Transition-Metal-Free Cross-Coupling of Aryl Halides with Arylstannanes

Article abstract of DOI:10.1021/acs.joc.6b01648

Transition-metal-free LiCl-promoted cross-coupling reactions of tetraphenyltin, trichlorophenyl-, dichlorodiphenyl-, and chlorotriphenylstannanes with aryl halides in DMF provided access to biaryls in good to high yields. Up to four phenyl groups were transferred from the organostannanes substrates. The aryls bearing electron-withdrawing groups in either halides or organotin substrates gave coupling products in higher yields. The methodology has been applied for the efficient synthesis of ipriflavones.

Full text of DOI:10.1021/acs.joc.6b01648

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Note
Transition-metal-free cross-coupling of aryl halides with arylstannanes
Qing He, Liwen Wang, Yong Liang, Zunting Zhang, and Stanislaw F Wnuk
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01648 • Publication Date (Web): 29 Aug 2016
Downloaded from http://pubs.acs.org on August 29, 2016
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Transition-metal-free cross-coupling of aryl halides with arylstannanes
Qing He,a,b Liwen Wang,a Yong Liang,†c Zunting Zhang,*,a Stanislaw F. Wnuk*,c
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aKey Laboratory of the Ministry of Education for Medicinal Resources and Natural Pharmaceutical Chemistry,
National Engineering Laboratory for Resource Development of Endangered Crude Drugs in Northwest of China,
School of Chemistry＆Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P.R.China. bCollege of
Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325027, P.R.China. cDepartment of Chemistry
and Biochemistry, Florida International University, Miami, FL 33199, USA.
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E-mail: zhangzt@snnu.edu.cn; wnuk@fiu.edu
TOC graphic
Abstract. Transition-metal free LiCl-promoted cross-coupling reactions of tetraphenyltin,
trichlorophenyl-, dichlorodiphenyl-, and chlorotriphenylstannanes with aryl halides in DMF
provided access to biaryls in good to high yields. Up to four phenyl groups were transferred from
the organostannanes substrates. The aryls bearing electron-withdrawing groups either in halides
or organotin substrates gave coupling products in higher yields. The methodology has been
applied for the efficient synthesis of ipriflavones.
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The transition-metal catalyzed cross-coupling of organomagnesium (Kumada), organozinc
(Negishi), organoboron (Suzuki), organotin (Stille), or organosilicon (Hiyama) with aryl, alkenyl
or alkyl halides is one of the most widely used methods for the formation of new carbon-carbon
bonds.1-2 In recent years, alternative approaches have begun to compete with these traditional
cross-coupling protocols. One such approach is the C-H functionalization based on the coupling
of one activated component (e.g, aryl halides) requiring direct C-H bond activation on the
counterpart.3-5 Cross dehydrogenative-coupling reactions, which require direct activation of C-H
bonds on both substrates (e.g., alkene and/or arenes), have been also developed.6-8 The
combination of transition metal catalysts with oxidants and ligands was found to be crucial for
efficient cross-coupling via direct C-H functionalization.
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Recently, there has also been a significant effort to develop cross-coupling reactions that
avoid the usage of a transition-metal catalyst, in order to facilitate the purification of products and
lower the costs.9-11 This includes cross-coupling of aryl halides with aryl Grignard,12-14
arylzinc,15-16 or organoaluminium17 reagents, among others.11 These transition-metal-free
synthesis of biaryls occurred via homolytic aromatic substitution (HAS),18-19 single electron
transfer (SET) processes via SRN1,12,15,20-22 or via benzyne-radical initiation.23
The effect of lithium halides on the transition-metal catalyzed Stille,24 Negishi,25-26
Suzuki,27-28 and other reactions29-32 have been studied. LiCl accelerates the formation of
organozinc reagents33 and enhances their reactivity towards transmetallation34 by forming more
nucleophilic lithium zincate complexes.33,35 Recently, the effect of LiCl on increasing
cross-coupling efficiency of Kumada- or Negishi-type transition-metal-free reactions with aryl or
alkenyl halides has also been reported.13,15 However, the analogous effect of LiCl in the transition
metal-free Stille cross-coupling reaction is still undeveloped. Herein, we report first
transition-metal-free LiCl-promoted cross-coupling of aryl halides and arylstannanes to give
access to biaryls.
Initially, we examined coupling of tetraphenyltin 2a with iodonaphthalene 1a in DMAC in
the presence of LiCl. Thus, heating of 2a with 1 equiv. of 1a in the presence of LiCl (5 equiv.) at
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140 C for 4 h produced the biaryl product 3 in 92% yield, along with minor quantities of the
reductive homocoupling byproduct 4 (3:4, 40:1; Table 1, entry 1). Coupling also proceeded
smoothly in DMF (entry 2), whereas no 3 was formed in refluxing toluene (entry 3). Screening of
the LiCl loading showed that 5 equiv. of LiCl are required to produce 3 in maximum yield
(entries 4-5). Coupling in the absent of LiCl led mainly to the recovery of 1a with only a trace
amount of 3 detected (entry 6). At least 3 h of heating was required to produce 3 in high yield
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(entry 7-9). Reaction at higher temperature (160 C) yielded substantial quantities of biphenyl
homocoupling byproduct 4 with decreased formation of 3 (32%; entry 10). Interestingly, at lower
o
temperature (120 C), product 3 was also obtained in lower yield (25%) but with excellent
selectivity of 3 over 4 (entry 11). Prolonged reaction time afforded 3 in higher yield with the
retention of good ratio of 3 to 4 (entry 11, footnote). Other lithium salts were less efficient (LiBr
or LiI) or failed (LiF) to promote coupling (entries 12-14). The coupling also proceeded less
successfully when chloride salts other than LiCl were used; with NaCl giving 3 in good yield,
while coupling basically failed in the presence of KCl or CsCl (entries 15-17).
Table 1. Optimization of the LiCl-promoted cross-coupling between iodonaphtalene 1a and tetraphenyltin 2aa
yield (%) b, c ratio b
additives
entry solvent
1
T/oC Time/h
3
3:4
salts equiv.
DMAC LiCl
5
5
5
3
1
0
5
5
5
5
140
140
110
140
140
140
140
140
140
160
4
4
4
4
4
4
1
2
3
4
92 (79)
98 (87)
-- d
40:1
99:1
-- e
2
3
DMF
LiCl
Toluene LiCl
4
DMF
DMF
DMF
DMF
DMF
DMF
DMF
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
LiCl
64
50:1
20:1
-- f
5
45
6
5
7
32
99:1
50:1
80:1
0.9:1
8
58
9
96 (82)
32
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DMF
DMF
DMF
DMF
DMF
DMF
DMF
LiCl
LiBr
LiI
5
5
5
5
5
5
5
120
140
140
140
140
140
140
4
4
4
4
4
4
4
25g
65
45
--d
76
10
12
99:1
2:1
10:1
-- f
LiF
NaCl
KCl
CsCl
8:1
-- f
-- f
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b
a Couplings were performed on 0.20 mmol scale of 2a (0.05 M) with 1 equiv of 1a. Determined by
1
c
d
e
GC/MS and/or H NMR. Isolated yield in parenthesis. Product 3 was not detected. Homocoupling
byproduct 4 was observed. f Not determined. g Coupling in 5 h, 6 h or 12 h yielded 3 in 32% (80:1), 40%
(80:1) or 48% (75:1), respectively.
We also examined coupling of 1a with various equivalents,36-38 of 2a to increase the atom
efficiency of the LiCl-promoted Stille cross-coupling reactions. Thus, couplings of 2a with 1-4
equiv. of 1a gave 3 in excellent yields, indicating transfer of up to four phenyl groups from 2a
(Table 2, entries 1-4). Treatment of 2a with less reactive 1-bromonaphthalene 1b gave the
coupling product in 48% yield (entry 5).
When chlorotriphenylstannane 2b and dichlorodiphenylstannane 2c are subjected to coupling
with different equiv. of 1a, multiple phenyl group transfer was also observed, even though the
coupling efficiency is lower compared to 2a (entries 6-10). Less coupling efficiency (25%) was
observed for the reaction of trichlorophenylstannane 2d with 1a (entry 11). In general, both the
yield and ratio increases with the number of phenyl groups present in the organostannanes
substrates.
Table 2. Coupling of arylstannanes 2 with different equivalency of 1-iodonaphthalene 1aa
yield (%)b ratio c
halides
entry
stannanes
3
3:4
equiv. (n)
1
1
2
1
2
98 d
92
99:1
30:1
1a
1a
2a
2a
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91 (84)
83 (75) e
48
99:1
99:1
9:1
1a
1a
1b
1a
1a
1a
1a
1a
1a
2a
2a
2a
2b
2b
2b
2c
2c
2d
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20:1
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40:1
40:1
20:1
50:1
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a Couplings were performed on 0.20 mmol scale of 2a-2d (0.05 M) with 5 equiv. of LiCl at 140 oC for 12 h.
b Yields for product 3 are based upon transferring four, three, two or one phenyl groups from tin reagents 2a,
2b, 2c, or 2d respectively. b Determined by GC/MS. Isolated yield in the parenthesis. c Determined by NMR.
d Heated for 4 h. e 3 was obtained in 26% (3:4, 80:1) for 4 h and 50% (3:4, 90:1) for 8 h.
Next, the LiCl-promoted coupling reactions of tetraphenyltin 2a with a series of aryl halides
5a-5k have been examined (Table 3). Coupling of 2a with 4 equiv. of aryl iodides 5a-5c, having
o
EWG at the para-position, proceeded efficiently in the presence of LiCl (140 C/12 h) to give
biaryls 6a-6c in good yields with transfer of four phenyl groups from the Sn center (entries 1-3,
60-76%). Analogous coupling of 2a with iodide 5d, having EDG at the para-position yielded the
biaryl 6d in only 31% yield along with large quantities of 4 (entry 4). Similarly, aryl iodides
bearing EWGs at the ortho-position, 5e and 5f, gave the coupling products in better yields and
ratios as compared to those having EDG 5g (entries 5-7). The same trend was also observed for
the meta-substituted iodides 5h-5j (entries 8-10). In general, both yields of biaryls 6 and ratios of
6 to 4 were higher for aryl halides with EWG in the phenyl ring. However, the position of the
substituent (o-, m-, p-) has less effect. It is noteworthy that compared to the transition-metal-free
cross-couplings of Grignard reagents, which are also reactive with the electrophilic substituents,
such as cyano, ester or ketone,12 the organostannane coupling described here demonstrates higher
functional group tolerance, similarly to the reactions with arylzinc reagents.15 The aryl bromide
5k also undergoes coupling with 2a to give 6k but in lower yield (entry 11).
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Table 3. LiCl-promoted couplings of tetraphenyltin 2a with different aryl halides 5a-5k a
5
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yield ratio
entry halides
X
R
product
(%)b (6:4) c
1
2
I
I
4-COOCH3
4-COCH3
4-CN
76
60
72
31
80
79
44
62
75
40
36
10:1
7:1
5a
5b
5c
5d
5e
5f
6a
6b
6c
6d
6e
6f
3
I
12:1
4:5
4
I
4-OCH3
2-NO2
2-CF3
5
I
50:1
15:1
5:4
6
I
7
I
2-CH3
5g
5h
5i
6g
6h
6i
8
I
3-CN
8:1
9
I
3-CF3
13:1
5:4
10
11
I
3-CH3
5j
6j
Br
2-CN
5:2
5k
6k
a Couplings were performed on 0.20 mmol scale of 2a (0.05 M) with 4.0 equiv. of 5a-5k at the presence of
LiCl (5 equiv.) at 140 C for 12 h. b Calculated based on transferring four phenyl groups from 2a.
o
c
Determined by NMR.
The LiCl-promoted Stille coupling is also efficient in transferring phenyl groups substituted
with EDG or EWG from the Sn center. The results for coupling of tetra-(p-tolyl)tin 7,
tetra-(m-methoxyphenyl)tin 8, or tetra-(p-chlorophenyl)tin 9 with various aryl iodides (4.0 equiv.)
are presented in Table 4 (entries 1-12). Coupling of aryltins having EDG 7 or 8 gave better yields
and ratios with aryl halides bearing EWGs (5a-c, or 5i) as compared to the one with EDG (5d, 5g,
or 5j), with efficient transfer of up to four aryl groups from organotin substrates (entries 1-7).
Coupling of p-chloro substituted aryltin 9 yielded products 12 generally in higher yields than
when 7 and 8 were used. Again, the products were obtained in higher yields and better ratio with
iodides having EWG (entries 6-10). Atom-efficient Pd-catalyzed Stille couplings with Ar4Sn are
known.36-38 However, transfer of multiple Ar groups from a Sn center, in the absence of a
Pd-catalyst, has not been reported.
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Table 4. LiCl-promoted couplings of tetraaryltins 7-9 with different aryl halides 5a-5ka
5
6
7
8
9
I
Ar
Ar
DMF, LiCl
140 oC, 12 h
Ar Sn Ar
Ar
+
+
Ar Ar
R
4
4
R
10
11
12
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5a-5k
7-9
10-12
13-15
halides
R
stannane
Ar-
entry
product yield (%)b ratioc
5
7-9
7
1
2
4-COOCH3
4-CN
71
48
26
25
63
55
34
65
42
82
79
38
15:2
3:2
5a
5c
5d
5g
5i
10a
10c
10d
10g
10i
3
4-OCH3
2-CH3
5:4
4
2:1
5
3-CF3
8:1
6
4-COCH3
3-CH3
7:1
5b
5j
11b
11j
8
9
7
3:1
8
4-COCH3
4-OCH3
2-CF3
20:1
5:2
5b
5d
5f
12b
12d
12f
12h
12j
9
10
11
12
50:1
15:1
5:3
3-CN
5h
5j
3-CH3
a Couplings were performed on 0.20 mmol scale of 7-9 (0.05 M) with 4 equiv of 5 at the presence of LiCl
o
b
c
(5 equiv.) at 140 C for 12 h. Calculated based on transferring four aryl groups from tin reagents 7-9.
Ratio of 10:13, or 11:14, or 12:15 was determined by 1H NMR and GC-MS.
The LiCl-promoted cross-coupling reaction with stannanes was successfully applied for the
synthesis of ipriflavone 17, which is in clinical studies for postmenopausal osteoporosis.39 Thus,
treatment of 3-iodo-7-isopropoxychromone 16 (1 equiv.) with 2a (0.25 equiv.)/LiCl (1.25 equiv.)
afforded ipriflavone 17 (92%) with the efficient transfer of four phenyl groups (Scheme 1).
Scheme 1. Synthesis of ipriflavone 17 by LiCl-promoted couplings of 2a with 16
The LiCl-promoted cross-coupling of aryl halides with arylstannanes might occur via single
electron transfer (SET) induced radical-nucleophilic aromatic substitution (SRN1)40 mechanism,
similar to the pathway proposed for the transition-metal-free coupling between aryl halides and
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Grignard12,20,22 or arylzinc15 reagents. This assumption is supported by the fact that: (i) no
rearranged coupling product was formed, which excludes the aryne mechanistic pathway,41-42 and
(ii) couplings proceed with aryl halides bearing EDG, which should eliminate nucleophilic
aromatic substitution (SNAr). The addition of LiCl has been proven to be beneficial for the
coupling of organotin with vinyl triflates. The role of the lithium has been explained by the
formation of a more reactive palladium complex involving the coordination of a chloride ion.43
Shirakawa et al. attributed enhancement of LiCl on the reactivity of PhZnI in the
transition-metal-free coupling with aryl halides on the generation of nucleophilic lithium zincates
complexes,35 such as Li+[PhZnICl]-.15 It is noteworthy that hypervalent fluoro tin44-45
(e.g.,difluorotriphenylstannate), silicon46-47 and germane38 species have been established as active
intermediates in Pd-catalyzed couplings.
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It is noteworthy that LiCl-promoted coupling requires anhydrous conditions and pre-dried
LiCl of high purity for the optimal efficiency. Moreover, it was found that coupling under
oxygen-free conditions, every so often, led to irreproducible results. Murarka and Studer noted
that initiation for the transition-metal-free growth polymerization of haloaryl Grignard reagents
can be achieved in the presence of traces of oxygen or by adding TEMPO radical.14,48 Efforts
have been made to further optimize conditions. However, experiments under Ar vs N2 vs
atmospheric conditions vs oxygen introduced by syringe did not improve the yields of coupling
products and their selectivity to homocoupling49 byproducts. It is noteworthy that best results
were obtained when the reaction suspension was heated with a drying tube, filled with anhydrous
CaCl2, attached to the condenser.
In summary, we have demonstrated that aryl halides undergo transition-metal-free
LiCl-promoted coupling with tetraaryltins (or chloroarylstannanes) to give biaryls in moderate to
high yield with the transfer of all four phenyl groups from the Sn center. This atom-efficient
protocol eliminates the usage of a transition-metal catalyst and proceeds without the addition of
extra ligands or other additives. In general, the aryls bearing electron-withdrawing groups, either
in halides or organotin substrates, give coupling products in better yields. This LiCl-promoted
coupling is believed to occur via SET-induced radical-nucleophilic aromatic substitution.
EXPERIMENTAL SECTION
1H NMR spectra at 300 MHz and proton-decoupled 13C{1H} NMR data at 75 MHz were
determined with solutions in CDCl3. TLC was performed on Merck kieselgel 60-F254 and
products were detected with 254 nm light or by development of color with I2. Merck kieselgel 60
(230-400 mesh) was used for column chromatography. Purity, yields and ratio of the products
(crude and/or purified) were established with GC/MS [EI; capillary column RTX-1MS (30 m ×
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0.25 mm × 25 µm)] using calibrated standards. HRMS data were recorded by electrospray
ionization with a TOF mass analyzer. LiCl (catalog number 449881, ≥99.9%), tetraphenyltin
(T26727, 97%), and phenyltin chlorides [2b, 245712, 95%; 2c, 229202, 96%; 2d, 277231, 98%)
as well as anhydrous DMF (227056, 99.8%) were purchased from Aldrich-Sigma Co.
9
1-(Phenyl)naphthalene (3). Typical Procedure. LiCl (42.4 mg, 1 mmol) was placed in a 10
mL round-bottom flask fitted with a septum and was flame-dried under Ar atmosphere for 1 min.
After cooling to an ambient temperature (~ 5 min), DMF (4 mL) and 1-iodonaphthalene 1a (116.8
µL, 203.2 mg, 0.8 mmol) were added via syringe followed by tetraphenyltin 2a (85.4 mg, 0.2
mmol). The septum was removed and the condenser, fitted with a drying tube on the top filled
with anhydrous CaCl2, was quickly attached to the flask. The stirred suspension was heated at 140
oC (oil bath) for 12 h. Volatiles were evaporated and the residue was partitioned (H2O/EtOAc).
The organic layer was dried (Na2SO4), evaporated and purified by column chromatography
(hexane) to give 338 (61.3 mg, 75%): 1H NMR δ 7.40-7.44 (m, 3H), 7.46-7.54 (m, 6H), 7.84-7.86
(m, 1H), 7.87-7.91(m, 2H); 13C NMR δ 125.4, 125.8, 126.0, 126.9, 127.2, 127.6, 128.3, 130.1,
131.7, 133.8, 140.3, 140.8. GC-MS (tR 10.1 min) m/z 204 (100, [M]+). GC-MS of the crude
reaction mixture showed ratio of 3:4 as 100 to 1: GC-MS (tR 10.1 min, 3) m/z 204 (100, [M]+) and
(tR 5.8 min, 4) m/z 154 (100, [M]+). HRMS [M+H]+ for C16H13, calcd: 205.1012; found:
205.1013.
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Note: See Table 1 for the reaction conditions used during optimization studies and Table 2 for
the coupling conditions of stannanes 2 with different equivalents of 1-iodonaphthalene 1a.
Methyl Biphenyl-4-carboxylate (6a). Treatment of tetraphenyltin 2a (85.4 mg, 0.20 mmol)
with methyl 4-iodobenzoate 5a (209.6 mg, 0.80 mmol) by Typical Procedure gave 6a50 (128.9 mg,
76%): 1H NMR δ 3.94 (s, 1H), 7.39 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.6 Hz, 2H), 7.62 (d, J = 7.2
Hz, 2H), 7.66 (d, J = 8.4 Hz, 2H), 8.10 (d, J = 8.4 Hz, 2H); 13C NMR δ 52.3, 127.1, 127.3, 128.2,
128.9, 130.1, 140.0, 145.7, 167.1. GC-MS (tR 10.4 min) m/z 212 (60, M+). HRMS [M+H]+ for
C14H13O2, calcd: 213.0910; found: 213.0911.
4-Acetylbiphenyl (6b). Treatment of 2a (85.4 mg, 0.20 mmol) with 4-iodoacetophenone 5b
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(196.8 mg, 0.8 mmol) by Typical Procedure gave 6b50 (94.1 mg, 60%): H NMR δ 2.64 (s, 3H),
7.40 (t, J = 8.0 Hz, 1H),7.47 (t, J = 8.0 Hz, 2H), 7.63 (d, J = 8.0 Hz, 2H), 7.69 (d, J = 8.0 Hz, 2H),
8.03 (d, J = 8.0 Hz, 2H);13C NMR δ 26.6, 127.2, 127.3, 128.2, 128.9, 129.0, 136.0, 139.9, 145.8,
197.8; GC-MS (tR 9.8 min) m/z 196 (50, M+). HRMS [M+H]+ for C14H13O, calcd: 197.0961;
found: 197.0963.
4-Cyanobiphenyl (6c). Treatment of 2a (85.4 mg, 0.20 mmol) with 1-cyano-4-iodobenzene
5c (183.2 mg, 0.8 mmol) by Typical Procedure gave 6c50 (103.1 mg, 72%): 1H NMR δ 7.42 (t, J =
7.3 Hz, 1H), 7.48 (t, J = 7.5 Hz, 2H), 7.58 (d, J = 7.8 Hz, 2H), 7.68 (d, J = 8.2 Hz, 2H), 7.72 (d, J
= 8.0 Hz, 2H); 13C NMR δ 110.0, 118.9, 127.2, 127.7, 128.7, 129.1, 132.6, 139.2, 145.7. GC-MS
(tR 9.0 min) m/z 179 (100, M+). HRMS [M+H]+ for C13H10N, calcd: 180.0808; found: 180.0810.
4-Methoxybiphenyl (6d) Treatment of 2a (85.4 mg, 0.20 mmol) with
4-iodo-1-methoxybenzene 5d (187.2 mg, 0.8 mmol) by Typical Procedure gave 6d51 (45.6 mg,
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31%): 1H NMR δ 3.84 (s, 3H), 6.97 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 8.0 Hz, 3H), 7.41 (t, J = 8.0
Hz, 2H), 7.51-7.56 (m, 4H); 13C NMR δ 55.4, 114.2, 126.7, 126.8, 128.2, 128.7, 133.8, 140.9,
159.2. GC-MS (tR 8.4 min) m/z 184 (100, M+). HRMS [M+H]+ for C13H13O, calcd: 185.0961;
found: 185.0961.
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2-Nitrobiphenyl (6e). Treatment of 2a (85.4 mg, 0.20 mmol) with 2-iodo-1-nitrobenzene 5e
(199.2 mg, 0.80 mmol) by Typical Procedure gave 6e37 (127.4 mg, 80%): 1H NMR δ 7.32 (d, J =
7.2 Hz, 2H), 7.41-7.50 (m, 2H), 7.61 (t, J = 8.0 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H); 13C NMR δ
124.1, 127.9, 128.1, 128.2, 128.7, 132.0, 132.2, 136.4, 137.4, 149.4. GC-MS (tR 8.7 min) m/z 199
(20, M+). HRMS [M+H]+ for C12H10NO2, calcd: 200.0706; found: 200.0707.
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2-(Trifluoromethyl)biphenyl (6f). Treatment of 2a (85.4 mg, 0.20 mmol) with
2-iodo-1-trifluoromethylbenzene 5f (112.2 µL, 217.6 mg, 0.8 mmol) by Typical Procedure gave
6f52 (140.3 mg, 79%): 1H NMR δ 7.38-7.48 (m, 7H), 7.53-7.58 (m, 1H), 7.74 (d, J = 8.0 Hz, 1H);
13C NMR δ 124.1 (q, 1J = 272.0 Hz), 126.0 (q, 3J = 5.4 Hz), 127.3, 127.6, 127.7, 128.9, 128.4 (q,
2J = 28.5 Hz), 131.3, 132.0, 139.9, 141.5. GC-MS (tR 5.2 min) m/z 222 (100, M+). HRMS [M+H]+
for C13H10F3, calcd: 223.0729; found: 223.0731.
2-Methylbiphenyl (6g). Treatment of 2a (85.4 mg, 0.20 mmol) with 2-iodo-1-methylbenzene
5g (101.8 µL, 174.4 mg, 0.8 mmol) by Typical Procedure gave 6g50 (59.1 mg, 44%?): 1H NMR δ
2.27 (s, 3H), 7.25-7.27 (m, 2H), 7.31-7.34 (m, 3H), 7.39-7.45 (m, 3H), 7.59 (d, J = 8.0 Hz, 1H);
13C NMR δ 20.5, 125.8, 126.8, 127.2, 127.3, 128.1, 128.8, 129.2, 129.8, 130.3, 135.4, 142.0.
GC-MS (tR 6.0 min) m/z 168 (100, M+). HRMS [M+H]+ for C13H13, calcd: 169.1012; found:
169.1011.
3-Cyanobiphenyl (6h). Treatment of 2a (85.4 mg, 0.20 mmol) with 1-cyano-3-iodobenzene
5h (183.2 mg, 0.8 mmol) by Typical Procedure gave 6h37 (88.8 mg, 62%): 1H NMR δ 7.39-7.43
(m, 1H), 7.46-7.49 (m, 2H), 7.52-7.56 (m, 3H), 7.62 (d, J = 8.0 Hz, 1H), 7.81(d, J = 8.0 Hz, 1H),
7.86 (s, 1H); 13C NMR δ 113.0, 118.8, 127.1, 128.4, 129.1, 129.6, 130.7, 131.5, 138.9, 140.5,
141.9, 142.5. GC-MS (tR 8.8 min) m/z 179 (95, M+). HRMS [M+H]+ for C13H10N, calcd:
180.0808; found: 180.0812.
3-(Trifluoromethyl)biphenyl (6i). Treatment of 2a (85.4 mg, 0.20 mmol) with
3-iodo-1-trifluoromethylbenzene 5i (115.3 µL, 217.6 mg, 0.8 mmol) by Typical Procedure gave
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6i38 (133.2 mg, 75%): H NMR δ 7.38-7.60 (m, 7H), 7.76 (d, J = 8.0 Hz, 1H), 7.83(s, 1H); 13C
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NMR δ 124.95 (q, J = 3.2 Hz), 124.98 (q, J = 3.2 Hz), 124.3 (q, J = 271.0 Hz), 127.2, 128.0,
129.0, 129.2, 130.4, 131.2 (q, 2J = 32.6 Hz), 139.8, 142.1. GC-MS (tR 5.6 min) m/z 222 (100, M+).
HRMS [M+H]+ for C13H10F3, calcd: 223.0729; found: 223.0730.
3-Methylbiphenyl (6j). Treatment of 2a (85.4 mg, 0.20 mmol) with 3-iodo-1-methylbenzene
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5j (102.7 µL, 174.4 mg, 0.8 mmol) by Typical Procedure gave 6j50 (53.8 mg, 40%): H NMR δ
2.41 (s, 3H), 7.14-7.16 (m, 1H), 7.30-7.35 (m, 2H), 7.38-7.45 (m, 4H), 7.57-7.59 (m, 2H); 13C
NMR δ 21.6, 124.3, 127.2, 127.3, 128.0, 128.7, 128.7,128.8, 138.3, 141.3, 141.4. GC-MS (tR 6.8
min) m/z 168 (85, M+). HRMS [M+H]+ for C13H13, calcd: 169.1012; found: 169.1014.
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2-Cyanobiphenyl (6k). Treatment of 2a (85.4 mg, 0.20 mmol) with
1-cyano-2-bromobenzene 5k (183.2 mg, 0.8 mmol) by Typical Procedure gave 6k37 (51.6mg,
36%): 1H NMR δ 7.42-7.57 (m, 7H), 7.65 (t, J = 7.6 Hz, 1H), 7.76 (d, J = 7.6 Hz, 1H), 7.41(t, J =
8.0 Hz, 2H), 7.51-7.56 (m, 4H); 13C NMR δ 111.3, 118.7, 127.6, 128.73, 128.76, 130.1, 132.8,
133.7, 133.9, 138.2, 145.5. GC-MS (tR 8.2 min) m/z 179 (100, M+). HRMS [M+H]+ for C13H10N,
calcd: 180.0808; found: 180.0810.
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3,4'-Dimethylbiphenyl (10a). Treatment of tetra-(p-methylphenyl)tin 7 (96.6 mg, 0.20 mmol)
with 1-methyl-3-iodobenzene 5a (102.7 µL, 174.4 mg, 0.8 mmol) by Typical Procedure gave
10a53 (36.4 mg, 25%): 1H NMR δ 2.41 (s, 3H), 2.43 (s, 3H), 7.16 (d, J = 7.5 Hz, 1H), 7.26 (d, J =
7.8 Hz,1H), 7.33 (t, J = 7.5 Hz, 1H), 7.40 (d, J = 12.7 Hz, 2H), 7.56 (t, J = 6.5 Hz, 3H); 13C NMR
δ 20.1, 20.5, 123.1, 125.8, 126.0, 126.7, 126.8, 127.6, 128.4, 135.9, 137.2, 140.1. GC-MS (tR 8.4
min) m/z 182 (100, M+). HRMS [M+H]+ for C15H15O2, calcd: 227.1067; found: 227.1071.
4-Cyano-4'-methybiphenyl (10c). Treatment of 7 (96.6 mg, 0.20 mmol) with
1-cyano-4-iodo-benzene 5c (183.2 mg, 0.8 mmol) by Typical Procedure gave 10c53 (74.1 mg,
48%): 1H NMR δ 2.41 (s, 3H), 7.28 (d, J = 7.6 Hz, 2H), 7.48 (d, J = 7.7 Hz, 2H), 7.65 (d, J = 8.1
Hz, 2H), 7.69 (d, J = 7.8 Hz, 2H); 13C NMR δ 21.2, 110.6, 119.0, 127.1, 127.5, 129.9, 132.6,
136.3, 138.8, 145.6. GC-MS (tR 10.4 min) m/z 193 (100, M+). HRMS [M+H]+ for C14H12N, calcd:
194.0964; found: 194.0969.
4-Methoxyl-4'-methybiphenyl (10d). Treatment of 7 (96.6 mg, 0.20 mmol) with
4-iodo-1-methoxylbenzene 5d (187.2 mg, 0.8 mmol) by Typical Procedure gave 10d53 (41.2 mg,
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26%): H NMR δ 2.38 (s, 3H), 3.83 (s, 3H), 6.96 (d, J = 8.2Hz, 2H), 7.22 (d, J = 7.7 Hz, 2H),
7.44 (d, J = 7.6 Hz, 2H), 7.50 (d, J = 8.2Hz, 2H); 13C NMR δ 21.1, 55.4, 114.2, 126.6, 128.0,
129.5, 133.8, 136.4, 138.0, 159.0. GC-MS (tR 9.8 min) m/z 198 (100, M+). HRMS [M+H]+ for
C14H15O, calcd: 199.1117; found: 199.1120.
3',4-Dimethybiphenyl (10g). Analogous treatment of 7 (96.6 mg, 0.20 mmol) with
2-iodo-1-methylbenzene 5g (174.4 mg, 0.8 mmol) by Typical Procedure gave 10g53 (36.4 mg,
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25%): H NMR δ 2.41 (s, 3H), 2.42 (s, 3H), 6.96 (d, J = 8.2Hz, 2H), 7.22 (d, J = 7.7 Hz, 2H),
7.44 (d, J = 7.6 Hz, 2H), 7.50 (d, J = 8.2Hz, 2H); 13C NMR δ 20.1, 20.5, 123.1, 125.8, 126.0,
126.7, 126.8, 127.6, 128.4, 135.9, 137.2, 140.1. GC-MS (tR 8.4 min) m/z 182(100, M+). HRMS
[M+Na]+ for C14H14Na, calcd: 205.0988; found: 205.0991.
4'-Methyl-3-(trifluoromethyl)biphenyl (10i). Treatment of 7 (96.6 mg, 0.20 mmol) with
3-iodo-1-trifluoromethylbenzene 5i (115.3 µL, 217.6 mg, 0.8 mmol) by Typical Procedure gave
10i54 (118.9 mg, 63%): 1H NMR δ 2.42 (s, 3H), 7.29 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.1 Hz, 2H),
7.54 (t, J = 7.7 Hz, 1H), 7.59 (d, J = 7.8 Hz, 1H), 7.75 (d, J = 7.7 Hz, 1H), 7.83 (s, 1H); 13C NMR
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δ 21.3, 123.77 (q, J = 3.0 Hz), 123.86 (q, J = 3.0 Hz), 124.4 (q, J = 271.5 Hz), 127.1, 129.3,
129.9, 130.3, 131.3 (q, 2J = 31.5 Hz), 137.0, 138.1, 142.1. GC-MS (tR 7.3 min) m/z 236 (100, M+).
HRMS [M+H]+ for C14H12F3, calcd: 237.0886; found: 237.0889.
4'-Acetyl-3-methoxylbiphenyl (11b). Treatment of tetra-(m-methoxyphenyl)tin 8 (109.4 mg,
0.20 mmol) with 4-iodoacetophenone 5b (196.8 mg, 0.8 mmol) by Typical Procedure gave 11b55
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(99.4 mg, 55%): 1H NMR δ 2.63 (s,3H), 3.87 (s,3H), 6.94 (d, J = 8.2 Hz, 1H), 7.12-7.18 (m,1H),
7.21 (d, J = 7.4 Hz, 1H), 7.38 (t, J = 7.9 Hz, 1H), 7.67 (d, J = 8.5 Hz, 2H)，8.02 (d, J = 8.5 Hz,
2H); 13C NMR, δ 26.64, 55.4, 113.1, 113.6, 119.8, 127.3, 128.9, 130.0, 136.0, 141.4, 145.7, 160.1,
197.7. GC-MS (tR 12.2 min) m/z 226 (56, M+). HRMS [M+H]+ for C15H15O2, calcd: 227.1067;
found: 227.1069.
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3-Methoxyl-3'-methylbiphenyl (11j). Treatment of 8 (109.4 mg, 0.20 mmol) with
3-iodo-1-methylbenzene 5j (102.7 µL, 174.4 mg, 0.8 mmol) by Typical Procedure gave 11j56
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(53.9 mg, 34%): H NMR δ 2.44 (s, 3H),3.88 (s,3H), 6.90-6.92 (m, 1H), 7.13-7.16 (m, 1H),
7.17-7.22 (m,2H), 7.33-7.38 (m,2H), 7.42 (d, J = 8.1 Hz, 2H); 13C NMR, δ 20.5, 54.3, 111.6,
111.9, 118.7, 123.3, 127.0, 127.1, 127.6, 128.6, 137.3, 140.1, 141.9. GC-MS (tR 9.6 min) m/z 198
(100, M+). HRMS [M+H]+ for C14H15O, calcd: 199.1117; found: 199.1121.
4'-Acetyl-4-chlorobiphenyl (12b). Treatment of tetra-(p-chlorophenyl)tin 9 (113 mg, 0.20
mmol) with 4-iodoacetophenone 5b (196.8 mg, 0.8 mmol) by Typical Procedure gave 12b55
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(119.6 mg, 65%): H NMR δ 2.62 (s, 3H), 7.42 (d, J = 8.6Hz, 2H), 7.54 (d, J = 8.6 Hz, 2H),
7.63(d, J = 8.6Hz, 2H), 8.02 (d, J = 8.6 Hz, 2H); 13C NMR δ 25.6, 126.0, 127.5, 128.0, 128.1,
133.4, 135.1, 137.3, 143.4, 196.5. GC-MS (tR 11.8 min) m/z 230 (50, M+). HRMS [M+H]+ for
C14H12ClO, calcd: 231.0571; found: 231.0572.
4-Methoxyl-4'-chlorobiphenyl (12d). Treatment of 9 (113 mg, 0.20 mmol) with
4-iodo-1-methoxylbenzene 5d (187.2 mg, 0.8 mmol) by Typical Procedure gave 12d57 (73.2 mg,
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42%): H NMR δ 3.84 (s, 3H), 6.96 (d, J = 8.8Hz, 2H), 7.38 (d, J = 8.6 Hz, 2H), 7.44-7.50 (m,
4H); 13C NMR δ 55.4, 114.4, 128.0, 128.0, 128.9, 132.5, 132.7, 139.3, 159.4. GC-MS (tR 10.6
min) m/z 218 (100, M+). HRMS [M+H]+ for C13H12ClO, calcd: 219.0571; found: 219.0571.
4-Chloro-2'-(trifluoromethyl)biphenyl (12f). Treatment of 9 (113 mg, 0.20 mmol) with
2-iodo-1-(trifluoromethyl)benzene 5f (112.2 µL, 217.6 mg, 0.8 mmol) by Typical Procedure gave
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12f (167.9 mg, 82%): H NMR δ 7.27 (d, J = 4.7Hz, 2H), 7.31 (d, J = 5.1 Hz, 1H), 7.38 (d, J =
5.6 Hz, 2H), 7.49 (t, J = 4.8 Hz, 1H), 7.57 (t, J = 5.0 Hz, 1H), 7.75 (d, J = 5.3 Hz, 1H); 13C NMR
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δ 131.2 (q, J = 272 Hz), 125.2 (q, J = 5.0 Hz), 126.7, 127.0, 127.3 (q, J = 31.3 Hz), 129.3,
130.4, 130.9, 132.8, 137.2, 139.1. GC-MS (tR 7.5 min) m/z 256 (100, M+). HRMS [M+H]+ for
C13H9ClF3, calcd: 257.0339; found: 257.0343.
4-Chloro-3'-cyanobiphenyl (12h). Treatment of 9 (113 mg, 0.20 mmol) with
1-cyano-3-iodobenzene 5h (183.2 mg, 0.8 mmol) by Typical Procedure gave 12h58 (134.6 mg,
79%): 1H NMR δ 7.44-7.50 (m, 4H), 7.52-7.57 (m, 1H), 7.60-7.67 (m, 1H), 7.76 (s, 1H), 7.82 (s,
1H);13C NMR δ 113.2, 118.6, 128.3, 129.3, 129.8, 130.5, 131.0, 131.3, 134.7, 137.3, 141.2.
GC-MS (tR 11.0 min) m/z 213 (100, M+). HRMS [M+H]+ for C13H9ClN, calcd: 214.0418; found:
214.0421.
4-Chloro-3'-methylbiphenyl (12j). Treatment of 9 (113 mg, 0.20 mmol) with
3-iodo-1-methylbenzene 5j (102.7 µL, 174.4 mg, 0.8 mmol) by Typical Procedure gave 12j59
(61.4 mg, 38%): 1H NMR δ 2.44 (s, 3H), 7.20 (d, J = 4.7 Hz, 1H), 7.33-7.39 (m, 3H), 7.41 (d, J =
13
4.7 Hz, 2H), 7.52 (d, J=5.3 Hz, 2H); C NMR δ 20.5, 126.7, 127.3, 127.4, 127.8, 127.8, 132.2,
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137.5, 138.8, 139.0. GC-MS (tR 9.2 min) m/z 202 (100, M+). HRMS [M+H]+ for C13H12Cl, calcd:
203.0622; found: 203.0625.
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7-Isopropoxyisoflavone (Ipriflavone, 17). Treatment of tetraphenyltin 2a (85.4 mg, 0.20
mmol) with 3-iodo-7-isopropylchromone 1660 (174.4 mg, 0.8 mmol) by Typical Procedure gave
1761 as a white solid (206 mg, 92%): m.p., 121.9-123.0 ºC; IR (KBr), ν (cm-1) 3060, 2985, 2972,
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2928, 1637, 1592, 1561, 1491, 1439, 1369, 1325, 1261, 1034, 907, 881, 820, 780, 738, 694; H
NMR δ 1.40 (d, J = 6.0 Hz, 6H), 4.62-4.70 (m, 1H), 6.83 (s, 1H), 6.95 (dd, J = 9.0, 3.0 Hz, 1H),
7.34-7.45 (m, 3H), 7.56 (d, J = 9.0 Hz, 2H), 7.92 (s, 1H), 8.20 (d, J = 9.0 Hz, 1H); 13C NMR
175.6, 162.5, 158.0, 152.6, 132.1, 129.0, 128.4, 128.1, 127.8, 125.2, 118.2, 115.6, 101.6, 70.8,
21.8. HRMS [M+Na]+ for C18H16O3Na, calcd: 303.0997; found: 303.0969.
AUTHOR INFORMATION
Corresponding Author: *E-mail: wnuk@fiu.edu ; E-mail: zhangzt@snnu.edu.cn
Present Address †(Y. L.) Department of Molecular Medicine, Beckman Research Institute of the
City of Hope Duarte, CA 91010
Notes The authors declare no competing financial interest.
ACKNOWLEDGMENTS
ZTZ and YL are grateful to the Oversea Scholarship Program of Shaanxi Normal University and
FIU University Graduate School for Dissertation Year Fellowship, respectively.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publication website at DOI:
10.1021/acs.joc.
1H and 13C NMR spectra for all compounds (PDF).
REFERENCES
(1) de Meijere, A.; Diederich, F.; Wiley-VCH: Weinheim, Germany, 2004.
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1359-1470.
(3) Fagnou, K. Top. Curr. Chem. 2010, 292, 35-56.
(4) Li, B.; Dixneuf, P. H. Chem. Soc. Rev. 2013, 42, 5744-5767.
(5) Liang, Y.; Wnuk, S. F. Molecules 2015, 20, 4874-4901.
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