Synthesis of Aryl Trimethylstannane via BF3·OEt2-Mediated Cross-Coupling of Hexaalkyl Distannane Reagent with Aryl Triazene at Room Temperature

Article abstract of DOI:10.1021/acs.joc.8b02766

BF₃·OEt₂-mediated cross-coupling of (SnMe₃)₂ with aryl triazene offers a new strategy for the synthesis of aryl stannane. A variety of synthetically useful aryl trimethylstannanes were produced in moderate to good yields with this metal-free approach. One-pot sequential Stille cross-coupling with different aryl bromides provides a short entry to both symmetrical and unsymmetrical biaryl compounds.

Full text of DOI:10.1021/acs.joc.8b02766

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Note
Synthesis of Aryl Trimethylstannane via BF3·OEt2-mediated Cross-Coupling
of Hexaalkyl Distannane Reagent with Aryl Triazene at Room Temperature
Shuai Mao, Zhengkai Chen, Lu Wang, Daulat Bikram Khadka, Minhang Xin, Pengfei Li, and San-Qi Zhang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02766 • Publication Date (Web): 12 Dec 2018
Downloaded from http://pubs.acs.org on December 16, 2018
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Synthesis
of
Aryl
Trimethylstannane
via
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BF3·OEt2-mediated Cross-Coupling of Hexaalkyl
Distannane Reagent with Aryl Triazene at Room
Temperature
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†,#
‡ #
,
†
§
†
Shuai Mao, Zhengkai Chen, Lu Wang, Daulat Bikram Khadka, Minhang Xin,
,
,†
‖
Pengfei Li,* and San-Qi Zhang*
†Department of Medicinal Chemistry, School of Pharmacy, Xi’an Jiaotong University, Xi’an 710061, China.
‡Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China.
ǁFrontier Institute of Science and Technology, Xi’an Jiaotong University, Xi’an, Shaanxi 710054, China.
§Department of Medicinal Chemistry, College of Pharmacy, University of Michigan, Ann Arbor, MI 48109, USA
R2
OEt
BF3
2
SnMe3
[Pd]
N
N
R1 Het
+
(SnMe3)2
N
R1 Het
Ar'Br
Readily Acessible Reagents
Broad Substrate Scope
Insensitive to Air and Moisture
Scale Up
R1
R = alkyl, aryl, halo,
ester, amino...
26 examples
Symmetrical and
unsymmetrical biaryls
in 45-72% isolate yields
ABSTRACT: BF3·OEt2-mediated cross-coupling of (SnMe3)2 with aryl triazene
offers a new strategy for the synthesis of aryl stannane. A variety of synthetically
useful aryl trimethylstannanes were produced in moderate to good yields with this
metal-free approach. One-pot sequential Stille cross-coupling with different aryl
bromides provides a short entry to both symmetrical and unsymmetrical biaryl
compounds.
Considering the great importance of well-known Stille coupling reaction in the
formation of C–C bond, the rapid assembly of organotin reagents has attracted
considerable interest among the organic chemists.1 Apart from the construction of C–
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C bond, the organotin reagents can also be applied in other useful transformation.2
The conventional methods to access aryl stannane compounds mainly rely on the
reaction of air and moisture sensitive aryl-metal reagents with trialkyl tin chloride,
under harsh reaction conditions.3 In this aspect, transition metal-catalyzed
stannylation of aryl halides which possesses tremendous versatility and functional
group compatibility is a more reliable route.4 Remarkably, this methodology has been
recently expanded to include a C–H bond activation strategy and significant progress
has been achieved.5 However, transition metal catalysts are expensive and sometimes
sometimes result into metal contaminants in the final products. Thus, more attention
was beginning to shift to the transition-metal free process in organic synthesis.
Recently, stannylation of arylamine via oxidative deamination by alkylnitrite has been
reported.6 It provides a direct conversion of arylamine to aryl stannanes under
metal-free conditions which is an innovative development in aryl stannanes synthesis.
More recently, our group reported an efficient metalcatalyst-free approach to
synthesize trimethylarylstannanes from aryl halides promoted by UV light.7 However,
given the great importance of aryl stannanes and the limited number of available
synthetic methods, the development of novel and practical methods to access these
compounds is still highly desirable.
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Aryl triazenes are an important class of molecules that have drawn a lot of
attention from the organic chemists.8 Owing to the low cost and easy availability of
aryl triazenes, C–N electrophiles have emerged as powerful alternatives to aryl
halides as coupling partners in the cross-coupling arena. In the last two decades,
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aryltriazene has been used as equiverlant of aryldiazonium salt in the presence of
Lewis or Brønsted acid in nucleophilic substitution reactions and transition
metals-catalyzed coupling reactions.9 In particular, BF3·OEt2 has proven to be an
efficient reagent to activate aryltriazene in Pd-catalyzed Suzuki-Miyaura coupling
reaction.10 Although the use of triazane as a coupling partner in coupling reaction has
increased, only aryl triazenes substituted with electron-donating groups can be
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subjected to
a
coupling reaction efficiently; aryl triazenes with the
electron-withdrawing group usually give poor yields10a,10b. In comparison, Stille
coupling reaction represents one of the most reliable methods in syntheses of complex
molecules where great substrate compatibility, mild reaction conditions and good
yields have been the main features. Moreover, in the transition metal-catalyzed
cross-coupling reactions, aryltriazenes usually behave only as the electrophile instead
of a nucleophile. Therefore, effective transformation of aryltriazenes to aryl stannanes
could facilitate the targeted coupling reactions by overcoming the limitations
associated with aryl triazenes.” In this context, we demonstrate a BF3·OEt2-mediated
deaminostannylation of a series of functionalized aryl triazenes for the assembly of
corresponding aryl stannane derivatives. This method may potentially have wide
application in combinatorial chemistry.
We commenced the investigation by choosing aryl triazene 1a with (SnMe3)2
(1,1,1,2,2,2-hexamethyldistannane) as model substrates to optimize the reaction
conditions. The reaction was conducted by the employment of BF3·OEt2 as additive in
EtOH at room temperature (rt) under air (Table 1, entry 1). To our delight, the reaction
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Table 1 Optimization of reaction conditionsa
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additive
solvent, temp, time
EtO2C
N
N
EtO2C
Sn
+
(SnMe3)2
N
1a
2a
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entry
additive
(equiv)
solvent
temp
(°C)
time
yieldb (%)
(min)
1
2c
3
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
BF3·OEt2 (1.0)
Other acids (1.0)
BF3·OEt2 (0.5)
BF3·OEt2 (1.5)
none
EtOH
Dioxane
DME
rt
rt
60
60
60
60
60
60
60
60
30
10
90
180
60
60
30
30
30
34
trace
26
rt
4
THF
rt
23
5
DMF
rt
trace
trace
30
6
DMSO
CH2Cl2
Toluene
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
rt
7
rt
8
rt
19
9
rt
67
10
11
12
13d
14
15
16
17e
40
0
59
68
-10
rt
65
<32
32
rt
rt
70
rt
nr
BF3·OEt2 (1.0)
rt
<5% (18%)f
a
Reaction conditions: 1a (0.5 mmol), (SnMe3)2 (1.1 equiv) in
solvent (2.5 mL) at the specified temperature. b Isolated yields are
c
d
given. Aryltriazene was recovered. Other acids: AcOH, 26%
yield; TsOH, 19% yield; AlCl3, 12% yield; BCl3, 32% yield;
BBr3, 10% yield. e(SnBu3)2 was used instead of (SnMe3)2.
fEstimated by 1H NMR analysis of the crude reaction mixtures. nr
= no reaction.
proceeded smoothly to give the aryl trimethylstannane (2a) in 34% yield after 60
minutes. Then, various solvents were screened to examine their effect on the reaction.
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Acetonitrile was identified as the best candidate, affording the highest yield (67%)
after 30 minutes (Table 1, entries 2-9). We also performed the reaction at different
temperatures. Longer reaction time was required to obtain comparable yield at lower
temperatures (0 °C and -10 °C) (Table 1, entries 10-12). Use of various acids like
AcOH, TsOH, AlCl3, BCl3, and BBr3 were not beneficial as the yield was no more
than 32% (Table 1, entry 13). Further investigation toward the amount of BF3·OEt2
revealed that 1.5 equivalent of BF3·OEt2 yielded a slightly more product and the
control experiment confirmed that BF3·OEt2 was necessary for the reaction (Table 1,
entries 14-16). The progress of the reaction was also examined using different source
of tin. (SnMe3)2 was preferred over (SnBu3)2 which resulted into only a small amount
of aryl(tributyl)stannane (Table 1, Entry 17).
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With the optimized reaction conditions in hand, the scope and limitations of the
transformation were examined (Table 2). A wide variety of aryl triazenes bearing
electron-withdrawing or -donating groups were subjected to the standard conditions to
obtain products in moderate to good yields (2a-s). It should be noted that no obvious
difference in reactivity was observed between electron-deficient (2a-f, 2m-p and 2r)
and electron-rich aryl triazenes (2g-l, 2q and 2s). The results suggest that the
electronic factors had negligible influence on the reaction. More importantly, some
sensitive functional groups, such as allyl, propargyl, hydroxyl and amino group were
well tolerated under the reaction system (2i-j, 2q and 2s), underscoring the good
functional group compatibility of the methodology. Moreover, the
trimethyl(naphthalen-1-yl)stannane (2t) could be assembled in 61% yield. It should be
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mentioned that the scope of the protocol was further expanded for the construction of
heterocyclic aryl stannane compounds, which are usually used as coupling reagents in
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Table 2. The scope of the stannylation reaction of diverse (hetero)aryl triazenes.a,b
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OEt (1 equiv)
SnMe3
BF3
2
N
N
+
(SnMe3)2
R
N
R
MeCN, RT, 30-90 min
2
1
(82%)c
Et, 67%b
2g
2h
2i
2a
2b
2c
2d
2e
, R = H, 63% (80%)
, R = OMe, 72% (89%)
, R = CO2
Me, 69% (85%)
, R = CO2
SnMe3
CH=CH
C
, R = OCH2
2, 65% (81%)
CH, 69% (86%)
, R = Ac, 61% (78%)
, R = CN, 60% (75%)
, R = F, 55% (72%)
, R = CF3, 50% (74%)
2j
, R = OCH2
2k
2l
R
, R = NHAc, 58% (79%)
, R = Ph, 55% (72%)
2f
NH2
N
2m
Me, 63% (80%)
2H, 61% (82%)
, R = CO2
, R = CO
R
SnMe
3 2n
2o
SnMe3
, R = F, 52% (70%)
, R = CN, 68% (84%)
, R = OH, 53% (76%)
2p
2q
SnMe3
2r
2s
, 56% (73%)
SnMe3
, 56% (75%)
SnMe3
SnMe3
N
N
SnMe3
, 59%
H2N
2w
N
d,
d,e (81%)
d,e (84%)
e (71%)
2t
2u
2v
, 66%
, 61% (77%)
, 51%
N
SnMe3
O
S
SnMe3
d (80%)
SnMe3
N
d (85%)
d,e (77%)
2x
, 56%
2y
, 62%
2z
, 64%
aReaction conditions: aryltriazene (0.5 mmol), (SnMe3)2 (0.55 mmol), BF3•OEt2 (0.5 mmol),
MeCN (2.5 mL). b Isolated yields. c Estimated by 1H NMR analysis of the crude reaction mixtures.
d The reactions were performed at 40 oC. e The reactions were performed for 2 h.
organic synthesis, in acceptable yields (2u-z). In general, the present transformation is
efficient and practical. In addition, we investigated the effect of aryltriazenes
substituted with pyrrolidine and piperidine on the reaction. The results show that the
triazenes also gave good yields of the aryl trimethylstannanes (triazene with
pyrrolidine: 74% NMR yield of the crude reaction mixtures and with piperididine: 76%
NMR yield of the crude reaction mixtures).
Biaryls are important structural elements in numerous bioactive natural products,
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medicinal agents, and polymers.11 Accordingly, a new and efficient process for the
region-defined synthesis of symmetrical and unsymmetrical biaryl compounds is
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Table 3. Sequential stannylation and Pd-catalyzed Stille cross-coupling reactions.a,b
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R2
Sn
OEt (1.0 equiv)
N
N
[Pd(PPh )4] (5 mol%)
3 (2 equiv)
BF3
2 (1.1 equiv)
K2CO3
(SnMe3)2
N
Ar'Br (1.2 equiv)
15 h
MeCN, rt
DMF, 90 oC,
R1
R1
R1
3
1
2
entry
1
aryl triazene
product
yield
80%
N
N
N
O
O
3a
O
N
N
2
N
71%
3b
N
N
N
N
N
3
4
5
N
N
N
71%
68%
58%
O
3c
OH
3d
N
NH2
3e
N
N
N
N
NH2
NH2
6
7
N
N
66%
61%
55%
3f
3g
OH
N
8
O
N
N
O
3h
9
74% (66%)c
77%
O
O
O
O
3i
3j
O
O
N
N
10
N
O
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O
F
F
N
N
N
11
12
67%
65%
3k
OH
N
N
N
NC
NC
3l
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a Reaction conditions for the first step: aryltriazene (0.5 mmol),
(SnMe3)2 (0.55 mmol), BF3·OEt2 (0.5 mmol), MeCN (2.5 mL), at
room temperature for 1 hour; second step: Ar′Br (1.2 equiv),
[Pd(PPh3)4] (5 mol%), K2CO3 (2 equiv), toluene (3 mL), at 90 oC
in oil bath for 15 h. b Isolated yields are given. c The reaction was
performed at 5 mmol scale.
highly desirable. Herein, we describe a direct method of biaryls synthesis from aryl
triazene in one pot. We investigated the compatibility of our stannylation reactions
with the conventional Pd-catalysed Stille coupling reaction conditions. After
extensivescreenings, we were pleased to find a desirable protocol. After the synthesis
of aryl triazene, the reaction system was filtered through celite and the filtrate was
evaporated to dryness under reduced pressure. The crude product was then directly
subjected to the Stille reaction to afford the final coupling products. By the use of this
facile methodology, various biaryl derivatives were readily synthesized in moderate to
good yields (Table 3). Both symmetrical and unsymmetrical biaryls were produced
effectively. The transformation can be performed at 5 mmol scale to furnish
acceptable amount of the product 3i.
To gain further insight into the reaction mechanism, several control experiments
were conducted as shown in Scheme 1. The addition of radical initiators, such as
benzoyl peroxide (BPO), 2,2’-azobisisobutyronitrile (AIBN), resulted in no obvious
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improvement of the reaction yield. Similarly, the addition of radical scavengers, such
as 2,2,6,6-tetramethyl- piperidin-1-yl) oxyl (TEMPO), 1,1- diphenylethylene(DPE),
had negligible effect on the reaction yield.7,12 The results implied that the reaction
possibly did not involve a single electron transfer (SET) process, and is different from
the radical type Sandmeyer reaction.
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Scheme 1 Control experiments for mechanistic study.
additive
OEt
BF3
MeO2C
N
N
2
+
(SnMe3)2
MeO2C
Sn
N
MeCN, rt
2a
1a
BPO (0.1 equiv): 68%
TEMPO (2 equiv): 69%
AIBN (0.1 equiv): 70%
DPE (2 equiv): 67%
On the basis of our preliminary mechanistic investigation and the literatures
reported previouly,10,13 a plausible mechanism was proposed as depicted in Scheme 2.
The BF3·OEt2 could activate the N–N bond though coordination with N atom to form
the triazene-BF3 complex A. Then, the cleavage of N–N bond occurs to furnish
diazonium salt B.10c,10d Afterwards, the fluoride anion transfers from the
trifluoroborate anion onto (SnMe3)2 to give rise to the diazonium- (SnMe3)2 complex
C. Finally, the desired stannylation product 2 is afforded by the nucleophilic attack of
Sn-Me3 onto the aryl ring with the release of N2.
Scheme 2 Plausible reaction mechanism.
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Et
BF3
2O
N
N
N
N
Ar N2 F3B
N
Ar
N
Ar
N
F3B
6
1
A
B
7
8
9
(SnMe3)2
Me
3Sn SnMe3
F
Ar N2
Ar SnMe3
- N2
-
-
F
SnMe3
N
BF2
2
C
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In conclusion, we have developed a direct and attractive method for the
efficient synthesis of aryl trimethylstannane derivatives from aryltriazene with
(SnMe3)2. The transformation features mild reaction conditions, readily
available starting materials and excellent functional group tolerance. It is
expected that the methodology will be widely applied in organic synthesis
because of the high significance of the aryl stannane compounds in
cross-coupling reactions. Further studies toward the detailed reaction
mechanism and practical application of this protocol are underway.
EXPERIMENTAL SECTION
General Information.
All triazenes were prepared according to standard literature procedures.15 All other
reagents were received from commercial sources without further purification.
Solvents were freshly dried according to the purification handbook Purification of
Laboratory Chemicals before using. All of the reaction temperatures reported are oil
bath temperatures.
The progress of the reactions was monitored by TLC with silica gel plates
(GF254), and the visualization was carried out under UV light. NMR spectra were
measured on a Varian Unity Inova-400 spectrometer and chemical shifts (δ) are
1
reported in parts per million (ppm). H NMR spectra were recorded at 400 MHz in
NMR solvents (CDCl3) and referenced internally to corresponding solvent resonance,
13
and C NMR spectra were recorded at 100 MHz and referenced to corresponding
solvent resonance, coupling constants are reported in Hz with multiplicities denoted
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as s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet) and br (broad). Infrared
(IR) data were recorded as films on potassium bromide plates with a Bruker Tensor 27
FT-IR spectrometer. Absorbance frequencies are reported in reciprocal centimeters
(cm–1). High resolution mass spectra (HRMS) were acquired with a Bruker Daltonics
MicroTof-Q II mass spectrometer. Products purification was done using silica gel
column chromatography or basic alumina column chromatography.
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Typical experimental procedures for the preparation of the reaction substrates
For 1a-1r, 1t-1v, and 1x-1z: A solution of arylamine 4 (10.5 mmol) in 6 M HCl (6 mL)
was cooled in an ice bath while a solution of NaNO2 (11.8 mmol, 814 mg) in water (6
mL) was added dropwise. The resulting solution of the diazonium salt was stirred
under ice bath for 10 min and then added all at once to a chilled solution of
diisopropylamine (21 mmol, 2.9 mL) and K2CO3 (16.3 mmol, 2.25 g) in water (15
mL). The reaction mixture was stirred for 1 h in an ice bath and the resulting
precipitate isolated by filtration. The damp solid was purified by column
chromatography to obtain the desired products 1a-1r, 1t-1v, and 1x-1z.
For 1s and 1w: A solution of arylamine 4 (10.5 mmol) in 6 M HCl (6 mL) was cooled
in an ice bath while a solution of NaNO2 (11.8 mmol, 814 mg) in water (6 mL) was
added dropwise. The resulting solution of the diazonium salt was stirred under ice
bath for 10 min and then added all at once to a chilled solution of diisopropylamine
(21 mmol, 2.9 mL) and K2CO3 (16.3 mmol, 2.25 g) in water (15 mL). The reaction
mixture was stirred for 1 h in an ice bath and the resulting precipitate isolated by
filtration. The damp solid was purified by column chromatography to obtain the
nitro-substituted products. Nitro-substituted products (0.2 mmol) was dissolved in
EtOH (5 mL) and 10% Pd/C was added. The suspension was stirred 2 h under
hydrogen (1 atm) at rt and filtered through celite and the solvent evaporated in vacuo
to give the product 1s and 1w.
Typical experimental procedure for synthesis of aryl trimethylstannanes:
Aryl triazenes 1a (139 mg, 0.5 mmol), (SnMe3)2 (114 µL, 0.55 mmol), were added to
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a 10 mL round bottom flask which was purged thoroughly with N2. Anhydrous MeCN
(2.5 mL) was added via syringe and the reaction mixture was kept at room
temperature. Then BF3•OEt2 (63 µL, 0.5 mmol) was added dropwise. The resulting
reaction mixture was allowed to stir for 30 min at room temperature (TLC confirmed
that the reaction was complete). The solution was then concentrated under reduced
pressure and the crude residue was purified by flash column chromatography over
basic alumina to afford corresponding aryl trimethylstannanes 2a in 67% isolated
yield (105 mg) as a pale-yellow liquid.
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Ethyl 4-(trimethylstannyl) benzoate (2a):6 According to the general procedure A, 2a
(105 mg) was synthesized in 67% yield from aryl triazenes 1a (139 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). The residue was purified by flash chromatography over basic alumina
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(Petroleum ether/EtOAc = 50/1): Pale yellow liquid. H NMR (400 MHz, CDCl3) δ
7.98 (d, J = 8.0, 2H), 7.57 (d, J = 8.0, 2H), 4.40 – 4.35 (m, 2H), 1.39 (t, J = 7.0, 3H),
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0.32 (s, 9H); C{1H} NMR (100 MHz, CDCl3) δ 166.9, 149.4, 135.7, 130.1, 128.4,
60.8, 14.3, -9.5; IR (cm-1): 2982, 1718, 1276, 1103, 1066, 771, 753. HRMS (ESI)
calcd for C12H19O2Sn [M+H]+ 315.0402; found 315.0400.
Methyl 4-(trimethylstannyl) benzoate (2b):7 According to the general procedure A, 2b
(104 mg) was synthesized in 69% yield from aryl triazenes 1b (132 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). The residue was purified by flash chromatography over basic alumina
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(Petroleum ether/EtOAc = 50/1): Pale yellow liquid. H NMR (400 MHz, CDCl3) δ
7.97 (d, J = 7.2, 1H), 7.56 (d, J = 6.8, 1H), 3.91 (s, 1H), 0.32 (s, 9H); 13C{1H} NMR
(100 MHz, CDCl3) δ 167.4, 149.6, 135.7, 129.7, 128.4, 52.0, -9.5; IR (cm-1): 2985,
1725, 1591, 1435, 1386, 1279, 1185, 1066, 1047, 772. HRMS (ESI) calcd for
C11H17O2Sn [M+H]+ 301.0245; found 301.0240.
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1-(4-(trimethylstannyl)phenyl)ethan-1-one (2c):6 According to the general procedure
A, 2c (87 mg) was synthesized in 61% yield from aryl triazenes 1c (124 mg, 0.5
mmol) with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in
MeCN (2.5 mL). The residue was purified by flash chromatography over basic
alumina (Petroleum ether/EtOAc = 50/1): Pale yellow liquid. 1H NMR (400 MHz,
CDCl3) δ 7.89 (d, J = 8.0, 2H), 7.60 (d, J = 8.0, 2H), 2.59 (s, 3H), 0.32 (s, 9H);
13C{1H} NMR (100 MHz, CDCl3) δ 198.4, 150.1, 136.7, 135.9, 127.1, 26.5, -9.5; IR
(cm-1): 2984, 1738, 1684, 1587, 1386, 1270, 1188, 1057, 955, 772. HRMS (ESI) calcd
for C11H17OSn [M+H]+ 285.0296; found 285.0295.
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4-(trimethylstannyl)benzonitrile (2d):6 According to the general procedure A, 2d (87
mg) was synthesized in 61% yield from aryl triazenes 1d (115 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over basic alumina
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(Petroleum ether/EtOAc = 50/1): Pale yellow liquid. H NMR (400 MHz, CDCl3) δ
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7.60 (d, J = 8.0, 2H), 7.57 (d, J = 8.4, 2H), 0.33 (s, 9H); C{1H} NMR (100 MHz,
CDCl3) δ 150.2, 136.2, 130.7, 119.0, 111.7, -9.5; IR (cm-1): 2921, 2228, 1740, 1383,
1244, 1066, 1046, 1018, 816, 772, 731. HRMS (ESI) calcd for C10H14NSn [M+H]+
268.0143; found 268.0144.
(4-fluorophenyl)trimethylstannane (2e):6 According to the general procedure A, 2e
(73 mg) was synthesized in 55% yield from aryl triazenes 1e (112 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over basic alumina
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(Petroleum ether/EtOAc = 50/1): Pale yellow liquid. H NMR (400 MHz, CDCl3) δ
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7.45 (dd, J = 6.4, 6.4 Hz, 2H), 7.05 (dd, J = 8.4, 8.4 Hz, 2H), 0.30 (s, 9H); C{1H}
NMR (100 MHz, CDCl3) δ 163.3 (d, J = 245 Hz), 137.3 (d, J = 6.0 Hz), 137.0 (d, J =
4.0 Hz), 115.1 (d, J = 19 Hz), -9.4; IR (cm-1): 2923, 1740, 1580, 1491, 1373, 1242,
1163, 1049, 816, 767. HRMS (ESI) calcd for C9H14FSn [M+H]+ 261.0096; found
261.0094.
Trimethyl(4-(trifluoromethyl) phenyl)stannane (2f):6 According to the general
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procedure A, 2f (78 mg) was synthesized in 50% yield from aryl triazenes 1f (137 mg,
0.5 mmol) with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol)
in MeCN (2.5 mL). The residue was purified by flash chromatography over basic
alumina (Petroleum ether): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ 7.62 (d,
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J = 7.6, 2H), 7.57 (d, J = 6.0, 2H), 0.33 (s, 9H); C{1H} NMR (100 MHz, CDCl3) δ
147.7, 136.0, 130.2 (q, J = 32 Hz), 125.6, 124.3 (q, J = 4.0 Hz), -9.6; 19F NMR (376.5
MHz, CDCl3) δ -62.8; IR (cm-1): 2980, 1742, 1600, 1403, 1389, 1273, 1162, 1119,
1018, 857, 769. HRMS (ESI) calcd for C10H14F3Sn [M+H]+ 311.0064; found
311.0063.
Trimethyl(phenyl)stannane (2g):6 According to the general procedure A, 2g (76 mg)
was synthesized in 63% yield from aryl triazenes 1g (103 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over basic alumina
(Petroleum ether): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 5.6
Hz, 2H), 7.36 – 7.31 (m, 3H), 0.29 (s, 9H); 13C{1H} NMR (100 MHz, CDCl3) δ 142.3,
135.8, 128.2, 128.0, -9.6; IR (cm-1): 2925, 1742, 1661, 1460, 1376, 1242, 1046, 938,
731. HRMS (ESI) calcd for C9H15Sn [M+H]+ 243.0190; found 243.0192.
(4-methoxyphenyl) trimethylstannane (2h):6 According to the general procedure A, 2h
(98 mg) was synthesized in 72% yield from aryl triazenes 1h (118 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). The residue was purified by flash chromatography over basic alumina
(Petroleum ether): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 8.4
Hz, 2H), 6.94 (d, J = 8.4 Hz, 2H), 3.82 (s, 3H), 0.29 (s, 9H); C{1H} NMR (100
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MHz, CDCl3) δ 159.8, 136.8, 132.3, 113.9, 54.9, -9.5; IR (cm-1): 2913, 2834, 1589,
1496, 1277, 1244, 1180, 1076, 1034, 769. HRMS (ESI) calcd for C10H17OSn [M+H]+
273.0296; found 273.0293.
(4-(allyloxy) phenyl) trimethylstannane (2i):7 According to the general procedure A, 2i
(97 mg) was synthesized in 65% yield from aryl triazenes 1i (131 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
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mL). The residue was purified by flash chromatography over basic alumina
(Petroleum ether/EtOAc = 50/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
7.41 (d, J = 8.4, 2H), 6.94 (d, J = 8.4, 2H), 6.11 – 6.02 (m, 1H), 5.42 (dd, J = 1.6, 1.6,
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1H), 5.30 (dd, J = 1.2, 1.6, 1H), 4.55 (d, J = 5.2, 2H), 0.28 (s, 9H); C{1H} NMR
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(100 MHz, CDCl3) δ 158.8, 136.8, 133.3, 132.6, 117.6, 114.7, 68.5, -9.5; IR (cm-1):
3011, 2982, 1741, 1586, 1495, 1276, 1180, 1076, 769. HRMS (ESI) calcd for
C12H19OSn [M+H]+ 299.0452; found 299.0452.
Trimethyl(4-(prop-2-yn-1-yloxy) phenyl)stannane (2j):7 According to the general
procedure A, 2j (102 mg) was synthesized in 69% yield from aryl triazenes 1j (130
mg, 0.5 mmol) with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5
mmol) in MeCN (2.5 mL). The residue was purified by flash chromatography over
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basic alumina (Petroleum ether/EtOAc = 50/1): Pale yellow liquid. H NMR (400
MHz, CDCl3) δ 7.44 (d, J = 8.4, 1H), 7.01 (d, J = 8.4, 1H), 4.70 (s, 2H), 2.53 (s, 1H),
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0.29 (s, 9H); C{1H} NMR (100 MHz, CDCl3) δ 157.8, 136.8, 133.6, 114.8, 78.6,
75.4, 55.5, -9.5; IR (cm-1): 3297, 2982, 1585, 1495, 1276, 1221, 1076, 924, 769.
HRMS (ESI) calcd for C12H17OSn [M+H]+ 297.0296; found 297.0299.
N-(4-(trimethylstannyl)phenyl)acetamide (2k):7 According to the general procedure A,
2k (87 mg) was synthesized in 58% yield from aryl triazenes 1k (131 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). The residue was purified by flash chromatography over neutral alumina
(Petroleum ether/EtOAc = 10/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
7.47 (d, J = 8.8, 2H), 7.43 (d, J = 8.4, 2H), 7.15 (s, 1H), 2.17 (s, 3H), 0.27 (s, 9H);
13C{1H} NMR (100 MHz, CDCl3) δ 168.2, 137.9, 136.4, 129.0, 119.5, 24.8, -9.5; IR
(cm-1): 3295, 2920, 1724, 1538, 1386, 1281, 1074, 1043, 941, 756. HRMS (ESI):
Calculated for C11H17NNaOSn [M+Na]+: 322.0224, Found: 322.0225.
[1,1'-biphenyl]-4-yltrimethylstannane (2l):6 According to the general procedure A, 2l
(87 mg) was synthesized in 55% yield from aryl triazenes 1l (141 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over basic alumina
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(Petroleum ether/ EtOAc = 100/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
7.64 – 7.62 (m, 6H), 7.47 (t, J = 7.6, 2H), 7.40 – 7.36 (m, 1H), 0.36 (s, 9H); 13C{1H}
NMR (100 MHz, CDCl3) δ 141.2, 141.1, 141.0, 136.2, 128.7, 127.2, 127.1, 126.7,
-9.8; IR (cm-1): 2980, 2913, 1741, 1653, 1455, 1378, 1280, 1005, 910, 757, 737.
HRMS (ESI): Calculated for C15H18SnNa [M+Na]+: 341.0323, Found: 341.0325.
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Methyl 3-(trimethylstannyl) benzoate (2m):15a According to the general procedure A,
2m (95 mg) was synthesized in 63% yield from aryl triazenes 1m (132 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). The residue was purified by flash chromatography over basic alumina
(Petroleum ether): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ 8.16 (s, 1H),
7.97 (d, J = 8.0, 1H), 7.67 (d, J = 6.8, 1H), 7.42 – 7.38 (m, 1H), 3.92 (s, 1H), 0.32 (s,
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9H); C{1H} NMR (100 MHz, CDCl3) δ 167.5, 142.7, 140.3, 136.6, 129.4, 129.3,
127.8, 52.0, -9.5; IR (cm-1): 2981, 2950, 1724, 1583, 1434, 1275, 1044, 972, 771.
HRMS (ESI): Calculated for C11H16O2SnNa [M+Na]+: 323.0064, Found: 323.0064.
3-(trimethylstannyl) benzoic acid (2n):7 According to the general procedure A, 2n (87
mg) was synthesized in 61% yield from aryl triazenes 1n (125 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over neutral alumina
(MeOH/DCM = 30/1): Pale yellow liquid; 1H NMR (400 MHz, CDCl3) δ 8.23 (s, 1H),
8.04 (d, J = 7.6, 1H), 7.72 (d, J = 6.8, 1H), 7.42 (t, J = 7.2, 1H), 0.33 (s, 9H); 13C{1H}
NMR (100 MHz, CDCl3) δ 172.2, 142.9, 141.1, 137.3, 130.0, 128.6, 127.9, -9.5; IR
(cm-1): 2989, 2853, 1681, 1431, 1260, 1135, 943, 766, 741. HRMS (ESI): Calculated
for C10H14O2SnNa [M+Na]+: 308.9908, Found: 308.9909.
(3-fluorophenyl) trimethylstannane (2o):7 According to the general procedure A, 2o
(68 mg) was synthesized in 52% yield from aryl triazenes 1o (112 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over basic alumina
(Petroleum ether): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ 7.31 – 7.27 (m,
1H), 7.22 – 7.20 (m, 1H), 7.17 – 7.14 (m, 1H), 6.98 – 6.93 (m, 1H), 0.28 (s, 9H);
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13C{1H} NMR (100 MHz, CDCl3) δ 162.6 (d, J = 249 Hz), 145.1 (d, J = 3.0 Hz),
131.2 (d, J = 3.0 Hz), 129.4 (d, J = 6 Hz), 122.0 (d, J = 17 Hz), 115.0 (d, J = 21 Hz),
-9.5; IR (cm-1): 2989, 1741, 1653, 1591, 1470, 1371, 1256, 1206, 783. HRMS (ESI):
Calculated for C9H13FSnNa [M+Na]+: 282.9915, Found: 282.9919.
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3-(trimethylstannyl) benzonitrile (2p):7 According to the general procedure A, 2p (91
mg) was synthesized in 68% yield from aryl triazenes 1p (115 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over basic alumina
(Petroleum ether): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ 7.75 (s, 1H),
7.70 (d, J = 7.6, 1H), 7.59 – 7.56 (m, 1H), 7.41 (t, J = 7.6, 1H), 0.33 (s, 9H); 13C{1H}
NMR (100 MHz, CDCl3) δ 144.2, 139.8, 139.0, 131.5, 128.1, 119.2, 112.1, -9.5; IR
(cm-1): 2985, 2920, 1731, 1681, 1538, 1387, 1255, 1242, 1073, 737. HRMS (ESI):
Calculated for C10H13NSnNa [M+Na]+: 289.9962, Found: 289.9966.
3-(trimethylstannyl) phenol (2q):7 According to the general procedure A, 2q (68 mg)
was synthesized in 53% yield from aryl triazenes 1q (111 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over neutral alumina
(Petroleum ether/EtOAc = 10/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
7.22 (t, J = 7.2, 1H), 7.04 (d, J = 6.8, 1H), 6.69 (d, J = 2.8, 1H), 6.79 – 6.76 (m, 1H),
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4.88 (s, 1H), 0.27 (s, 9H); C{1H} NMR (100 MHz, CDCl3) δ 154.9, 141.1, 129.2,
128.0, 122.2, 115.1, -9.5; IR (cm-1): 3376, 2981, 2910, 1740, 1651, 1573, 1472, 1044,
993, 775. HRMS (ESI): Calculated for C9H15OSn [M+H]+: 259.0139, Found:
259.0136.
2-(trimethylstannyl) benzonitrile (2r):6 According to the general procedure A, 2r (75
mg) was synthesized in 56% yield from aryl triazenes 1r (115 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over basic alumina
(Petroleum ether/EtOAc = 50/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
7.65 (d, J = 7.2, 1H), 7.57 (d, J = 7.2, 1H), 7.50 (t, J = 7.2, 1H), 7.36 (t, J = 7.6, 1H),
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0.44 (s, 9H); C{1H} NMR (100 MHz, CDCl3) δ 147.9, 136.3, 132.6, 131.4, 128.5,
120.2, 119.9, -9.0; IR (cm-1): 2985, 2917, 1740, 1576, 1456, 1252, 1049, 762. HRMS
(ESI): Calculated for C10H13NSnNa [M+Na]+: 289.9962, Found: 289.9966.
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2-(trimethylstannyl) aniline (2s):15b According to the general procedure A, 2s (72 mg)
was synthesized in 56% yield from aryl triazenes 1s (110 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over neutral alumina
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(Petroleum ether/EtOAc = 6/1): Pale yellow liquid. H NMR (400 MHz, CDCl3) δ
7.25 (d, J = 7.6, 1H), 7.14 (t, J = 7.6, 1H), 6.78 (t, J = 7.2, 1H), 6.67 (d, J = 8.0, 1H),
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3.62 (s, 2H), 0.33 (s, 9H); C{1H} NMR (100 MHz, CDCl3) δ 151.8, 136.7, 129.8,
125.8, 118.9, 114.9, -9.2; IR (cm-1): 3367, 2980, 1716, 1615, 1278, 1064, 751.
HRMS (ESI): Calculated for C9H16NSn [M+H]+: 258.0299, Found: 258.0300.
Trimethyl(naphthalen-1-yl) stannane (2t):15c According to the general procedure A, 2t
(89 mg) was synthesized in 61% yield from aryl triazenes 1t (128 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over basic alumina
(Petroleum ether/EtOAc = 100/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
7.88 – 7.65 (m, 3H), 7.57 (d, J = 6.4, 1H), 7.50 – 7.46 (m, 3H), 0.45 (s, 9H); 13C{1H}
NMR (100 MHz, CDCl3) δ 142.5, 138.4, 134.4, 133.6, 129.8, 129.0, 128.7, 125.8,
125.4, 125.2, -8.4; IR (cm-1): 3046, 2980, 2915, 1740, 1556, 1371, 1242, 1044, 771.
HRMS (ESI): Calculated for C13H16SnNa [M+Na]+: 315.0166, Found: 315.0168.
2-(trimethylstannyl) pyridine (2u):15d According to the general procedure A, 2u (72
mg) was synthesized in 59% yield from aryl triazenes 1u (103 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over neutral alumina
(Petroleum ether/EtOAc = 10/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
8.73 (d, J = 4.8, 1H), 7.53 – 7.49 (m, 1H), 7.44 (d, J = 7.2, 1H), 7.15 – 7.12 (m, 1H),
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0.34 (s, 9H); C{1H} NMR (100 MHz, CDCl3) δ 173.5, 150.5, 133.5, 131.6, 122.2,
-9.5; IR (cm-1): 3354, 2921, 1741, 1505, 1456, 1371, 1271, 1047, 757. HRMS (ESI):
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Calculated for C8H13NSnNa [M+Na]+: 265.9962, Found: 265.9963.
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3-(trimethylstannyl) pyridine (2v):15d According to the general procedure A, 2v (80
mg) was synthesized in 66% yield from aryl triazenes 1v (103 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over neutral alumina
(Petroleum ether/EtOAc = 10/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
8.64 (s, 1H), 8.54 (d, J = 3.6, 1H), 7.78 (d, J = 7.6, 1H), 7.27 – 7.24 (m, 1H), 0.34 (s,
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9H); C{1H} NMR (100 MHz, CDCl3) δ 155.3, 149.1, 143.8, 137.4, 123.9, -9.5; IR
(cm-1): 2981, 2922, 2852, 1586, 1465, 1242, 1028, 772. HRMS (ESI): Calculated for
C8H14NSn [M+H]+: 244.0143, Found: 244.0142.
5-(trimethylstannyl)pyridin-2-amine (2w):7 According to the general procedure A, 2w
(66 mg) was synthesized in 51% yield from aryl triazenes 1w (111 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). The residue was purified by flash chromatography over neutral alumina
(Petroleum ether/EtOAc = 5/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
8.01 (s, 1H), 7.51 – 7.48 (m, 1H), 6.53 (d, J = 8.0, 1H), 4.78 (s, 2H), 0.26 (s, 9H);
13C{1H} NMR (100 MHz, CDCl3) δ 158.0, 153.0, 145.0, 123.7, 109.3, -9.5; IR
(cm-1): 3322, 2978, 1579, 1485, 1364, 1145, 1078, 820, 765. HRMS (ESI):
Calculated for C8H14N2SnNa [M+Na]+: 281.0071, Found: 281.0070.
2-(trimethylstannyl) pyrazine (2x):15e According to the general procedure A, 2x (68
mg) was synthesized in 56% yield from aryl triazenes 1x (104 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). The residue was purified by flash chromatography over neutral alumina
(Petroleum ether/EtOAc = 10/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
8.70 (t, J = 2.0, 1H), 8.58 (d, J = 1.6, 1H), 8.39 (d, J = 2.4, 1H), 0.39 (s, 9H); 13C{1H}
NMR (100 MHz, CDCl3) δ 169.1, 150.6, 146.6, 143.2, 123.8, -9.4; IR (cm-1): 3046,
2980, 1740, 1556, 1446, 1379, 1241, 1037, 774. HRMS (ESI): Calculated for
C7H12N2SnNa [M+Na]+: 266.9915, Found: 266.9916.
Benzofuran-2-yltrimethylstannane (2y):15d According to the general procedure A, 2y
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(87 mg) was synthesized in 62% yield from aryl triazenes 1y (123 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). The residue was purified by flash chromatography over basic alumina
(Petroleum ether/EtOAc = 70/1): Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ
7.54 (d, J = 7.2, 1H), 7.49 (d, J = 8.0, 1H), 7.24 – 7.15 (m, 2H), 6.91 (s, 1H), 0.40 (s,
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9H); C{1H} NMR (100 MHz, CDCl3) δ 164.9, 158.5, 127.9, 123.5, 122.1, 120.3,
117.5, 110.9, -9.2; IR (cm-1): 3060, 2983, 1740, 1575, 1486, 1246, 1152, 1029, 925,
751. HRMS (ESI): Calculated for C11H15OSn [M+H]+: 283.0139, Found: 283.0138.
Benzo[b]thiophen-2-yltrimethylstannane (2z):15d According to the general procedure
A, 2z (95 mg) was synthesized in 64% yield from aryl triazenes 1z (131 mg, 0.5
mmol) with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in
MeCN (2.5 mL). The residue was purified by flash chromatography over basic
alumina (Petroleum ether/EtOAc = 70/1): Pale yellow liquid. 1H NMR (400 MHz,
CDCl3) δ 7.90 (d, J = 7.6, 1H), 7.82 (d, J = 7.6, 1H), 7.42 (s, 1H), 7.35 – 7.26 (m, 2H),
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0.43 (s, 9H); C{1H} NMR (100 MHz, CDCl3) δ 144.1, 140.9, 140.3, 131.8, 123.8,
123.4, 122.7, 121.8, -8.3; IR (cm-1): 3053, 2983, 1790, 1556, 1434, 1286, 1242, 1045,
920, 742. HRMS (ESI): Calculated for C11H15SSn [M+H]+: 298.9911, Found:
298.9910.
Typical Experimental Procedure for sequential stannylation and Pd-catalyzed
Stille crosscoupling reactions:
Aryl triazenes 1c (124 mg, 0.5 mmol), (SnMe3)2 (114 µL, 0.55 mmol), were added to
a 10 mL round bottom flask which was purged thoroughly with N2. Anhydrous MeCN
(2.5 mL) was added via syringe and the reaction mixture was kept at room
temperature. Then BF3•OEt2 (63 µL, 0.5 mmol) was added dropwise. The resulting
reaction mixture was allowed to stir, TLC confirmed that the reaction was complete.
The reaction system was filtered through celite remove the insoluble substance,
followed by removing the MeCN under reduced pressure. Then under nitrogen
atmosphere, Pd (PPh3)4 (29 mg, 5 mol%), PhBr (94 mg, 0.6 mmol), K2CO3 (138 mg,
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2 equiv.) and toluene (3 mL) were added, the solution was stirred for 15 h at 90 °C in
oil bath. The solution was then concentrated by rotavapor under reduced pressure to
leave a crude residue, which was purified by silica gel column chromatography
(Petroleum ether-EtOAc = 40:1) to give 3a in 80% isolated yield (78 mg) as
pale-yellow solid.
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1-([1,1'-biphenyl]-4-yl)ethan-1-one (3a):16a According to the general procedure B, 3a
(76 mg) was synthesized in 78% yield from aryl triazenes 1c (124 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). and Pd (PPh3)4 (29 mg, 5 mol%), PhBr (94 mg, 0.6 mmol), K2CO3 (138 mg, 2
equiv.) in toluene (3 mL), The residue was purified by silica gel column
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chromatography (Petroleum ether-EtOAc = 20:1): white solid, mp 121−122 °C; H
NMR (400 MHz, CDCl3) δ = 8.07 – 8.01 (m, 2H), 7.72 – 7.67 (m, 2H), 7.66 – 7.61
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(m, 2H), 7.51 – 7.45 (m, 2H), 7.41 (dt, J=9.6, 4.3, 1H), 2.64 (s, 3H); C{1H} NMR
(100 MHz, CDCl3) δ 197.8, 145.8, 139.9, 135.9, 129.0, 128.9, 128.3, 127.3, 127.3,
26.7. IR (cm-1): 3208, 1742, 1650, 1381, 1279, 947, 774, 703. HRMS (ESI):
Calculated for C14H12ONa [M+Na]+: 219.0780, Found: 219.0781.
1-([1,1'-biphenyl]-4-yl)propan-1-one (3b):16b According to the general procedure B,
3b (82 mg) was synthesized in 71% yield from aryl triazenes 1g (103 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). and Pd (PPh3)4 (29 mg, 5 mol%), 4'-Bromopropiophenone (128 mg, 0.6
mmol), K2CO3 (138 mg, 2 equiv.) in toluene (3 mL), The residue was purified by
silica gel column chromatography (Petroleum ether-EtOAc = 20:1): pale yellow solid,
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mp 97−98 °C; H NMR (400 MHz, CDCl3) δ 8.10 – 8.05 (m, 2H), 7.73 – 7.69 (m,
2H), 7.68 – 7.63 (m, 2H), 7.53 – 7.47 (m, 2H), 7.46 – 7.40 (m, 1H), 3.07 (q, J = 7.2
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Hz, 2H), 1.29 (t, J = 7.2 Hz, 3H); C{1H} NMR (100 MHz, CDCl3) δ 200.5, 145.6,
140.0, 135.6, 129.0, 128.6, 128.2, 127.3, 127.2, 31.9, 8.3. IR (cm-1): 3201, 3123, 1729,
1651, 1298, 1245, 931, 753. HRMS (ESI): Calculated for C15H14ONa [M+Na]+:
233.0937, Found: 233.0935.
2-methoxy-5-methyl-1,1'-biphenyl (3c):16c According to the general procedure B, 3c
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(82 mg) was synthesized in 71% yield from aryl triazenes 1g (103 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). and Pd (PPh3)4 (29 mg, 5 mol%), 3-Bromo-4-methoxytoluene (121 mg, 0.6
mmol), K2CO3 (138 mg, 2 equiv.) in toluene (3 mL), The residue was purified by
silica gel column chromatography (Petroleum ether-EtOAc = 40:1): colorless liquid.
1H NMR (400 MHz, CDCl3) δ 7.83 – 7.78 (m, 2H), 7.68 – 7.62 (m, 2H), 7.59 – 7.53
(m, 1H), 7.41 (d, J = 2.2 Hz, 1H), 7.35 (ddd, J = 8.3, 2.3, 0.6 Hz, 1H), 7.10 (d, J = 8.3
Hz, 1H), 3.98 (s, 3H), 2.58 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 154.7, 138.9,
131.9, 130.7, 130.2, 129.8, 129.1, 128.3, 127.1, 111.6, 55.9, 20.7. IR (cm-1): 3194,
3081, 3009, 1551, 1298, 1279, 1083, 840, 703. HRMS (ESI): Calculated for
C14H14ONa [M+Na]+: 221.0937, Found: 221.0938.
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[1,1'-biphenyl]-4-ylmethanol (3d):16d According to the general procedure B, 3d (63
mg) was synthesized in 68% yield from aryl triazenes 1g (103 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). and Pd (PPh3)4 (29 mg, 5 mol%), 4-bromobenzyl alcohol (112 mg, 0.6 mmol),
K2CO3 (138 mg, 2 equiv.) in toluene (3 mL), The residue was purified by silica gel
column chromatography (Petroleum ether-EtOAc = 10:1): pale yellow solid, mp
101−102 °C; 1H NMR (400 MHz, CDCl3) δ 7.67 – 7.61 (m, 4H), 7.53 – 7.44 (m, 4H),
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7.43 – 7.38 (m, 1H), 4.76 (s, 2H); C{1H} NMR (100 MHz, CDCl3) δ 140.9, 140.6,
139.9, 128.9, 127.5, 127.4, 127.3, 127.1, 65.0. IR (cm-1): 3851, 3201, 2986, 1523,
1450, 1182, 835, 771, 703. HRMS (ESI): Calculated for C13H12ONa [M+Na]+:
207.0780, Found: 207.0782.
[1,1'-biphenyl]-2-amine (3e):16e According to the general procedure B, 3e (65 mg)
was synthesized in 58% yield from aryl triazenes 1g (103 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). and Pd (PPh3)4 (29 mg, 5 mol%), 2-bromoaniline (103 mg, 0.6 mmol), K2CO3
(138 mg, 2 equiv.) in toluene (3 mL), The residue was purified by silica gel column
chromatography (Petroleum ether-EtOAc = 10:1): pale yellow solid, mp 50−51 °C;
1H NMR (400 MHz, CDCl3) δ 7.51 (dd, J = 8.5, 5.8 Hz, 4H), 7.44 – 7.38 (m, 1H),
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2H); C{1H} NMR (100 MHz, CDCl3) δ 143.7, 139.7, 130.6, 129.3, 129.0, 128.7,
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127.7, 127.3, 118.8, 115.7. IR (cm-1): 3675, 3583, 3209, 1681, 1539, 1348, 801, 621.
HRMS (ESI): Calculated for C12H11NNa [M+Na]+: 192.0784, Found: 192.0784.
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[1,1'-biphenyl]-3-amine (3f):17a According to the general procedure B, 3e (56 mg)
was synthesized in 66% yield from aryl triazenes 1g (103 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). and Pd (PPh3)4 (29 mg, 5 mol%), 3-bromoaniline (103 mg, 0.6 mmol), K2CO3
(138 mg, 2 equiv.) in toluene (3 mL), The residue was purified by silica gel column
chromatography (Petroleum ether-EtOAc = 10:1): pale yellow solid, mp 31−32 °C;
1H NMR (400 MHz, CDCl3) δ 7.65 – 7.59 (m, 2H), 7.47 (dd, J = 9.6, 4.8 Hz, 2H),
7.38 (dd, J = 10.7, 3.8 Hz, 1H), 7.28 (dd, J = 10.4, 4.8 Hz, 1H), 7.04 (d, J = 7.6 Hz,
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1H), 6.95 (d, J = 1.7 Hz, 1H), 6.72 (dd, J = 7.9, 2.2 Hz, 1H), 3.77 (s, 2H); C{1H}
NMR (100 MHz, CDCl3) δ 146.8, 142.5, 141.4, 129.7, 128.7, 127.3, 127.2, 117.7,
114.1, 113.9. IR (cm-1): 3674, 3568, 3201, 1661, 1526, 1309, 762, 596. HRMS
(ESI): Calculated for C12H11NNa [M+Na]+: 192.0784, Found: 192.0786.
[1,1'-biphenyl]-4-amine (3g):16e According to the general procedure B, 3e (52 mg)
was synthesized in 61% yield from aryl triazenes 1g (103 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). and Pd (PPh3)4 (29 mg, 5 mol%), 4-bromoaniline (103 mg, 0.6 mmol), K2CO3
(138 mg, 2 equiv.) in toluene (3 mL), The residue was purified by silica gel column
chromatography (Petroleum ether-EtOAc = 10:1): pale yellow solid, mp 53−54 °C;
1H NMR (400 MHz, CDCl3) δ 7.68 – 7.59 (m, 2H), 7.56 – 7.44 (m, 4H), 7.42 – 7.32
(m, 1H), 6.87 – 6.78 (m, 2H), 3.77 (s, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 145.9,
141.2, 131.6, 128.8, 128.1, 126.5, 126.3, 115.5. IR (cm-1): 3202, 3175, 1675, 1534,
1314, 837, 769, 545. HRMS (ESI): Calculated for C12H11NNa [M+Na]+: 192.0784,
Found: 192.0785.
Methyl 4'-hydroxy-[1,1'-biphenyl]-4-carboxylate (3h):17b According to the general
procedure B, 3h (63 mg) was synthesized in 55% yield from aryl triazenes 1b (132
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mg, 0.5 mmol) with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5
mmol) in MeCN (2.5 mL). and Pd (PPh3)4 (29 mg, 5 mol%), 4-bromophbenol (104
mg, 0.6 mmol), K2CO3 (138 mg, 2 equiv.) in toluene (3 mL), The residue was purified
by silica gel column chromatography (Petroleum ether-EtOAc = 10:1): white solid,
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mp 227−228 °C; H NMR (400 MHz, DMSO) δ 9.76 (s, 1H), 8.03 – 7.92 (m, 2H),
7.80 – 7.69 (m, 2H), 7.59 (d, J = 8.7 Hz, 2H), 6.95 – 6.83 (m, 2H), 3.86 (s, 3H);
13C{1H} NMR (100 MHz, DMSO) δ 166.6, 158.5, 145.2, 130.2, 129.9, 128.6, 127.8,
126.4, 166.4. IR (cm-1): 3832, 3189, 3080, 1789, 1675, 1320, 1176, 875, 824.
HRMS (ESI): Calculated for C14H12O3Na [M+Na]+: 251.0679, Found: 251.0678.
Methyl [1,1'-biphenyl]-4-carboxylate (3i):16a According to the general procedure B, 3i
(78 mg) was synthesized in 74% yield from aryl triazenes 1b (132 mg, 0.5 mmol)
with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN
(2.5 mL). and Pd (PPh3)4 (29 mg, 5 mol%), BrPh (94 mg, 0.6 mmol), K2CO3 (138 mg,
2 equiv.) in toluene (3 mL), The residue was purified by silica gel column
chromatography (Petroleum ether-EtOAc = 30:1): pale yellow solid, mp 117−118 °C;
1H NMR (400 MHz, CDCl3) δ 8.18 – 8.10 (m, 2H), 7.72 – 7.68 (m, 2H), 7.67 – 7.63
(m, 2H), 7.53 – 7.47 (m, 2H), 7.44 (dd, J = 5.0, 3.7 Hz, 1H), 3.97 (s, 3H); C{1H}
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NMR (100 MHz, CDCl3) δ 167.0, 145.6, 140.0, 130.1, 128.96, 128.93, 128.2, 127.3,
127.1, 52.1. IR (cm-1): 3201, 3071, 1768, 1651, 1301, 1204, 1129, 765. HRMS
(ESI): Calculated for C14H12O2Na [M+Na]+: 235.0730, Found: 235.0733.
Typical experimental procedure for gram scale synthesis of 3i:
In nitrogen atmosphere, Aryl triazenes 1a (1.39 g, 5.0 mmol) and (SnMe3)2 (1.14 mL,
5.5 mmol) were added to a 100 mL round bottom flask. Anhydrous MeCN (25 mL)
was added via syringe and the reaction mixture was kept at 0 oC. Then BF3•OEt2 (0.63
mL, 5.0 mmol) was added dropwise. The resulting reaction mixture was allowed to
stir, TLC confirmed that the reaction was complete. The reaction system was filtered
through Celite remove the insoluble substance, followed by removing the MeCN
under reduced pressure. Then under nitrogen atmosphere, Pd (PPh3)4 (290 mg, 5
mol%), PhBr (940 mg, 6.0 mmol), K2CO3 (1.38 g, 10 mmol) and toluene (30 mL)
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were added, the solution was stirred for 20 h at 90 °C. The solution was then
concentrated by rotavapor under reduced pressure to leave a crude residue, which was
purified by silica gel column chromatography (Petroleum ether, then Petroleum
ether-EtOAc = 80:1) to give 3i in 66% isolated yield (699.6 mg) as white solid.
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2,2'-dimethoxy-1,1'-biphenyl (3j):17cAccording to the general procedure B, 3j (82 mg)
was synthesized in 77% yield from aryl triazenes 1aa (118 mg, 0.5 mmol) with
(SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in MeCN (2.5
mL). and Pd (PPh3)4 (29 mg, 5 mol%), 1-bromo-2-methoxybenzene (112 mg, 0.6
mmol), K2CO3 (138 mg, 2 equiv.) in toluene (3 mL), The residue was purified by
silica gel column chromatography (Petroleum ether-EtOAc = 20:1): pink solid, mp
155−156 °C; 1H NMR (400 MHz, CDCl3) δ 7.40 (qd, J = 8.6, 4.5 Hz, 2H), 7.32 (ddd,
J = 10.1, 7.4, 1.8 Hz, 2H), 7.12 – 7.01 (m, 4H), 3.84 (dd, J = 6.1, 2.6 Hz, 6H); 13C{1H}
NMR (100 MHz, CDCl3) δ 157.1, 131.5, 128.7, 127.9, 120.4, 111.2, 55.7. IR (cm-1):
3205, 3074, 3008, 1632, 1499, 1462, 1269, 1071, 752. HRMS (ESI): Calculated for
C14H14O2Na [M+Na]+: 237.0886, Found: 237.0886.
1-(2'-fluoro-[1,1'-biphenyl]-4-yl)propan-1-one (3k): According to the general
procedure B, 3k (76 mg) was synthesized in 67% yield from aryl triazenes 1ab (112
mg, 0.5 mmol) with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5
mmol) in MeCN (2.5 mL). and Pd (PPh3)4 (29 mg, 5 mol%), 4'-bromopropiophenone
(128 mg, 0.6 mmol), K2CO3 (138 mg, 2 equiv.) in toluene (3 mL), The residue was
purified by silica gel column chromatography (Petroleum ether-EtOAc = 10:1): pale
yellow solid, mp 76−77 °C; 1H NMR (400 MHz, CDCl3) δ 8.07 – 8.00 (m, 2H), 7.68
– 7.60 (m, 2H), 7.46 (td, J = 7.7, 1.8 Hz, 1H), 7.36 (tdd, J = 7.1, 5.0, 1.8 Hz, 1H), 7.26
– 7.14 (m, 2H), 3.04 (q, J = 7.2 Hz, 2H), 1.25 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 200.4, 159.8 (d, J = 248.8 Hz), 140.3, 135.9, 130.6 (d, J = 3.2 Hz),
129.9 (d, J = 8.3 Hz), 129.2 (d, J = 3.1 Hz), 128.2, 128.0 (d, J = 13.1 Hz), 124.6 (d, J
= 3.7 Hz), 116.4, 116.2, 31.9, 8.3. IR (cm-1): 3208, 3118, 3050, 1748, 1651, 1522,
1298, 1241, 1009, 945, 771. HRMS (ESI): Calculated for C15H13FONa [M+Na]+:
251.0843, Found: 251.0846.
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4'-hydroxy-[1,1'-biphenyl]-4-carbonitrile (3l):17d According to the general procedure
B, 3l (63 mg) was synthesized in 65% yield from aryl triazenes 1ac (115 mg, 0.5
mmol) with (SnMe3)2 (114 µL, 0.55 mmol), by using BF3·OEt2 (62 µL, 0.5 mmol) in
MeCN (2.5 mL). and Pd (PPh3)4 (29 mg, 5 mol%), 4-bromophbenol (104 mg, 0.6
mmol), K2CO3 (138 mg, 2 equiv.) in toluene (3 mL), The residue was purified by
silica gel column chromatography (Petroleum ether-EtOAc = 10:1): pale yellow solid,
mp 194−196 °C; 1H NMR (400 MHz, CDCl3) δ 7.75 – 7.69 (m, 2H), 7.69 – 7.63 (m,
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2H), 7.52 (d, J = 8.7 Hz, 2H), 6.97 (d, J = 8.6 Hz, 2H); C{1H} NMR (100 MHz,
CDCl3) δ 156.3, 145.2, 132.6, 131.8, 128.6, 127.2, 119.1, 116.1, 110.1. IR (cm-1):
3805, 3202, 2338, 1650, 1542, 1301, 1180, 832. HRMS (ESI): Calculated for
C13H9NONa [M+Na]+: 218.0576, Found: 218.0577.
Typical experimental procedure for mechanism exploration:
In nitrogen atmosphere, aryl triazenes 1a (139 mg, 0.5 mmol), (SnMe3)2 (114 µL,
0.55 mmol) and additive (0.1equiv or 2 equiv) were added to a 10 mL round bottom
flask. Anhydrous MeCN (2.5 mL) was added via syringe and the reaction mixture was
kept at room temperature. Then BF3•OEt2 (63 µL, 0.5 mmol) was added dropwise.
The resulting reaction mixture was allowed to stir for 30 min at room temperature
(TLC confirmed that the reaction was complete). The solution was then concentrated
under reduced pressure and the crude residue was purified by flash column
chromatography over basic alumina to afford corresponding aryl trimethylstannanes
2a as a pale-yellow liquid.
ASSOCIATED CONTENT
Supporting Information
13
1H and C NMR spectra of all synthesized compounds. The Supporting Information
is available free of charge on the ACS Publications website at DOI: xxxxxx
AUTHOR INFORMATION
Corresponding Authors
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*E-mail: lipengfei@mail.xjtu.edu.cn, sqzhang@xjtu.edu.cn. *Fax: (+86)-571-8684-3655.
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Notes
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The authors declare no competing financial interest.
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ACKNOWLEDGMENT
We thank the financial support from the National Nature Science Foundation of China
(Grant Nos. 21602169, 21602202), The China Postdoctoral Science Foundation
(2016M592775) and Xi’an Jiaotong University New Lecturer plan (334100038) for
financial support.
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