obtained as a white solid (84% yield). Mp = 117.3ꢀ117.9 C; Rf =
0.45 (PE/EtOAc = 6:1); 1H NMR (CDCl3; 500 MHz)：δ 7.91 (d, J = 7.7 Hz, 1 H), 7.51 (td, J = 7.8, 0.8 Hz, 1
H), 7.39 (td, J = 7.5, 0.6 Hz, 1 H), 7.30ꢀ7.35 (m, 4 H), 7.01ꢀ7.05 (m, 2 H), 6.68 (dd, J = 7.8, 0.5 Hz, 1H),
6.47 (dd, J = 8.4, 0.5 Hz, 1H), 4.46 (s, 2 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ 165.4, 149.0, 147.7, 142.7,
139.1, 137.7, 134.2, 132.4, 131.4, 130.7, 129.6, 129.5, 128.0, 126.3, 122.8, 119.4, 114.9, 113.7, 100.1 ppm;
IR (KBr) ν 3484, 3372, 1705, 1608, 1477, 1229, 1191, 753, 520 cm ꢀ1; HRMS m/z (ESI) : calcd for
C19H14ClINO2 [M + H]+ 449.9752, found: 449.9753, error 0.14 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀ(2ꢀaminobenzoyl) benzoate (8s): Following the general experiment
procedure, 8s was purified by PE/EtOAc (6:1) and obtained as a yellow solid (84% yield). Mp = 134.6ꢀ135.5
oC; Rf = 0.40 (PE/EtOAc = 3:1); 1H NMR (CDCl3; 500 MHz)：δ 7.87 (dd, J = 8.0, 0.5 Hz, 1 H), 7.79 (dd, J =
7.9, 0.4 Hz, 1H), 7.58 (td, J = 7.5, 0.6 Hz, 1 H), 7.43 (td, J = 7.7, 0.6 Hz, 1 H), 7.37 (td, J = 7.8, 0.8 Hz, 1 H),
7.33 (d, J = 7.6, 0.4, 1 H), 7.21ꢀ7.30 (m, 4 H), 7.12 (dd, J = 7.6, 0.8 Hz, 1 H), 7.03 (d, J = 8.1, 0.5 Hz, 1 H),
6.98 (td, J = 7.7, 0.9 Hz, 1 H), 6.93 (d, J = 8.0 , 0.7 Hz, 1 H), 6.67 (dd, J = 8.3, 0.3 Hz, 1 H), 6.47 (td, J = 7.5,
0.5 Hz, 1 H), 5.35 (s, 2 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ 198.9, 164.0, 150.9, 147.8, 143.3, 142.3,
138.9, 137.4, 134.5, 133.9, 132.8, 131.0, 130.5, 130.4, 129.4, 129.2, 129.1, 128.0, 127.8, 127.7, 126.0, 122.5,
118.4, 117.0, 115.6, 99.6 ppm; IR (KBr) ν3469, 3354, 1736, 1633, 1547, 1459, 1246, 1189, 527 cm ꢀ1;
HRMS m/z (ESI) : calcld for C26 H19INO3 [M + H]+ 520.0404, found: 520.0413, error ꢀ1.71 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀpivalate (8t): Following the general experiment procedure, 8t was purified by
PE/EtOAc (60:1) and obtained as a white oilꢀliquid (97% yield). Rf = 0.38 (PE/EtOAc = 25:1); 1H NMR
(CDCl3; 500 MHz): δ 7.92 (dd, J = 8.0, 0.5 Hz, 1 H), 7.46 (td, J = 7.8, 0.8 Hz,1 H), 7.31ꢀ7.38 (m, 2 H),
7.22ꢀ7.25 (m, 2 H), 7.16 (dd, J = 8.1, 0.5 Hz, 1 H), 7.04 (td, J = 7.7, 0.9 Hz,1 H), 1.02 (s, 9 H) ppm; 13C
NMR (CDCl3; 126 MHz): δ 176.5, 148.1, 142.8, 138.7, 137.7, 130.6, 129.3, 129.2, 127.8, 125.8, 122.5,
100.1, 38.9, 26.8 ppm; IR (KBr) ν 1749, 1582, 1461, 1193, 1122, 501 cm ꢀ1; HRMS m/z (ESI): calcd for
C17H17INaO2 [M + Na]+ 403.0165, found: 403.0168, error 0.74 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl 2ꢀphenylacetate (8u): Following the general experiment procedure, 8u was
o
purified by PE/EtOAc (100:1) and obtained as a white solid (71% yield). Mp = 93.5ꢀ94.2 C; Rf = 0.40
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(PE/EtOAc = 50:1); 1H NMR (CDCl3; 500 MHz): δ 7.85 (dd, J = 8.0, 0.5 Hz, 1 H), 7.44 (td, J = 7.8, 0.8 Hz,
1 H), 7.32 (td, J = 7.5, 0.6 Hz, 1 H), 7.27 (td, J = 7.5, 0.6 Hz, 1 H),7.22ꢀ7.24 (m, 4 H), 7.19 (dd, J = 8.1, 0.5
Hz, 1 H), 7.16 (dd, J = 7.6, 0.8 Hz, 1 H), 6.99ꢀ7.04 (m, 3 H), 3.57 (s, 2 H) ppm; 13C NMR (CDCl3; 126
MHz): δ 169.6, 147.8, 142.4, 138.9, 137.4, 133.1, 131.0, 130.4, 129.4, 129.3, 129.2, 128.7, 127.8, 127.1,
126.1, 122.5, 99.6, 41.3 ppm; IR (KBr) ν1756, 1495, 1459, 1189, 1128, 489 cmꢀ1; HRMS m/z (ESI): calcd
for C20H15INaO2 [M + Na]+ 437.0009, found: 437.0008, error 0.23 ppm.
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2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀisonicotinate (8v): Following the general experiment procedure, 8ν was
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purified by PE/EtOAc (4:1) and obtained as a white solid (73% yield). Mp = 106.9ꢀ107.8 C; Rf = 0.25
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(PE/EtOAc = 2:1); H NMR (CDCl3; 500 MHz): δ 8.72 (d, J = 5.9 Hz, 2 H), 7.87 (dd, J = 8.0, 0.5 Hz,1 H),
7.70 (dd, J = 4.5, 0.8 Hz, 2 H), 7.51 (td, J = 7.8, 0.6 Hz, 1 H), 7.40 (td, J = 7.5, 0.6 Hz, 1 H), 7.36 (dd, J =
8.1, 0.5 Hz, 1 H), 7.31 (td, J = 8.1, 0.8 Hz, 2 H), 7.25 (dd, J = 7.4, 0.8 Hz, 1 H), 6.97 (td, J = 7.8, 0.9 Hz, 1 H)
ppm; 13C NMR (CDCl3; 126 MHz): δ 163.3, 150.7, 147.6, 142.4, 139.0, 137.3, 136.6, 131.1, 130.5, 129.6,
129.5, 128.1, 126.5, 123.1, 122.3, 99.5 ppm; IR (KBr) ν 1740, 1562, 1463, 1405, 1266, 1189, 498 cm ꢀ1;
HRMS m/z (ESI): calcd for C18H13INO2 [M + H]+ 401.9985, found: 401.9984, error 0.25 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀnicotinate (8w): Following the general experiment procedure, 8w was
o
purified by PE/EtOAc (4:1) and obtained as a white solid (90% yield). Mp = 75.1ꢀ75.9 C; Rf = 0.25
(PE/EtOAc = 2:1); 1H NMR (CDCl3; 500 MHz): δ 9.08 (s,1 H), 8.74 (d, J = 3.6 Hz, 1 H), 8.17 (d, J = 8.0 Hz,
1 H), 7.87 (d, J = 7.8 Hz, 1 H), 7.51 (td, J = 7.7, 0.8 Hz, 1 H), 7.26ꢀ7.40 (m, 6 H), 6.96 (td, J = 7.6, 0.9 Hz, 1
H) ppm; 13C NMR (CDCl3; 126 MHz): δ 163.4, 153.8, 151.2, 147.6, 142.4, 139.0, 137.5, 137.3, 131.0, 130.4,
129.5, 129.4, 128.0, 126.4, 125.4, 123.4, 122.5, 99.5 ppm; IR (KBr) ν 1737, 1591, 1495, 1461, 1270, 1189,
497 cm ꢀ1; HRMS m/z (ESI): calcd for C18H13INO2 [M + H]+ 401.9985, found: 401.9986, error 0.25 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ1Hꢀindoleꢀ3ꢀcarboxylate (8x): Following the general experiment procedure,
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8x was purified by PE/EtOAc (6:1) and obtained as a white solid (75% yield). Mp = 218.5ꢀ219.1 C; Rf =
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0.25 (PE/EtOAc = 3:1); H NMR (DMSOꢀd6; 500 MHz): δ 12.02 (s, 1 H), 7.97 (d, J = 2.9 Hz, 1 H), 7.88
(dd, J = 7.9, 0.5 Hz,1 H), 7.76 (d, J = 7.9 Hz, 1 H), 7.52 (td, J = 7.8, 0.8 Hz, 1 H), 7.46 (d, J = 8.1 Hz, 1H),
7.34ꢀ 7.42 (m, 3 H), 7.27ꢀ7.30 (m, 2 H), 7.18 (t, J = 7.6 Hz, 1 H), 7.10 (t, J = 7.5 Hz, 1 H), 7.00 (td, J = 7.6,
0.9 Hz, 1 H) ppm; 13C NMR (DMSOꢀd6; 126 MHz): δ 162.0, 147.6, 142.5, 138.5, 137.2, 136.3, 133.4, 130.6,
130.3, 129.4, 129.1, 127.9, 125.4, 125.4, 123.2, 122.6, 121.4, 120.4, 112.4, 105.4, 100.1 ppm; IR (KBr) ν
3289, 1688, 1582, 1496, 1460, 1199, 1163, 1123, 485 cm ꢀ1; HRMS m/z (ESI): calcd for C21H14INNaO2 [M +
Na]+461.9961, found: 461.9962, error 0.22 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ1Hꢀindoleꢀ2ꢀcarboxylate (8y): Following the general experiment procedure,
8y was purified by PE/EtOAc (20:1) and obtained as a white solid (78% yield). Mp = 99.1ꢀ99.8 oC; Rf = 0.25
(PE/EtOAc = 10:1); 1H NMR (CDCl3; 500 MHz): δ 9.03 (s, 1 H), 7.89 (d, J = 7.9 Hz, 1 H), 7.68 (d, J = 8.0
Hz, 1 H), 7.54 (td, J = 7.8, 0.9 Hz,1H), 7.40ꢀ7.43(m, 2 H), 7.31ꢀ7.36 (m, 5 H), 7.21 (d, J = 2.0 Hz, 1 H),
7.14ꢀ7.17 (m, 1 H), 6.95ꢀ6.98 (m, 1 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 159.9, 147.5, 142.5, 139.0,
137.4, 137.3, 131.2, 130.6, 129.5, 129.4, 128.0, 127.4, 126.2, 126.2, 125.9, 122.9, 122.7, 121.0, 112.1,
110.4, 99.6 ppm; IR (KBr) ν 3340, 1709, 1620, 1526, 1462, 1241, 1192, 1146, 496 cmꢀ1; HRMS m/z (ESI):
calcd for C21H14INNaO2 [M + Na]+461.9961, found: 461.9966, error 1.08 ppm.
2'ꢀiodoꢀ4,4'ꢀdimethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀphenylacetate (9a): Following the general experiment
procedure, 9a was purified by PE/EtOAc (50:1) and obtained as a white oilꢀliquid (85% yield). Rf = 0.38
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(PE/EtOAc = 25:1); H NMR (CDCl3; 500 MHz): δ 7.67 (s, 1 H), 7.22ꢀ7.26 (m, 3 H), 7.10ꢀ7.15 (m, 2 H),
7.02ꢀ7.08 (m, 4 H), 7.01 (s, 1 H), 3.59 (s, 2 H), 2.43 (s, 3 H), 2.35 (s, 3 H) ppm; 13C NMR (CDCl3; 126
MHz): δ 169.6, 147.7, 139.4, 139.4, 139.3, 138.9, 134.4, 133.2, 130.9, 130.1, 129.3, 128.6, 128.5, 126.9,
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126.8, 122.9, 99.8, 41.3, 21.3, 20.7 ppm; IR (KBr) ν 1757, 1600, 1476, 1221, 1127, 519 cmꢀ1; HRMS m/z
(ESI): calcd for C22H19INaO2 [M + Na]+ 465.0322, found: 465.0323, error 0.28 ppm.
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2'ꢀiodoꢀ4,4'ꢀdimethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀbenzoate (9b): Following the general experiment procedure, 9b
was purified by PE/EtOAc (100:1) and obtained as a yellow oilꢀliquid (95% yield). Rf = 0.44 (PE/EtOAc =
50:1); 1H NMR (CDCl3; 500 MHz): δ 7.97 (dd, J = 8.4, 0.5 Hz, 2 H), 7.71 (s, 1 H), 7.54 (t, J = 7.5 Hz, 1 H),
7.40 (t, J = 7.9 Hz, 2 H), 7.15ꢀ7.18 (m, 4 H), 7.08 (d, J = 7.7 Hz, 1 H), 2.46 (s, 3 H), 2.26 (s, 3 H) ppm;13C
NMR (CDCl3; 126 MHz): δ 164.9, 147.9, 139.8, 139.6, 139.3, 139.1, 134.5, 133.4, 131.0, 130.3, 130.2,
129.6, 128.8, 128.5, 126.8, 123.2, 99.8, 21.4, 20.6 ppm; IR (KBr) ν 1736, 1621, 1600, 1476, 1451, 1127,
1063, 1025, 511 cm ꢀ1; HRMS m/z (ESI): calcld for C21H17INaO2 [M + Na ]+ 451.0165, found: 451.0168,
error 0.67 ppm.
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2'ꢀiodoꢀ4,4'ꢀdimethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀchlorobenzoate (9c): Following the general experiment
procedure, 9c was purified by PE/EtOAc (100:1) and obtained as a white solid (68% yield). Mp =
103.1ꢀ103.9 oC; Rf= 0.25 (PE/EtOAc = 50:1); 1H NMR (CDCl3; 500 MHz): δ 7.76 (s, 1 H), 7.51 (dd, J = 7.8,
0.7 Hz, 1 H), 7.36ꢀ7.41 (m, 2 H), 7.22 (td, J = 7.4, 0.9 Hz, 1 H), 7.17ꢀ7.19 (m, 3 H), 7.16 (s, 1 H), 7.12ꢀ7.14
(m, 1 H), 2.46 (s, 3 H), 2.31 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 163.7, 147.6, 139.7, 139.7, 139.3,
134.5, 134.2, 132.9, 131.6, 131.1, 131.0, 130.4, 129.3, 128.9, 127.1, 126.6, 123.2, 100.0, 21.4, 20.6 ppm; IR
(KBr) ν 1756, 1590, 1476, 1235, 1032, 743, 499 cm ꢀ1; HRMS m/z (ESI): calcd for C21H16ClINaO2 [M +
Na]+ 484.9776, found: 484.9775, error 0.21 ppm.
2'ꢀiodoꢀ4,4'ꢀdimethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (9d): Following the general
experiment procedure, 9d was purified by PE/EtOAc (15:1) and obtained as a yellow oilꢀliquid (90% yield).
Rf = 0.45 (PE/EtOAc = 6:1); 1H NMR (CDCl3; 500 MHz)：δ 7.74 (dd, J = 8.2, 0.6 Hz, 1 H), 7.71 (s, 1 H),
7.15ꢀ7.19 (m, 4 H), 7.08ꢀ7.11 (m, 2 H), 6.55 (t, J = 7.7 Hz, 1 H), 5.74 (s, 2 H), 2.46 (s, 3 H), 2.26 (s, 3 H),
2.13 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ 166.9, 149.6, 147.9, 139.8, 139.5, 139.4, 139.1, 135.4,
134.8, 131.1, 130.2, 129.8, 128.8, 126.7, 123.5, 122.9, 115.8, 109.4, 99.9, 21.5, 20.7, 17.5 ppm; IR (KBr)
ν3495, 3372, 1702, 1613, 1570, 1514, 1475, 1237, 1160, 499 cmꢀ1; HRMS m/z (ESI) : calcd for C22H21INO2
[M + H]+ 458.0611, found: 458.0615, error 0.73 ppm.
2'ꢀiodoꢀ4,4'ꢀdimethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ3a,7aꢀdihydroꢀ1Hꢀindoleꢀ3ꢀcarboxylate (9e): Following the
general experiment procedure, 9e was purified by PE/EtOAc (6:1) and obtained as a white solid (76% yield).
Mp = 230.9ꢀ231.6 oC; Rf = 0.30 (PE/EtOAc = 3:1); 1H NMR (DMSOꢀd6; 500 MHz): δ 12.00 (s,1 H), 7.98 (d,
J = 3.1 Hz, 1 H), 7.78 (d, J = 8.0 Hz, 1 H), 7.70 (s, 1 H), 7.46 (d, J = 8.1 Hz, 1 H), 7.16ꢀ7.20 (m, 3 H),
7.09ꢀ7.13 (m, 4 H), 2.40 (s, 3 H), 2.14 (s, 3 H) ppm; 13C NMR (DMSOꢀd6; 126 MHz): δ 162.1, 147.5, 139.6,
138.8, 138.7, 138.7, 136.3, 134.2, 133.3, 130.6, 130.0, 128.6, 126.0, 125.5, 123.6, 122.6, 121.4, 120.4, 112.4,
105.5, 100.2, 20.7, 19.9 ppm;IR (KBr) ν 3280, 1686, 1524, 1434, 1163, 1122, 499 cmꢀ1; HRMS m/z (ESI):
calcd for C23H18INNaO2 [M + Na]+ 490.0274, found: 490.0277, error 0.61 ppm.
2'ꢀiodoꢀ4,4'ꢀdimethoxyꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (9f): Following the general
experiment procedure, 9f was purified by PE/EtOAc (6:1) and obtained as a yellow solid (13% yield). Mp =
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40.6ꢀ41.5 C; Rf = 0.40 (PE/EtOAc = 3:1); 1H NMR (CDCl3; 500 MHz): δ 7.73 (dd, J = 8.1, 0.5 Hz, 1 H),
7.37 (d, J = 2.6 Hz, 1 H), 7.16ꢀ7.19 (m, 3 H), 6.88ꢀ6.90 (m, 1 H), 6.82ꢀ6.84 (m, 2 H), 6.55 (t, J = 7.7 Hz, 1
H), 5.73 (s, 2 H), 3.86 (s, 3 H), 3.74 (s, 3 H), 2.13 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 166.7, 160.2,
159.0, 149.6, 149.1, 135.4, 134.9, 132.0, 131.0, 130.0, 129.8, 124.0, 122.9, 115.9, 114.1, 111.8, 109.3, 108.4,
100.6, 55.6, 55.6, 17.5 ppm; IR (KBr) ν 3494, 3373, 1702, 1615, 1572, 1281, 1241, 1189, 1057, 487 cmꢀ1;
HRMS m/z (ESI): calcd for C22H21INO4 [M + H]+ 490.0510, found: 490.0507, error 0.61 ppm.
4,4'ꢀdichloroꢀ2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀpivalate (9g): Following the general experiment procedure, 9g
was purified by PE/EtOAc (100:1) and obtained as a white oilꢀliquid (91% yield). Rf = 0.37 (PE/EtOAc =
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50:1); 1H NMR (CDCl3; 500 MHz): δ 7.91(d, J = 2.1 Hz, 1 H), 7.35 (dd, J = 8.2, 1.1 Hz, 1 H), 7.30 (dd, J =
8.2, 1.1 Hz, 1 H), 7.19 (d, J = 2.0 Hz, 1 H), 7.13 (d, J = 3.7 Hz, 1 H), 7.11 (d, J = 3.7 Hz, 1 H), 1.04(s, 9 H)
ppm; 13C NMR (CDCl3; 126 MHz): δ 176.1, 148.5, 140.4, 138.1, 135.1, 134.8, 134.4, 131.4, 131.1, 128.1,
126.3, 123.3, 100.0, 39.0, 26.8 ppm; IR (KBr) ν1753, 1577, 1543, 1458, 1196, 1104, 777, 515 cmꢀ1; HRMS
m/z (ESI): calcd for C17H15Cl2INaO2 [M + Na]+ 470.9386, found: 470.9387, error 0.21 ppm.
9
4,4'ꢀdifluoroꢀ2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀnicotinate (9h): Following the general experiment procedure, 9h
was purified by PE/EtOAc (6:1) and obtained as a yellow solid (60% yield). Mp = 106.0ꢀ106.7 oC; Rf = 0.28
(PE/EtOAc = 3:1); 1H NMR (CDCl3; 500 MHz): δ 9.09 (d, J = 1.5 Hz, 1 H), 8.78 (dd, J = 4.8, 1.5 Hz, 1 H),
8.17 (dt, J = 8.0, 1.9 Hz, 1 H), 7.58 (dd, J = 8.0, 1.3 Hz, 1 H), 7.37 (dd, J = 7.8, 2.5 Hz, 1 H), 7.19ꢀ7.26 (m, 2
H), 7.15 (dd, J = 9.0, 1.3 Hz, 1 H), 7.10 (td, J = 8.3, 1.3 Hz, 1 H), 7.03 (td, J = 8.0, 1.3 Hz, 1 H) ppm; 13C
NMR (CDCl3; 126 MHz): δ 163.7, 163.0, 162.5, 161.7, 160.5, 154.2, 151.2, 148.4 (d, J = 11.0 Hz), 137.8 (d,
J = 3.6 Hz), 137.5, 132.5 (d, J = 3.8 Hz), 132.1 (d, J = 9.3 Hz), 131.3 (d, J = 8.2 Hz), 126.2, 126.0, 124.9,
123.6, 115.5, 115.3, 113.7, 113.6, 110.8, 110.6, 99.3 (d, J = 7.9 Hz) ppm; IR(KBr) ν 1742, 1590, 1489, 1266,
1195, 1101, 502cmꢀ1; HRMS m/z (ESI): calcd for C18H11F2INO2 [M + H]+ 437.9797, found: 437.9793, error
0.91 ppm.
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4,4'ꢀdifluoroꢀ2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀbenzoaten (9i): Following the general experiment procedure, 9i
o
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was purified by PE and obtained as a white solid (94% yield). Mp = 84.3ꢀ85.2 C; Rf = 0.2 (PE); H NMR
(CDCl3; 500 MHz): δ 7.93 (d, J = 7.3 Hz, 2 H), 7.56ꢀ7.61 (m, 2 H), 7.42 (t, J = 7.8 Hz, 2 H), 7.22ꢀ7.27 (m, 2
H), 7.15 (dd, J = 9.1, 1.2 Hz, 1 H), 7.09 (td, J = 8.3, 1.3 Hz, 1 H), 7.03 (td, J = 8.3, 1.4 Hz, 1 H) ppm; 13C
NMR (CDCl3; 126 MHz): δ 164.3, 163.7, 162.5, 161.7, 160.5, 149.0 (d, J = 11.2 Hz), 138.1 (d, J = 3.1 Hz),
133.9, 132.6 (d, J = 3.8 Hz), 132.0 (d, J = 9.3 Hz), 131.4 (d, J = 8.2 Hz), 130.1, 128.8, 128.7, 126.0, 125.9,
115.4, 115.2, 113.3, 113.2, 110.9, 110.7, 99.4(d, J = 8.0 Hz) ppm; IR (KBr) ν 1732, 1591, 1470, 1253, 1198,
1105, 510 cm ꢀ1; HRMS m/z (ESI): calcld for C19H11F2INaO2 [M + Na]+ 458.9664, found: 458.9666, error
0.44 ppm.
4,4'ꢀdichloroꢀ2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl benzoate (9j): Following the general experiment procedure, 9j
was purified by PE/EtOAc (80:1) and obtained as a yellow oilꢀliquid (67% yield). Rf = 0.25 (PE/EtOAc =
50:1); 1H NMR (CDCl3; 500 MHz): δ 7.94 (dd, J = 8.1, 0.5 Hz, 2H), 7.87 (d, J = 2.1 Hz, 1 H), 7.58 (t, J =
7.5 Hz, 1 H), 7.40ꢀ7.44 (m, 3 H), 7.36 (dd, J = 8.2, 1.0 Hz, 1 H), 7.29 (dd, J = 8.3, 1.1 Hz, 1 H), 7.17ꢀ7.22
(m, 2 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 164.3, 148.5, 140.3, 138.4, 135.0, 135.0, 134.4, 133.9, 131.8,
131.0, 130.2, 128.7, 128.7, 128.4, 126.5, 123.5, 99.5 ppm; IR (KBr) ν 1743, 1601, 1577, 1456, 1260, 1097,
705, 509 cm ꢀ1; HRMS m/z (ESI): calcd for C19H11Cl2INaO2 [M + Na]+ 490.9073, found: 490.9070, error
0.61 ppm.
4,4'ꢀdifluoroꢀ2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (9k): Following the general
experiment procedure, 9k was purified by PE/EtOAc (15:1) and obtained as a white solid (76% yield). Mp =
o
1
77.1ꢀ77.9 C; Rf =0.40 (PE/EtOAc = 6:1); H NMR (CDCl3; 500 MHz)：δ 7.62 (dd, J = 8.1,0.5 Hz, 1 H),
7.59 (dd, J =8.2, 1.3 Hz, 1 H), 7.19ꢀ7.25 (m, 3 H), 7.06ꢀ7.10 (m, 2 H), 7.03 (td, J = 8.3, 1.3 Hz, 1 H), 6.54 (t,
J = 7.7 Hz, 1 H), 5.54 (s, 2 H), 2.14 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ 166.3, 163.7, 162.5,
161.7, 160.5, 149.9, 149.0 (d, J = 11.0 Hz), 138.1(d, J = 3.5 Hz), 135.8, 132.9 (d, J = 3.7 Hz), 132.0 (d, J =
9.6 Hz), 131.3 (d, J = 8.3 Hz ), 129.5, 126.1, 125.9, 123.1, 115.9, 115.3 (d, J = 21.1 Hz), 113.1 (d, J = 21.1
Hz), 111.1 (d, J = 24.5 Hz), 108.5, 99.5 (d, J = 7.8 Hz), 17.3 ppm; IR (KBr) ν 3501, 3378, 1705, 1614, 1591,
1473, 1240，1143, 1102, 517 cm ꢀ1; HRMS m/z (ESI) : calcd for C20H15F2INO2 [M + H]+ 466.0110, found:
466.0112, error 0.47 ppm.
4,4'ꢀdichloroꢀ2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (9l): Following the general
experiment procedure, 9l was purified by PE/EtOAc (30:1) and obtained as a brown oilꢀliquid (71% yield).
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Rf = 0.42 (PE/EtOAc = 15:1); 1H NMR (CDCl3; 500 MHz)：δ 7.87 (d, J = 2.1 Hz, 1 H), 7.64 (dd, J = 8.2,0.6
Hz, 1 H), 7.33ꢀ7.36 (m, 2 H), 7.29 (dd, J = 8.3, 1.1 Hz, 1 H), 7.17ꢀ7.21 (m, 3 H), 6.55 (t, J = 7.7 Hz, 1H),
5.64 (s, 2 H), 2.14 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ 166.3, 149.9, 148.5, 140.4, 138.5, 135.9,
135.2, 134.9, 134.3, 131.8, 131.0, 129.5, 128.4, 126.2, 123.8, 123.1, 116.0, 108.4, 99.6, 17.5 ppm; IR (KBr)
ν 3502, 3377, 1704, 1614, 1571, 1459, 1240, 1197, 1156, 750, 462 cm ꢀ1; HRMS m/z (ESI): calcd for
C20H15Cl2INO2 [M + H]+ 497.9519, found: 497.9522, error 0.60 ppm.
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2'ꢀiodoꢀ3,3',5,5'ꢀtetramethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (9m): Following the general
experiment procedure, 9m was purified by PE/EtOAc (20:1) and obtained as a yellow solid (71% yield). Mp
o
= 150.3ꢀ151.2 C; Rf = 0.46 (PE/EtOAc = 10:1); 1H NMR (CDCl3; 500 MHz)：δ 7.77 (d, J = 7.8 Hz, 1 H),
7.16 (d, J = 7.3 Hz, 1 H), 7.14 (s, 1 H), 6.88ꢀ6.91 (m, 3 H), 6.55 (t, J = 7.7 Hz, 1 H), 5.70 (s, 2 H), 2.43 (s, 3
H), 2.38 (s, 3 H), 2.22 (s, 3 H), 2.18 (s, 3 H), 2.12 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz)：δ 166.6,
149.4, 144.5, 143.8, 141.5, 138.8, 137.2, 135.2, 131.3, 130.9, 129.8, 129.6, 129.1, 128.6, 122.8, 115.6,
109.4, 102.7, 29.6, 21.0, 20.7, 17.4, 16.7 ppm; IR (KBr) ν 3498, 3373, 1700, 1613, 1570, 1243, 1191, 466
cm ꢀ1; HRMS m/z (ESI) : calcd for C24H25INO2 [M + H]+ 486.0924, found: 486.0923, error 0.22 ppm.
2'ꢀiodoꢀ3,3',5,5'ꢀtetramethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀhydroxybenzoate (9n): Following the general
experiment procedure, 9n was purified by PE/EtOAc (100:1) and obtained as a white oilꢀliquid (55% yield).
Rf = 0.43 (PE/EtOAc = 50:1); 1H NMR (CDCl3; 500 MHz): δ 10.38 (s, 1 H), 7.86 (d, J = 8.0 Hz, 1 H), 7.44
(td, J = 7.8, 0.9 Hz, 1 H), 7.16 (s, 1 H), 6.92ꢀ 6.94 (m, 2 H), 6.89 (s, 1 H), 6.84ꢀ6.87 (m, 2 H), 2.42 (s, 3 H),
2.40 (s, 3 H), 2.25 (s, 3 H), 2.18 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 168.4, 162.0, 143.9, 143.3,
141.7, 138.5, 137.4, 136.4, 136.2, 136.0, 131.5, 130.6, 129.8, 129.3, 128.6, 119.4, 117.5, 111.7, 102.5, 29.6,
21.1, 20.7, 16.6 ppm; IR (KBr) ν 3193, 1683, 1614, 1484, 1454, 1297, 1189, 1132, 501 cm ꢀ1; HRMS m/z
(ESI): calcd for C23H21INaO3 [M + Na]+ 495.0428, found: 495.0426, error 0.40 ppm.
4ꢀfluoroꢀ2'ꢀiodoꢀ3',5'ꢀdimethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (9o): Following the
general experiment procedure, 9o was purified by PE/EtOAc (100:1) and obtained as a white oilꢀliquid (70%
yield). Rf = 0.43 (PE/EtOAc = 50:1); 1H NMR (CDCl3; 500 MHz): δ 7.57 (dd, J = 8.2, 0.5 Hz, 1 H),
7.23ꢀ7.26 (m, 1 H), 7.17 (d, J = 6.7 Hz, 1 H), 7.13 (dd, J = 9.3, 1.3 Hz, 1 H), 7.06 (dd, J = 8.3, 1.3 Hz, 1H),
6.97 (s, 1 H), 6.88 (s, 1 H), 7.51 (t, J = 7.7 Hz, 1 H), 5.72 (s, 2H), 2.44 (s, 3 H), 2.21 (s, 3 H), 2.13 (s, 3 H)
ppm; 13C NMR (CDCl3; 126 MHz): δ 166.3, 163.3, 161.4, 149.7, 148.8 (d, J = 11.1 Hz), 142.6, 141.9, 137.4,
135.6, 134.9 (d, J = 3.6 Hz), 131.8 (d, J = 9.3 Hz), 130.0, 129.7, 128.8, 122.9, 115.7, 112.8, 112.7, 110.9,
110.7, 108.9, 103.0, 29.6, 20.7, 17.4 ppm; IR (KBr) ν 3500, 3376, 1705, 1614, 1572, 1240, 1188, 1052, 464
cm ꢀ1; HRMS m/z (ESI): calcd for C22H20FINO2 [M + H]+ 476.0517, found: 476.0514, error 0.63 ppm.
4'ꢀ(tertꢀbutyl)ꢀ2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl 2ꢀaminoꢀ3ꢀmethylbenzoate (9p) and
4ꢀ(tertꢀbutyl)ꢀ2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (9p'): Following the general
experiment procedure, 9p and 9p' were purified by PE/EtOAc (20:1) and obtained as an inseparable mixture
1
of white solid (90% yield ). Rf = 0.44 (PE/EtOAc = 10:1); H NMR (CDCl3; 500 MHz): δ 7.95 (d, J = 1.9
Hz, 1 H), 7.91 (dd, J = 7.9, 0.5 Hz, 1 H), 7.82 (dd, J = 8.2, 0.6 Hz, 1 H), 7.66 (dd, J = 8.2, 0.6 Hz, 1 H), 7.53
(td, J = 7.4, 1.2 Hz, 1 H), 7.44 (td, J = 8.1, 1.0 Hz, 1 H), 7.35ꢀ7.41 (m, 5 H), 7.28ꢀ7.33 (m, 3 H), 7.18ꢀ7.20
(m, 2 H), 6.95 (td, J = 7.6, 0.9 Hz, 1 H), 6.59 (t, J = 7.7 Hz, 1 H), 6.55 (t, J = 7.7 Hz, 1 H), 5.67 (s, 4 H), 2.13
(s, 6 H), 1.47 (s, 13 H), 1.33 (s, 5 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 166.7, 152.8, 152.4, 149.4, 148.2,
147.6, 142.7, 139.7, 138.9, 137.5, 135.9, 135.3, 134.6, 131.1, 130.6, 130.5, 129.9, 129.7, 129.6, 129.0,
129.0, 127.8, 125.6, 125.0, 122.9, 122.8, 122.8, 122.7, 119.9, 115.7, 115.6, 109.2, 109.2, 99.9, 99.9, 34.9,
34.4, 31.4, 31.2, 27.0, 17.4 ppm; IR (KBr) ν 3504, 3388, 1700, 1615, 1569, 1463, 1241, 1188, 468 cmꢀ1.
2'ꢀiodoꢀ4'ꢀmethoxyꢀ4ꢀmethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate
(9q)
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2'ꢀiodoꢀ4ꢀmethoxyꢀ4'ꢀmethylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (9q'): Following the general
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experiment procedure, 9q and 9q' were purified by PE/EtOAc (30:1) and obtained as an inseparable mixture
of yellow solid (70% yield). Rf = 0.35 (PE/EtOAc = 15:1); 1HNMR (CDCl3; 500 MHz): δ 7.74 (t, J = 8.6 Hz,
2H), 7.70 (s, 1H), 7.40 (d, J = 2.6 Hz, 1 H), 7.15ꢀ7.20 (m, 7 H), 7.07ꢀ 7.10 (m, 2 H), 6.90 (dd, J = 8.5, 1.3
Hz, 1H), 6.83ꢀ6.85 (m, 2 H), 6.55 (td, J = 7.7, 1.1 Hz, 2 H), 5.72 (s, 4 H), 3.86 (s, 3 H), 3.74 (s, 3 H), 2.45 (s,
3 H), 2.26 (s, 3 H), 2.13 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 166.9, 166.7, 160.2, 159.0, 149.6,
149.6, 148.8, 148.1, 139.6, 139.4, 139.4, 139.0, 135.4, 135.4, 135.1, 134.5, 131.8, 131.3, 130.8, 130.4,
130.2, 129.8,129.8, 128.8, 126.6, 124.0, 123.4, 122.9, 115.8, 114.1, 111.8, 109.3, 109.2, 108.4, 100.4, 100.0,
55.6, 55.5, 21.4, 20.6, 17.4 ppm; IR (KBr) ν 3496, 3373, 1696, 1613, 1515, 1472, 1260, 1190, 1031, 466 cm
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4.3 General procedure for the arylation of aromatic acid derivatives with linear
diaryliodonium salts
The Olofsson's procedure: The carboxylic acid (0.25 mmol), linear diaryliodonium salt 5a (215 mg, 0.50
mmol) and KOtBu (28 mg, 0.25 mmol) were dissolved in anhydrous toluene (1.5 mL) in a pressure νessel.
The reaction mixture was stirred at 130 oC for 17 h before it was cooled to rt. The reaction mixture was then
transferred to a separatory funnel and diluted with Et2O (50 mL). The organic phase was washed with water
(10 mL) and brine (10 mL) respectively before it was dried over anhydrous Mg2SO4 and concentrated in
vacuo. The residue was purified by column chromatography to yield the product.
Our procedure: The carboxylic acid (0.25 mmol), linear diaryliodonium salt 5a (215 mg, 0.5 mmol),
Na2CO3 (39.75 mg, 0.38 mmol), CuI (4.8 mg, 0.025 mmol) and 1,10ꢀPhenanthroline (4.5 mg, 0.025 mmol)
were dissolved in anhydrous 1,4ꢀdioxane (1.5 mL) in a pressure νessel. 3 Å Molecular sieves (100 mg) were
o
then added. The reaction mixture was stirred at 95 C for 17 h before it was cooled to rt and filtered. The
mixture was then extracted with EtOAc (50 mL) and washed with water (10 mL) and brine (10 mL) before
the organic phase was dried over anhydrous Na2SO4 and concentrated in vacuo. The residue was purified by
column chromatography to yield the product.
phenyl 2ꢀaminoꢀ3ꢀmethylbenzoate (10): 10 was purified by PE/EtOAc (20:1) and obtained as a white
o
solid. Yield: 21% (Olofsson’s procedure) and 63% (our procedure); Mp = 106.3ꢀ107.4 C; Rf = 0.60
(PE/EtOAc = 10:1); 1H NMR (CDCl3; 500 MHz): δ 8.03 (dd, J = 8.1, 0.5 Hz, 1 H), 7.44 (t, J = 8.0 Hz, 2 H),
7.28 (t, J = 6.4 Hz, 2 H), 7.20 (dd, J = 8.7, 0.6 Hz, 2 H), 6.68 (t, J = 7.7 Hz, 1 H), 5.89 (s, 2 H), 2.21 (s, 3 H)
ppm; 13C NMR (CDCl3; 126 MHz): δ 167.4, 151.1, 150.0, 135.7, 129.7, 129.6, 125.9, 123.2, 122.2, 115.9,
109.3, 17.5 ppm; IR (KBr) ν 3452, 3348, 1696, 1613, 1584, 1242, 1192 cm ꢀ1; HRMS m/z (ESI) : calcd for
C14H14O2 [M + H] + 228.1019, found: 228.1021, error ꢀ0.86 ppm.
phenyl 2ꢀhydroxybenzoate (11): 11 was purified by PE/EtOAc (20:1) and obtained as a white oilꢀliquid.
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Yield: 62% (Olofsson’s procedure) and 85% (our procedure); Rf = 0.50 (PE/EtOAc = 10:1); H NMR
(CDCl3; 500 MHz): δ 10.53 (s, 1 H), 8.10 (dd, J = 8.0, 0.8 Hz, 1 H), 7.55 (t, J = 7.9 Hz, 1 H), 7.47 (t, J = 7.9
Hz, 2 H), 7.33 (t, J = 7.4 Hz, 1 H), 7.22ꢀ7.24 (m, 2 H), 7.06 (dd, J = 8.4, 0.4 Hz, 1 H), 6.99 (t, J = 7.6 Hz, 1
H) ppm; 13C NMR (CDCl3; 126 MHz): δ 169.1, 162.3, 150.2, 136.6, 130.5, 129.8, 126.5, 121.8, 119.6,
118.0, 112.0 ppm; IR (KBr) ν 3215, 1701,1630,1514,1260,1185 cmꢀ1; HRMS m/z (EI) : calcd for C13H10O3
[M] + 214.0630,found: 214.0645 error 7.0 ppm.
phenyl 2ꢀ(phenylthio)benzoate (12): 12 was purified by PE/EtOAc (20:1) and obtained as a yellow solid.
Yield: 22% (Olofsson’s procedure) and 14% (our procedure); Mp = 81.0ꢀ82.2 oC; Rf = 0.38 (PE/EtOAc =
10:1); 1H NMR (CDCl3; 500 MHz): δ 8.23 (dd, J = 7.9, 0.6 Hz, 1 H), 7.58ꢀ7.60 (m, 2 H), 7.43ꢀ7.45 (m, 5 H),
7.28ꢀ7.33 (m, 2 H), 7.25ꢀ7.27 (m, 2 H), 7.20 (td, J = 7.5, 0.6 Hz, 1 H), 6.87 (dd, J = 8.2, 0.5 Hz, 1 H) ppm;
13C NMR (126 MHz, CDCl3): δ 164.9, 150.9, 144.4, 135.8, 133.0, 132.5, 131.7, 129.9, 129.6, 129.4, 127.7,
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126.1, 124.5, 122.0, 116.5 ppm; IR (KBr) ν 1699, 1630, 1615, 1514, 1240, 1185 cmꢀ1; HRMS m/z (EI) :
calcd for C19H14O2S [M] + 306.0715, found: 306.0723 error 2.6 ppm.
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4.4 Experiments about selectivity and mechanistic studies. Synthesis of
2'ꢀiodoꢀNꢀphenylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀamine (14a): Aniline 13a (22.8 uL, 0.25 mmol), cyclic
diphenyleneiodonium 7a (210 mg, 0.50 mmol), Na2CO3 (39.75 mg, 0.375 mmol), CuI (4.8 mg, 0.025 mmol)
and 1,10ꢀPhenanthroline (4.5 mg, 0.025 mmol) were dissolved in anhydrous 1,4ꢀdioxane (1.5 mL) in a
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pressure νessel. 3 Å molecular sieves (100 mg) were then added. The reaction mixture was stirred at 95 C
for 17 h before it was cooled to rt and filtered. The mixture was then extracted with EtOAc (50 mL) and
washed with water (10 mL) and brine (10 mL) before the organic phase was dried over anhydrous Na2SO4
and concentrated in vacuo. The residue was purified by column chromatography (PE/EtOAc = 60:1) on
o
silica gel to provideprovide a yellow solid 14a (48.7 mg, 53% yield). Mp = 76.2ꢀ77.3 C; Rf = 0.35
(PE/EtOAc = 30:1); 1H NMR (CDCl3; 500 MHz): δ 8.00 (dd, J = 8.0, 0.5 Hz, 1 H), 7.45 (td, J = 7.5, 0.6 Hz,
1 H), 7.37 (dd, J = 8.2, 0.5 Hz, 1 H), 7.35 (dd, J = 7.6, 0.8 Hz, 1 H), 7.31 (td, J = 7.7, 0.8 Hz, 1 H), 7.26 (t, J
= 8.0 Hz, 2 H), 7.07ꢀ7.12 (m, 4 H), 7.00 (td, J = 7.5, 0.6 Hz, 1 H), 6.96 (t, J = 7.4 Hz, 1 H), 5.21(s, 1 H)
ppm; 13C NMR (CDCl3; 126 MHz): δ 144.0, 142.8,140.8, 139.7, 133.5, 130.9, 130.7, 129.5, 129.3, 129.0,
128.9, 121.8, 120.3, 119.5, 116.3, 101.1 ppm; IR (KBr) ν 3394,1573,1507,1459,512 cmꢀ1; HRMS m/z (ESI):
calcd for C18H15NI [M + H]+ 372.0244, found: 372.0245, error ꢀ0.35 ppm.
The procedure of scheme 3b: The procedure was similar to 14a, Aniline 13a (22.8 uL, 0.25 mmol), benzoic
acid (30.7 mg, 0.25 mmol) was used. 14a (3.7 mg, 4%) and 8b (95.0 mg, 95%) were obtained.
4.5 Procedures for the further transformations of products. Synthesis of
2'ꢀ((trimethylsilyl)ethynyl)ꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (16): Compound 8a (107.25mg,
0.25 mmol), 2ꢀTMSꢀacetylene (45uL, 0.3mmol), Pd(PPh3)2Cl2 (18 mg, 0.025 mmol) and Et3N (0.2 ml, 1.5
mmol) were dissolved in THF (2 ml). The reaction mixture was degassed and stirred under an N2 atmosphere
for 20 min before the addition of CuI (4.8 mg, 0.025 mmol). The reaction was then stirred at r.t.for 12 h
before itwas diluted with diethyl ether (10 mL). The content was poured into a separate funnel and washed
with 0.1 M HCl (10 mL), H2O (10 mL) and brine (10 mL) respectively. The organic phase was dried over
anhydrous Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography
(PE/EtOAc = 20:1) on silica gel to provide a yellow solid 16 (72.8 mg, 73% yield). Mp = 108.6ꢀ109.4 oC; Rf
1
= 0.40 (PE/EtOAc = 10:1); H NMR (CDCl3; 500 MHz): δ 7.85 (d, J = 8.1 Hz, 1 H), 7.52 (dd, J = 7.6, 0.4
Hz, 1 H), 7.45ꢀ7.48 (m, 2 H), 7.27ꢀ 7.35 (m, 4 H), 7.22 (td, J = 7.5, 0.7 Hz, 1H), 7.18 (d, J = 7.1 Hz, 1 H),
6.56 (t, J = 7.7 Hz, 1 H), 5.72 (s, 2 H), 2.13 (s, 3 H), 0.13 (s, 9 H) ppm; 13C NMR (CDCl3; 126 MHz): δ
166.9, 149.5, 148.4, 140.8, 135.3, 134.1, 132.2, 131.5, 129.9, 129.8, 128.8, 128.4, 127.4, 125.5, 123.0,
122.8, 122.7, 115.7, 109.5, 104.5, 97.5, 17.4, ꢀ0.2 ppm; IR (KBr) ν 3478, 3363, 2158, 1704, 1615, 1475,
1246, 1198 cm ꢀ1; HRMS m/z (ESI) : calcd for C25H26NO2Si [M + H] + 400.1727，found: 400.1733, error
1.46 ppm.
(E)ꢀ2'ꢀstyrylꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (17): Compound 8a (107.25 mg, 0.25 mmol),
styrene (32 mg, 0.3 mmol), Pd(OAc)2 (2.8 mg, 0.0125 mmol) and AgOAc (83.5 mg, 0.5 mmol) were
o
dissolved in HOAc (2 mL). The reaction mixture was stirred at 110 C for 12 h. After that, the reaction
mixture was cooled to rt and neutralized with saturated Na2CO3 solution (10 mL). The reaction mixture was
extracted by EtOAc (3 ×10 mL), the combined organic phase was washed with H2O (2 × 10 mL) and brine
(10 mL), dried over anhydrous Na2SO4, and concentrated in vacuo. The residue was purified by column
chromatography (PE/EtOAc = 20:1) on silica gel to providea white oilꢀliquid 17 (53.7 mg, 53% yield). Rf =
0.40 (PE/EtOAc = 10:1); 1H NMR (CDCl3; 500 MHz): δ 7.69 (d, J = 7.8 Hz, 1 H), 7.59 (dd, J = 8.1, 0.6 Hz,
1 H), 7.49 (td, J = 7.6, 1.0 Hz, 1 H), 7.27ꢀ7.40 (m, 10 H), 7.22 (t, J = 7.3 Hz, 1 H), 7.13 (d, J = 7.3 Hz, 1 H),
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6.92ꢀ7.03 (m, 2 H), 6.44 (t, J = 7.7 Hz, 1 H), 5.38 (s, 2 H), 2.08 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz):
δ 166.8, 149.7, 148.6, 137.7, 136.7, 136.2, 135.3, 134.2, 132.0, 130.8, 129.8, 129.7, 128.8, 128.6, 128.1,
127.6, 127.5, 127.3, 126.8, 125.9, 125.2, 123.2, 122.8, 115.6, 109.4, 17.4 ppm; IR (KBr) ν 3498, 3373, 1695,
1611, 1572, 1240, 1199, 1157 cm ꢀ1; HRMS m/z (ESI): calcd for C28H24NO2 [M + H]+ 406.1802, found:
406.1799, error 0.74 ppm.
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2'ꢀcyanoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀyl 2ꢀaminoꢀ3ꢀmethylbenzoate (18): Compound 8a (107.25 mg, 0.25 mmol) and
CuCN (67.5 mg, 0.75 mmol) were dissolνed in anhydrous Nꢀmethyl pyrrolidone (2 mL). The reaction
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mixture was refluxed at 180 C for 12 h before it was cooled to rt and diluted with water (10 mL). The
mixture was extracted with EtOAc (3 ×10 mL), the combined organic phase was washed with H2O (3 × 10
mL) and brine (10 mL), dried over anhydrous Na2SO4, and concentrated in νacuo. The residue was purified
by column chromatography (PE/EtOAc = 15:1) on silica gel to provide a white solid 18 (41.0 mg, 50%
yield). Mp = 116.8ꢀ117.4 oC; Rf = 0.50 (PE/EtOAc = 3:1); H NMR (CDCl3; 500 MHz): δ 7.84 (dd, J= 8.1,
1
0.6 Hz, 1 H), 7.69 (dd, J = 7.8, 0.4 Hz, 1H), 7.51ꢀ7.56 (m, 2 H), 7.46ꢀ7.48 (m, 2 H), 7.33ꢀ7.42 (m, 3 H), 7.19
(d, J = 7.2 Hz, 1 H), 6.58 (t, J = 7.7 Hz, 1 H), 5.61 (s, 2 H), 2.12 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz):
δ 166.5, 149.7, 148.0, 141.3, 135.5, 133.0, 132.5, 131.9, 131.0, 130.8, 130.2, 129.5, 128.1, 126.3, 123.5,
123.0, 118.3, 115.9, 112.9, 108.6, 17.4 ppm; IR (KBr) ν 3468, 3368, 2224, 1697, 1616, 1573, 1238, 1192,
1061 cm ꢀ1; HRMS m/z (ESI): calcd for C21 H17N2O2 [M + H]+ 329.1285, found: 329.1291, error ꢀ1.82 ppm.
2'ꢀ(diphenylphosphino)ꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀaminoꢀ3ꢀmethylbenzoate (19): Compound 8a (107.25 mg,
0.25 mmol), HPPh2 (87 ul, 0.5 mmol), Pd(OAc)2 (5.6 mg, 0.025 mmol) and KOAc (49 mg, 0.3 mmol) were
o
dissolνed in anhydrous DMA (2 mL). The reaction mixture was stirred at 100 C for 12 h under N2
atmosphere. The reaction mixture was cooled to rt and diluted with water (10 mL). The mixture was
extracted with EtOAc (3 × 10 mL). The combined organic phase was washed with H2O (2 ×10 mL) and
brine (10 mL), dried over anhydrous Na2SO4, concentrated in vacuo. The residue was purified by column
chromatography (PE/EtOAc =20:1) on silica gel to provide a white solid 19 (65.8 mg, 54% yield). Mp =
112.7ꢀ113.8 oC, Rf = 0.22 (PE/EtOAc = 10:1). 1H NMR (CDCl3; 500 MHz): δ 7.54 (dd, J = 8.2, 0.6 Hz, 1 H),
7.38 (td, J = 7.8, 0.9 Hz, 1 H), 7.27ꢀ7.30 (m, 5 H), 7.16ꢀ7.25 (m, 10 H), 7.12 (td, J = 7.5, 0.6 Hz, 1 H),
7.04ꢀ7.07 (m, 2 H), 6.48 (t, J = 7.7 Hz, 1 H), 5.72 (s, 2 H), 2.13 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz):
δ 166.9, 149.6, 148.2, 143.6, 143.4, 137.4ꢀ137.6 (m), 137.3, 137.2, 135.3, 134.9 (d, J = 2.8 Hz), 134.2,
134.0, 133.9, 133.7, 132.1 (d, J = 3.9 Hz), 130.3 (d, J = 5.2 Hz), 129.8, 128.8, 128.6, 128.3ꢀ128.5(m), 128.0,
125.2, 122.9, 122.8, 115.6, 109.4, 17.5 ppm; IR (KBr) ν 3499, 3373, 2247, 1702, 1613, 1570, 1242, 1191,
1061 cm ꢀ1; HRMS m/z (ESI): calcd for C32H27NO2P [M + H]+ 488.1774, found: 488.1777, error 0.61 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ3ꢀmethylbenzoate (20): To a stirred solution of 8a (107.25 mg, 0.25 mmol) in
THF (6 mL) was added 4 M aqueous HCl (6 mL), and the solution was cooled in an ice water bath. A
solution of NaNO2 (0.25 g, 3.6 mmol) in H2O (1 mL) was added dropwise. The reaction mixture was stirrer
for 1 h. After that, stannous chloride dihydrate (345.2 mg, 1.5 mmol) was added. The reaction mixture was
stirred for 0.5 h in an iceꢀbath. The mixture was neutralized with 40% NaOH solution before it was extracted
with EtOAc (3 × 10 mL). The combined organic phase were washed with H2O (2 × 10 mL) and brine (10
mL), dried over anhydrous Na2SO4, and concentrated under in vacuo. The residue was purified by column
chromatography (PE/EtOAc = 20:1) on silica gel to provide a white solid 20 (64.2 mg, 62% yield). Mp =
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82.7ꢀ83.9 C; Rf = 0.60 (PE/EtOAc = 10:1); H NMR (CDCl3; 500 MHz): δ 7.89 (d, J = 7.6 Hz, 1 H),
7.73ꢀ7.74 (m, 2 H), 7.51 (td, J = 7.8, 0.9 Hz, 1 H), 7.36ꢀ7.39 (m, 2 H), 7.34 (s, 1 H), 7.28ꢀ7.33 (m, 4 H),
6.95ꢀ6.99 (m, 1 H), 2.36 (s, 3 H) ppm; 13C NMR (CDCl3; 126 MHz): δ 164.9, 148.1, 142.8, 138.9, 138.3,
137.5, 134.2, 131.0, 130.7, 130.6, 129.4, 129.3, 129.2, 128.4, 128.0, 127.2, 126.0, 122.7, 99.7, 21.3 ppm; IR
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(KBr) ν1738, 1590, 1462, 1276, 1197, 1070, 490 cmꢀ1; HRMS m/z (ESI): calcd for C20H15INaO2 [M + Na]+
437.0009，found: 437.0011, error 0.51 ppm.
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2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀazidoꢀ3ꢀmethylbenzoate (21): Compound 8a (107.25 mg, 0.25 mmol) was
dissolνed in acetonitrile (2 mL) and cooled in a ice bath. TertꢀButyl nitrite (80 ul, 0.6 mmol) and
Trimethylsilylazide (43 ul, 0.3 mmol) were added in dropwise. The resulting solution was stirred 20 min at
r.t. Saturated NaHCO3 solution (5 mL) was then added. The mixture was extracted with EtOAc (3 ×10 mL).
The combined organic layers were washed with water (10 mL) and brine (10 mL), dried oνer anhydrous
Na2SO4, and concentrated in vacuo. The crude residue was purified by silica gel chromatography (PE/EtOAc
= 20:1) to provide a white solid 21 (91.0 mg, 80% yield). Mp = 81.4ꢀ82.3 oC; Rf = 0.50 (PE/EtOAc = 10:1);
1H NMR (CDCl3; 500 MHz): δ 7.92 (d, J = 7.5 Hz, 1 H), 7.53 (td, J = 7.8, 0.9 Hz, 1 H), 7.41 (td, J = 7.0, 0.5
Hz, 2 H), 7.37 (td, J = 6.8, 0.6 Hz, 1 H), 7.31ꢀ7.33 (m, 4 H), 6.99ꢀ7.05 (m, 2 H), 2.33 (s, 3 H) ppm; 13C
NMR (CDCl3; 126 MHz): δ 163.7, 147.7, 142.6, 139.3, 138.9, 137.5, 135.3, 133.5, 131.1, 130.6, 129.6,
129.5, 129.4, 128.1, 126.3, 125.1, 123.4, 122.9, 99.8, 18.3 ppm; IR (KBr) ν 2120, 1722, 1583, 1454, 1242,
1185, 1118, 495 cm ꢀ1; HRMS m/z (ESI): calcd for C20H14IN3NaO2 [M + Na]+ 478.0023, found: 478.0027,
error 0.93 ppm.
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2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ1Hꢀindazoleꢀ7ꢀcarboxylate (22): Compound 8a (107.25 mg, 0.25 mmol) was
dissolνed in acetonitrile (2 mL). The mixture was added tertꢀButyl nitrite (67 ul, 0.5 mmol) dropwise. The
reaction mixture was stirred at rt for 20 h. The mixture was diluted with water (10 mL) and extracted with
EtOAc (3 × 10 mL). The combined organic layers were washed with water (2 × 10 mL) and brine (10 mL),
dried over anhydrous Na2SO4, and concentrated under in vacuo. The crude residue was purified by silica gel
chromatography (PE/EtOAc = 6:1) to provide a yellow solid 22 (59.4 mg, 54% yield). Mp = 84.3ꢀ85.4 oC; Rf
= 0.23 (PE/EtOAc = 3:1); 1H NMR (CDCl3; 500 MHz): δ 11.06 (s, 1 H), 8.12 (s, 1 H), 8.02 (dd, J = 7.3, 0.4
Hz, 1 H), 7.97 (dd, J = 8.0, 0.3 Hz, 1 H), 7.86 (d, J = 7.8 Hz, 1 H), 7.54 (td, J = 7.8, 0.8 Hz, 1 H), 7.40ꢀ7.45
(m, 2 H), 7.28ꢀ7.35 (m, 3 H), 7.19 (t, J = 7.7 Hz, 1 H), 6.94 (td, J = 7.4, 1.2 Hz, 1 H) ppm; 13C NMR (CDCl3;
126 MHz): δ 164.3, 147.6, 142.6, 139.0, 138.8, 137.5, 135.2, 131.1, 130.4, 130.1, 129.6, 129.5, 128.2, 127.4,
126.4, 124.6, 122.7, 120.7, 111.7, 99.6 ppm; IR (KBr) ν 3433, 1717, 1616, 1495, 1462, 1191, 1130, 497 cmꢀ1;
HRMS m/z (ESI): calcd for C20H14IN2O2 [M +H]+ 441.0094, found: 441.0093, error 0.23 ppm.
2'ꢀiodoꢀ[1,1'ꢀbiphenyl]ꢀ2ꢀylꢀ2ꢀiodoꢀ3ꢀmethylbenzoate (not shown in the manuscript): To a stirred
solution of 8a (429 mg, 1.0 mmol) in THF (3 mL) was added 4 M aqueous HCl (2.4 mL), and the solution
was cooled in an ice water bath. A solution of NaNO2 (0.10 g, 1.45 mmol) in H2O (1 mL) was added
dropwise. After 20 min, a solution of KI (0.40 g, 2.4 mmol) in H2O (1 mL) was added. The reaction mixture
was stirred for 10 min in the ice water bath, then slowly warmed up to r.t. and stirred overnight before 1 M
aqueous Na2S2O3 was added until the color of the mixture didn’t change. The phases were separated, and the
aqueous phase extracted with EtOAc (10 mL× 3). The combined organic layers were washed with H2O (10
mL × 2) and brine (10 mL), dried over anhydrous Na2SO4, and concentrated in vacuo. The residue was
purified by column chromatography on silica gel (PE/EtOAc = 20:1) to provide the diꢀiodo compound as a
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white solid (485.9 mg, 90%). Mp = 128.8ꢀ129.4 C; Rf = 0.50 (PE/EtOAc = 10:1); H NMR (CDCl3; 500
MHz): δ 7.94 (dd, J= 8.0, 0.5 Hz, 1 H), 7.52 (td, J= 7.8, 0.9 Hz, 1 H), 7.37ꢀ7.40 (m, 2H), 7.35 (dd, J= 7.1,
0.5 Hz, 1 H), 7.32 (td, J= 7.9, 1.0 Hz, 2 H), 7.29 (dd, J= 7.6, 0.5 Hz, 1 H), 7.14 (t, J= 7.6 Hz, 1 H), 7.04 (td,
J= 7.5, 1.0 Hz, 1 H), 6.86 (dd, J= 7.6, 0.6 Hz, 1 H), 2.48(s, 3H) ppm;13CNMR (CDCl3; 126 MHz): δ 166.2,
147.8, 143.6, 142.6, 139.0, 137.6, 137.1, 132.2, 131.2, 130.8, 129.6, 129.5, 128.1, 127.8, 127.3, 126.4,
122.8, 100.4, 99.9, 29.8 ppm; IR (KBr) ν 1743, 1571, 1458, 1216, 1120, 510 cmꢀ1; HRMS m/z (ESI): calcd
for C20H14I2NaO2 [M + Na]+ 562.8975, found: 562.8974, error 0.18 ppm.
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0.25 mmol), Pd(OAc)2 (5.6 mg, 0.025 mmol) and NaOAc (24.61 mg, 0.3 mmol) were dissolved in
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anhydrous DMF (1 mL). The reaction mixture was stirrer at 150 C for 3 h. Then the reaction mixture was
diluted with water (10 mL) and extracted with EtOAc (10 mLｘ3), washed with water (10 mLｘ2), brine
(10 mL), dried over anhydrous Na2SO4, concentrated in vacuo. The residue was purified by column
chromatography on silica gel (PE/EtOAc = 20:1) to provide a white solid 23 (52.5 mg, 51% yield). Mp =
181.3ꢀ182.4 oC; Rf = 0.28 (PE/EtOAc = 10:1); 1H NMR(CDCl3; 500 MHz): δ 8.40 (dd, J = 8.3, 0.7 Hz, 1 H),
8.37 (dd, J = 7.8, 0.6 Hz, 1 H), 7.98 (dd, J = 8.0, 0.5 Hz, 1 H), 7.68 (dd, J = 7.5, 0.4 Hz, 1 H), 7.49 (t, J = 7.7
Hz, 1 H), 7.45 (td, J = 7.5, 0.6 Hz, 1 H), 7.41 (t, J = 7.8 Hz, 1 H), 7.33ꢀ7.36(m, 2 H), 7.11 (td, J= 7.7, 0.9
Hz, 1 H), 2.97(s, 3 H) ppm; 13C NMR(CDCl3; 126 MHz): δ 161.1, 148.1, 142.0, 139.2, 139.2, 135.1, 133.7,
131.4, 130.5, 129.5, 129.2, 128.4, 128.1, 127.2, 123.4, 122.9, 120.0, 100.0, 25.5 ppm; IR(KBr) ν 1712, 1463,
1409, 1282, 1079, 505 cmꢀ1; HRMS m/z (ESI): calcd for C20H14IO2 [M +H ]+ 413.0033, found: 413.0038,
error ꢀ1.22 ppm.
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website.
1H and 13C NMR spectra of compounds (PDF)
AUTHOR INFORMATION
Corresponding Author
* Email: zhangfengzhi@zjut.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We thank the Natural Science Foundation for Distinguished Young Scholars of Zhejiang Province
(LR15H300001), ThousandꢀTalent Program of Zhejiang Province and Zhejiang University of Technology for
financial support.
REFERENCES
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