Palladium/Norbornene Chemistry: Synthesis of Norbornene-Containing Arylsilanes Involving Double C-Si Bond Formation

Article abstract of DOI:10.1021/acs.joc.8b02282

A novel palladium-catalyzed three-component cascade reaction of aryl halides with norbornene and hexamethyldisilane has been described, which allows the simultaneous construction of two C-Si bonds and one C-C bond. The method achieves ortho C-H functionalization of aryl halides through the formation of the five-membered palladacycle, leading to norbornene-containing arylsilanes.

Full text of DOI:10.1021/acs.joc.8b02282

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Article
Palladium/Norbornene Chemistry: Synthesis of Norbornene-
Containing Arylsilanes Involving Double C-Si Bonds Formation
Yankun Xu, Xiaodong Liu, Wenqi Chen, Guobo Deng, Yun Liang, and Yuan Yang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02282 • Publication Date (Web): 17 Oct 2018
Downloaded from http://pubs.acs.org on October 17, 2018
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Palladium/Norbornene Chemistry: Synthesis of Norbornene-Containing Arylsilanes
Involving Double C-Si Bonds Formation
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Yankun Xu, Xiaodong Liu, Wenqi Chen, Guobo Deng, Yun Liang*, and Yuan Yang*
National & Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of
Resources, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of
Education, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan
Province, Hunan Normal University, Changsha, Hunan 410081, China
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* E-mail: yliang@hunnu.edu.cn. and yangyuan071@126.com.
Supporting Information Placeholder
R1
R1
TMS
X
[Pd]
NBE
Ar
TMS
TMS-TMS
Ar
Ar
PdII
R1
H
X = I, Br
ABSTRACT:
A novel palladium-catalyzed three-component cascade reaction of aryl halides with
norbornene and hexamethyldisilane has been described, which allows the simultaneous
construction of two C-Si bonds and one C-C bond. The method achieves ortho C-H
functionalization of aryl halides through the formation of the five-membered
palladacycle, leading to norbornene-containing arylsilanes.
 INTRODUCTION
Palladium/norbornene chemistry represents an attractive and efficient strategy
and has widely employed in the synthesis of polysubstituted arenes and diverse
heterocycles.1 Among them, considerable efforts have been devoted to the
development of palladium/norbornene-catalyzed ortho C-H functionalization of
aryl iodides (the Catellani reaction; Scheme 1-1).1-4 This type of reaction, which
allows sequential functionalization of both the ortho- and ispo-position of aryl
iodides, was initially found by Catellani,2 and significant progress was made in the
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past two decades by the groups of Catellani,1a,1b Lautens,1c-1e and others.3,4
Generally, the five-membered palladacycle, as the key intermediate of the reaction,
is firstly formed by sequential oxidative addition of Pd(0) to the aryl C-I bond,
insertion of the norbornene, and C-H bond activation. Subsequently, sequential
reaction with electrophiles and nucleophiles gives straightforward access to
polyfunctionalized arenes. Alternatively, palladium-catalyzed ortho C-H
functionalization of aryl iodides using norbornene as reaction substrate has also
been reported.5-8 However, most of efficient transformations have focused on
C-C/C-N bonds formation (Scheme 1-2a)4,5 and multiple C-C bonds formation
(Scheme 1-2b).5,6 Very recently, two papers reported on transformation of C-H
bond toward C-Si bond. Cheng group devoloped a palladium-catalyzed
ortho-silylation of aryl iodides/arylsilylation of oxanorbornadiene reaction for
assembling functionalized (Z)-β-substituted vinylsilanes.9a Zhang group described
a single example of bissilyation of 2-iodoanisole and NBE.15c To date, such
methods for constructing C-Si bond via palladium-catalyzed three-component
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cascade reaction of aryl iodides with norbornene are rather rare.
Scheme 1. Palladium/norbornene chemistry
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(1) Norbornene as catalyst for ortho C-H functionalization of aryl iodides (The Catellani Reaction)
R1
R1
R1
E X
Nu Y
I
+
Nu
E
[Pd(0)]
R2
R2
R2
- norbornene
norbornene
H
PdII
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(2) Norbornene as substrate for ortho C-H functionalization of aryl iodides
(a) C-C bond and C-N bond formation
R4
R3
N
R3
R1
N
I
[Pd]
R2
R2
R2
or
+
+
N source
H
R1
R1
N source = 2-bromoanilines N source = arylamine
or 2-bromosulfoximine
or diaziridinone
R3
(b) Multiple C-C bonds formation
R1
R4
I
[Pd]
R2
R2
or
R2
C source
+
+
H
R1
aryl or alkenyl halides
R1
(c) This work: double C-Si bonds and one C-C bond formation
R1
TMS
Pd(OAc)2 (10 mol %)
X
Ar
TMS
PPh3 (20 mol %)
+
Ar
X = I, Br
+
TMS-TMS
K3PO4 (5 equiv)
CH3CN, N2, 5 h
H
R1
Organosilicon compounds not only are important synthetic intermediates in organic
synthesis, but also have extensive application in medicinal chemistry and materials
science.10-12 Recently, transition-metal-catalyzed C-H silylation has become a powerful
tool for the synthesis of organosilicon compounds.13 Among the reported methods, the
protocol which empolyed hexamethyldisilane as trimethylsilyl source has attracted
tremendous attention.14,15 Based on previous research progress and our ongoing interest
in the cross-coupling reactions involving palladacycles,16 we thought of developing an
efficient palladium/norbornene strategy, which uses hexamethyldisilane as a
trimethylsilyl source to achieve construction of C-Si bond, to assemble functionalized
arylsilanes. Herein, we reported a new palladium-catalyzed three-component cascade
reaction of aryl halides with norbornene and hexamethyldisilane for the synthesis of
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norbornene-containing arylsilanes (Scheme 1-2c).9b
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 RESULTS AND DISCUSSION
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We initially investigated the three-component reaction of 2-iodotoluene 1b with
norbornene and hexamethyldisilane for optimizing the reaction conditions (Table 1).
Delightedly, the norbornene-containing arylsilanes 2b was obtained in a 75% yield in the
presence of 10 mol % of Pd(OAc)2, 20 mol % of PPh3, and 5 equiv of K3PO4 in CH3CN
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o
at 120 C under nitrogen atmosphere (entry 1). Inspired by the result, a range of
palladium catalysts, namely Pd(OCOCF3)2, [PdCl(π-allyl)]2, PdCl2 and Pd(dba)2, were
tested, and all of them displayed catalytic activity, but were less effective than Pd(OAc)2
(entries 2-5). The effect of P-ligands was subsequently screened. We found that
ligand-free and a number of other ligands, including P(o-tolyl)3, S-Phos, Pt-Bu3,
Xantphos, and Dppp, exhibited lower efficiency (entries 7-11). Control experiments
demonstrated that base is essential for the three-component reaction, which could not
occur without base (entry 12). Performing the reaction with other bases, such as K2CO3,
Cs2CO3, KOAc, and LiOt-Bu, resulted in a lower yield (entries 13-16). Finally, solvents
and reaction temperatures were examined, the results showed that the reaction using
o
CH3CN as medium at 110 C prove to be preferential (entries 17-22). Accordingly, the
optimal reaction conditions were as follows: Pd(OAc)2 (10 mol %), PPh3 (20 mol %), and
K3PO4 (5 equiv) in CH3CN at 110 oC under nitrogen atmosphere.
Table 1. Optimization of the Reaction Conditionsa
TMS
I
[Pd], Ligand
Base, Solvent, 120 oC
+
+
TMS-TMS
TMS
2b
H
1b
Entry Catalyst
Ligand
Base
Solvent
Yield
75
62
57
44
1
2
3
4
Pd(OAc)2
PPh3
PPh3
PPh3
PPh3
K3PO4
K3PO4
K3PO4
K3PO4
CH3CN
CH3CN
CH3CN
CH3CN
Pd(OCOCF3)2
[PdCl(π-allyl)]2
PdCl2
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Pd(dba)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PPh3
K3PO4
K3PO4
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
Toluene
DMF
32
40
58
33
32
49
62
ND
41
70
10
15
7
P(o-tol)3 K3PO4
S-Phos
Pt-Bu3
Xantphos K3PO4
K3PO4
K3PO4
10
11
12
13
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15
16
17
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19
20
21b
22c
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Dppp
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
K3PO4
K2CO3
Cs2CO3
KOAc
LiOt-Bu
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
50
5
ND
83
75
DMSO
Dioxane
CH3CN
CH3CN
a
1b (0.1 mmol), NBE (0.2 mmol), TMS-TMS (0.2 mmol), catalyst (10 mol %), ligand (20 mol %),
o
base (0.5 mmol), solvent (1 mL) at 120 C under nitrogen atmosphere for 5 h. Yields of isolated are
given. b 110 oC. c 100 oC.
With the optimal reaction conditions in hand, we turned our attention to
examine the substrate scope of the reaction with regard to aryl iodides 1 (Scheme
2). Iodobenzene 1a was initially investigated, and the desired product 2a was
obtained in 57% yield. Then, a series of substituents, including electron-donating
groups (Et, i-Pr, and OMe) and electron-withdrawing groups (F, Cl, and CF3), at
ortho-position on the aryl ring of aryl iodides were well tolerated under the
standard conditions (2c-h). Other monosubstituted aryl iodides 1i-k with 3-Me,
4-Me, or 4-F group could smoothly be converted into the corresponding products
2i-k in moderate yields. Importantly, disubstituted aryl iodides, such as
1-iodo-2,3-dimethylbenzene
1l,
1-iodo-2,4-dimethylbenzene
1m,
4-fluoro-1-iodo-2-methylbenzene 1n, and 4-chloro-2-fluoro-1-iodobenzene 1o,
proved to be competent substrates, delivering the products 2l-o in 60-89% yields.
The reaction of polycyclic aryl iodides could also afforded the target products in
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57% and 38% yields (2p and 2q), respectively. Notably, norbornene-containing
heteroarylsilanes 2r-t were synthesized in the presence of norbornene,
hexametyldisilane, Pd(OAc)2, PPh3, and K3PO4.
9
Scheme 2. Variation of the Aryliodidesa
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TMS
Pd(OAc)2 (10 mol %)
PPh3 (20 mol %)
I
Ar
Ar
+
TMS-TMS
+
K3PO4 (5 equiv)
CH3CN, N2, 5 h
TMS
H
1
2
1
TMS
2c
2d
2e
, R = Et, 82%
R1
TMS
1
TMS
, R = i-Pr, 64%
1
, R = OMe, 65%
TMS
, R = 3-Me, 62%
1
1
2f
, R = F, 83%
TMS
2i
2j
TMS
R1
1
1
2g
, R = Cl, 82%
2a
, 57%
, R = 4-Me, 63%
1
1
2h
, R = CF3, 81%
2k
, R = 4-F, 51%
TMS
R1
TMS
TMS
Cl
TMS
TMS
TMS
TMS
TMS
, 85%
F
1
2m
, R = Me, 89%
2l
2p
, 57%
2o
, 60%
1
2n
, R = F, 83%
TMS
TMS
TMS
TMS
S
S
N
TMS
2q
TMS
TMS
TMS
, 69%
, 38%
2t
, 56%
2s
2r
, 51%
a
1 (0.2 mmol), NBE (0.4 mmol), TMS-TMS (0.4 mmol), Pd(OAc)2 (10 mol %), PPh3 (20 mol %),
K3PO4 (1 mmol), CH3CN (2 mL) at 110 oC under nitrogen atmosphere for 5 h.
Next, the reaction was applicable to aryl bromides (Scheme 3). Gratifyingly, An
array of aryl bromides bearing electron-donating groups (Me and OMe) or
electron-withdrawing groups (F, Cl, and NO2) were viable for furnishing the
corresponding products in moderate to excellent yields (2b, 2f, 2g, 2u, and 2v). For
bromobenzene 3a, norbornene-containing phenylsilane 2a was also generated in 88%
yield. Furthermore, when 1-bromonaphthalene and 2-bromothiophene were used, the
products 2p and 2r were obtained in decreased yields.
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Scheme 3. Variation of the Arylbromidesa
5
6
7
8
TMS
Pd(OAc)2 (10 mol %)
PPh3 (20 mol %)
Br
H
Ar
Ar
+
+
TMS-TMS
K3PO4 (5 equiv)
CH3CN, N2, 5 h
TMS
9
3
2
10
11
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60
TMS
TMS
TMS
TMS
TMS
TMS
F
TMS
TMS
Cl
2a
, 88%
2b
, 83%
2f
, 90%
2g
, 78%
TMS
TMS
TMS
OMe
TMS
NO2
S
TMS
TMS
, 40%
3 (0.2 mmol), NBE (0.4 mmol), TMS-TMS (0.4 mmol), Pd(OAc)2 (10 mol %), PPh3 (20 mol %),
TMS
TMS
2u
, 70%
2v
2r
, 50%
2p
, 48%
a
K3PO4 (1 mmol), CH3CN (2 mL) at 110 oC under nitrogen atmosphere for 5 h.
Our previous work15e and Zhang’s studies15a simultaneously achieved
bissilyation of the 2 and 2’ position of 2-iodo-1,1’-biphenyls. Therefore,
2-iodo-1,1’-biphenyl 4a was further explored. However, the bissilyation product of
the 2 and 2’ position was not detected, and the corresponding product 5a was
produced in a 69% yield by sequence functionalization of the 2 and 3 position of
2-iodo-1,1’-biphenyl. Encouraged by the result, a wide range of 2-iodobiphenyls
4b-j bearing Me, OMe, F, Cl, or CO2Me group were screened (Scheme 4).
Substrates 4b-d with 5-Me, 5-F, or 5-Cl smoothly be translated into the target
products 5b-5d in good yields. The structure of 5d was unambiguously confirmed
by single-crystal X-ray analysis (CCDC 1872222). When 2-iodobiphenyls with
electron-donating groups (2’-Me and 4’-OMe) were used, the corresponding
products were obtained in 79% and 81% yields (5e and 5f), respectively. In
contrast, 2-iodobiphenyls 4g-i having an electron-withdrawing group (3’-F, 4’-Cl,
or even 4’-CO2Me) delivered the products 5g-i in diminished yields. These results
showed that the electronic nature of substituents on the 1’-phenyl had a significant
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effect on the reactivity. Importantly, with respect to 4-(2-iodophenyl)pyridine 4j,
the desired product 5j was afforded in 57% yield.
7
8
Scheme 4. Variation of the 2-Iodobiphenyls 4 a
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12
13
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15
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60
Ar'
Pd(OAc)2 (10 mol%)
Ar'
PPh3 (20 mol%)
TMS-TMS
+
+
Ar
TMS
Ar
K3PO4 (5 equiv)
CH3CN, N2, 5h
I
TMS
4
5
R1
1
5b
5c
5d
, R = Me, 80%
1
, R = F, 83%
1
TMS
TMS
TMS
, R = Cl, 78%
TMS
TMS
TMS
5a
5e
, 79%
, 69%
F
R2
N
2
5f
, R = OMe, 81%
2
5g
, R = Cl, 60%
2
5h
, R = CO2Me, 35%
TMS
TMS
TMS
TMS
TMS
TMS
5j
, 57%
5i
, 69% (1:1)
a
4 (0.2 mmol), NBE (0.4 mmol), TMS-TMS (0.4 mmol), Pd(OAc)2 (10 mol %), PPh3 (20 mol %),
K3PO4 (1 mmol), CH3CN (2 mL) at 110 oC under nitrogen atmosphere for 5 h.
Finally, we investigated the reactivity of 2-bromobiphenyls (Scheme 5). The
experimental results demonstrated that 2-bromobiphenyls exhibited similar
reactivity comparing with 2-iodobiphenyls. Both 2-bromo-1,1’-biphenyl and
substituted 2-bromobiphenyls with Me, OMe, F, or Cl could react with norbornene
and hexamethyldisilane, furnishing the desired products in 25-81% yields (5a-c,
5f, and 5g).
Scheme 5. Variation of the 2-Bromobiphenyls 6 a
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7
Ar'
Pd(OAc)2 (10 mol %)
PPh3 (20 mol %)
Ar'
+
Ar
TMS
Ar
K3PO4 (5 equiv)
CH3CN, N2, 5 h
TMS-TMS
Br
8
TMS
9
6
5
10
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R2
R1
TMS
TMS
TMS
TMS
TMS
TMS
1
2
5b
5c
, R = Me, 80%
5f
, R = OMe, 81%
5a
, 79%
1
2
, R = F, 73%
5g
, R = Cl, 25%
a
6 (0.2 mmol), NBE (0.4 mmol), TMS-TMS (0.4 mmol), Pd(OAc)2 (10 mol %), PPh3 (20 mol %),
K3PO4 (1 mmol), CH3CN (2 mL) at 110 oC under nitrogen atmosphere for 5 h.
Further utilization of the products 2a and 5a was carried out, and the corresponding
products 7 and 8 were afforded in excellent yields through selective iodination (Scheme
6, eq 1 and 2).17 Notably, the reaction scale up to 5 mmol of 6a could also give the
product 5a in a 76% yield (Scheme 6, eq 3).
Scheme 6. Utilization of the Products and Gram-Scale Experiment
I
TMS
ICl (2.2 equiv)
CH2Cl2, rt
(1)
TMS
TMS
(0.2 mmol)
2a
7,
93%
ICl (2.2 equiv)
CH2Cl2, rt
(2)
TMS
(0.2 mmol)
TMS
96%
I
5a
8,
H
Pd(OAc)2 (10 mol %)
PPh3 (20 mol %)
(3)
TMS
+
K3PO4 (5 equiv)
CH3CN, N2, 5 h
TMS-TMS
Br
(5 mmol)
TMS
6a
5a
, 76%
A possible mechanism is proposed on the basis of the previous reports and
present results (Scheme 7). Firstly, the intermediate A is formed by sequential
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oxidation addition of Pd(0) to C-X bond and migration insertion of norbornene.
Next, intermediate A undergoes intramolecular ortho C-H activation to afford the
five-membered palladacycle B, which produces the intermediate C through the
oxidative addition to hexamethyldisilane (path a). Subsequently, the first reductive
elimination of intermediate C gives the intermediate D. Finally, intermediate D
undergoes the second reductive elimination to furnish products 2 and 5 and
regenerate Pd(0). Furthermore, the sigma bond metathesis pathway involving
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intermediate F cannot be ruled out (path b).
Scheme 7. Possible Reaction Mechanism
R1
2 or 5
Pd0
X
NBE
R1
R1
PdII
TMS
TMS
R1
PdIIX
D
A
PdII
TMS
TMS
R1
R1
F
path b
PdIV
TMS
PdII
B
TMS
path a
C
TMS-TMS
 CONCLUSION
In summary, this research reported the synthesis of diverse
norbornene-containing arylsilanes from aryl halides, norbornene, and
hexamethyldisilane via a palladium-catalyzed three-component cascade reaction.
The method gave straightforward access to norbornene-containing arylsilanes with
good functionalization tolerance in moderate to excellent yields. In the
transformation, three chemical bonds, including two C-Si bonds and one C-C
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bond, were constructed. Further application of the method are currently underway
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in our laboratory.
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 Experimental Section
1
13
General Information. H NMR, C{1H} NMR and spectra were recorded on a Bruker
400 MHz or 500 MHz advance spectrometer at room temperature in CDCl3 with
tetramethylsilane as internal standard. Chemical shifts (δ) are reported in ppm, and
coupling constants (J) are in Hertz (Hz). Multiplicities are reported using the following
abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet.
High-resolution mass spectra (HRMS) were recorded on an Agilent 1290 or GCT
primierr Mass spectrometer using ESI-TOF or EI (electrospray ionizationtime of flight).
Reactions were monitored by thin-layer chromatography Column chromatography
(petroleum ether/ethyl acetate) was performed on silica gel (200-300 mesh). Analytical
grade solvents and commercially available reagents were purchased from commercial
sources and used directly without further purification unless otherwise stated.
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Typical Experimental Procedure for the Synthesis 2-iodobiphenyls.15e,18a
A 100 mL schlenk tube was charged with substituted 2-iodoaniline (3.0 mmol, 1 equiv),
substituted phenylboronic acid (3.9 mmol, 1.3 equiv), Pd(OAc)2, (0.15 mmol, 0.05 equiv),
dppf (0.3 mmol, 0.1 equiv), Na2CO3 (12.0 mmol, 4 equiv), 1,4-dioxane (15.0 mL) and
o
water (6.0 mL). The mixture was heated in an oil bath at 65 C overnight. After the
completion of the reaction, it was allowed to attain to room temperature, then the reaction
mixture was filtered and the filtrate diluted in ethyl acetate, and washed with water. The
combined organic layers were dried over anhydrous Na2SO4 and evaporated under
vacuum. The crude product was purified by silica gel column chromatography (petroleum
ether/EtOAc) to give the corresponding substituted 2-aminobiphenyls.
A solution of concn HCl (36-38%; 2.7 mmol, 1.35 equiv, 1mL) in water (4 mL) was
o
added slowly to the prepared 2-aminobiphenyl (2.0 mmol, 1 equiv) at 0 C in portions.
o
After stirring for 1 h at 0 C, the aqueous solution of NaNO2 (3.0 mmol, 1.5 equiv) was
added to the reaction mixture below 5 °C within 10 min and stirred for 1 h. Then an
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aqueous solution of KI (4.0 mmol, 2 equiv) in water (4 mL) was added and the reaction
mixture was stirred at room temperature overnight. After the completion of the reaction,
saturated aqueous NaHCO3 was added to neutralize the acid and adjust the solution to
pH > 7. Then the residue was extracted into ethyl acetate (3×5 mL). The combined
organic phases were dried over anhydrous Na2SO4 and concentrated in vacuo. The crude
product was purified by silica gel column chromatography (petroleum ether unless
otherwise noted) to give the desired 2-iodobiphenyls.
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Typical Experimental Procedure for the Synthesis 2-Bromobiphenyls.18b
A 25 mL schlenk tube was charged with substituted 1-bromo-2-iodobenzene (1.0 mmol,
1 equiv), substituted phenylboronic acid (1.05 mmol, 1.05 equiv), PdCl2(PPh3)2 (0.015
mmol, 0.015 equiv), K2CO3 (2.5 mmol, 2.5 equiv), DME (3 mL) and water (0.4 mL). The
mixture was heated in an oil bath at 80 oC for 5 h. After the completion of the reaction, it
was allowed to cool to r.t., DME was evaporated, and water (12 mL) and ether (8 mL)
were added. The layers were separated and the aqueous layer was extracted with
diethylether (3 x 8 mL). The combined organic layers were washed with brine, dried over
magnesium sulfate, filtered, and evaporated in vacuo. The crude product was purified by
silica gel column chromatography (petroleum ether unless otherwise noted) to give
2-Bromobiphenyls.
Typical Experimental Procedure for the Synthesis of 2 or 5. To a Schlenk tube were
added Aryl halides (0.2 mmol, 1equiv), hexamethyldisilane (0.4 mmol, 2 equiv, 58.5
mg), norbornene (0.4 mmol, 2 equiv, 37.6 mg), Pd(OAc)2 (0.02 mmol, 0.1 equiv, 4.5 mg),
PPh3 (0.04 mmol, 0.2 equiv, 10.5 mg), K3PO4 (1.0 mmol, 5 equiv, 212.3 mg) and CH3CN
o
(2 mL). Then the tube was charged with nitrogen, and was stirred at 110 C (oil bath
temperature) for the indicated time until complete consumption of starting material as
monitored by TLC analysis. After the completion of the reaction, the resulting suspension
was filtered and washed with ethyl acetate. The combined filtrates were concentrated
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under reduced pressure and purified on a silica-gel column chromatography (petroleum
ether/ethyl acetate) to give the desired products 2 or 5.
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trimethyl(2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)silane
(2a) (1a: 36 mg, 57%; 3a: 55.7 mg, 88%) was prepared according to the typical
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procedure (petroleum ether) as a colorless oil. H NMR (500 MHz, CDCl3, δ ppm)
7.42-7.40 (m, 2H), 7.33-7.29 (m, 1H), 7.17-7.14 (m, 1H), 3.17 (d, J = 10.5 Hz, 1H), 2.36
(dd, J = 3.5 Hz, 11.0 Hz, 2H), 1.99 (d, J = 10.0 Hz, 1H), 1.80-1.75 (m, 1H), 1.64-1.59 (m,
1H), 1.46-1.41 (m, 1H), 1.39-1.34 (m, 2H), 1.29-1.27 (m, 1H), 0.34 (s, 9H), -0.35 (s, 9H).
13C{1H} NMR (125 MHz, CDCl3, δ ppm) 152.7, 138.9, 134.2, 129.2, 126.6, 125.1, 51.1,
+
44.9, 43.5, 38.9, 38.5, 32.8, 32.2, 1.0, -0.8. HRMS (ESI-TOF) m/z calcd for C19H33Si2
(M+H)+ 317.2115, found 317.2116.
trimethyl(3-methyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)si
lane (2b) (1b: 54.7 mg, 83%; 3b: 54.7 mg, 83%) was prepared according to the typical
procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.40 (d,
J = 5.0 Hz, 1H), 7.14-7.10 (m, 2H), 3.53 (d, J = 11.0 Hz, 1H), 2.75 (s, 1H), 2.56 (s, 3H),
2.42 (s, 1H), 2.04 (d, J = 9.5 Hz, 1H), 1.91-1.85 (m, 1H), 1.67-1.54 (m, 2H), 1.48 (d, J =
11.0 Hz, 1H), 1.45-1.38 (m, 2H), 0.41 (s, 9H), -0.34 (s, 9H). C{1H} NMR (125 MHz,
13
CDCl3, δ ppm) 148.5, 142.1, 135.2, 134.2, 133.1, 125.4, 53.9, 44.9, 41.0, 39.8, 38.9, 33.5,
32.2, 23.1, 2.1, -0.6. HRMS (EI) m/z calcd for C20H34Si2 (M)+ 330.2199, found
+
330.2196.
(3-ethyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethylsila
ne (2c) (56.5 mg, 82%) was prepared according to the typical procedure (petroleum ether)
1
as a colorless oil. H NMR (500 MHz, CDCl3, δ ppm) 7.35-7.34 (m, 1H), 7.18-7.17 (m,
1H), 7.15-7.12 (m, 1H), 3.47 (d, J = 11.0 Hz, 1H), 3.16-3.09 (m, 1H), 2.63-2.56 (m, 2H),
2.38 (s, 1H), 2.01 (d, J = 9.5 Hz, 1H), 1.87-1.82 (m, 1H), 1.61-1.56 (m, 1H), 1.53-1.49
(m, 1H), 1.43 (d, J = 11.0 Hz, 1H), 1.40-1.36 (m, 2H), 1.24-1.21 (m, 3H), 0.36 (s, 9H),
-0.42 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) δ 147.7, 142.3, 141.9, 133.0,
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131.9, 125.5, 53.6, 45.2, 41.7, 40.2, 38.8, 33.8, 31.9, 27.1, 17.3, 2.2, -0.8. HRMS (EI)
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+
m/z calcd for C21H36Si2 (M)+ 344.2356, found 344.2356.
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(3-isopropyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimeth
ylsilane (2d) (46 mg, 64%) was prepared according to the typical procedure (petroleum
ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.37-7.31 (m, 2H), 7.18-7.14
(m, 1H), 3.60-3.52 (m, 2H), 2.68 (s, 1H), 2.39 (s, 1H), 1.97 (d, J = 12.0 Hz, 1H),
1.88-1.82 (m, 1H), 1.59 (m, 1H), 1.53-1.47 (m, 2H), 1.40 (d, J = 12.0 Hz, 2H), 1.34 (d, J
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= 8.0 Hz, 3H), 1.22 (d, J = 7.5 Hz, 3H), 0.38 (s, 9H), -0.36 (s, 9H). C{1H}NMR (125
MHz, CDCl3, δ ppm) 147.4, 147.1, 142.5, 133.2, 128.0, 125.6, 53.8, 44.5, 42.0, 40.5, 39.2,
+
34.0, 31.9, 28.3, 27.9, 23.5, 2.4, -0.8. HRMS (EI) m/z calcd for C22H38Si2 (M)+
358.2512, found 358.2511
(3-methoxy-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethyl
silane (2e)12c (45 mg, 65%) was prepared according to the typical procedure (petroleum
ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.18-7.15 (m, 1H), 7.07 (d, J
= 7.0 Hz, 1H), 6.85 (d, J = 8.0 Hz, 1H), 3.74 (s, 3H), 3.22 (d, J = 10.5 Hz, 1H), 2.45 (m,
1H), 2.33 (m, 1H), 2.26 (d, J = 9.5 Hz, 1H), 1.83-1.78 (m, 1H), 1.56-1.51 (m, 1H),
1.44-1.40 (m, 1H), 1.34-1.27 (m, 2H), 1.18 (d, J = 9.0 Hz, 1H), 0.35 (s, 9H), -0.39 (s, 9H).
13C{1H} NMR (125 MHz, CDCl3, δ ppm) 157.8, 142.3, 138.4, 126.8, 126.5, 112.2, 53.9,
+
51.6, 44.0, 42.6, 39.2, 38.7, 33.1, 32.7, 1.5, -0.9. HRMS (EI) m/z calcd for C20H34OSi2
(M)+ 346.2148, found 358.2150.
(3-fluoro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethylsil
ane (2f) (1f: 55.5 mg, 83%; 3f: 60.2 mg, 90%) was prepared according to the typical
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procedure (petroleum ether) as a colorless oil. H NMR (400 MHz, CDCl3, δ ppm) 7.26
(d, J = 7.2 Hz, 1H), 7.20-7.15 (m, 1H),7.04-7.00 (m, 1H), 3.24 (d, J = 10.4 Hz, 1H), 2.52
(s, 1H), 2.41 (s, 1H), 2.20 (d, J = 9.2 Hz, 1H), 1.87-1.82 (m, 1H), 1.67-1.61 (m, 1H),
1.48-1.43 (m, 1H), 1.36-1.26 (m, 2H), 1.27 (d, J = 10.0 Hz, 1H), 0.39 (s, 9H), -0.30 (s,
9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) δ 161.3 (d, J = 246.4 Hz), 143.6 (d, J= 3.0
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Hz), 137.0 (d, J = 12.1 Hz),130.2 (d, J = 2.7 Hz), 127.1 (d, J = 7.9 Hz), 117.6 (d, J = 24.7
Hz), 50.1, 44.0, 42.8, 39.3, 38.2 (d, J = 14.8 Hz), 33.0, 32.5 (d, J = 1.6 Hz), 1.3, -1.0 (d, J
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+
= 1.0 Hz). HRMS (EI) m/z calcd for C19H31FSi2 (M)+ 334.1948, found. 334.1951.
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(3-chloro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethylsi
lane (2g) (1g: 57.5 mg, 82%; 3g: 54.6 mg, 78%) was prepared according to the typical
procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.38 (d,
J = 7.5Hz, 1H), 7.31 (d, J = 7.5Hz, 1H), 7.10-7.07 (m, 1H), 3.42 (d, J = 11.0 Hz, 1H),
2.82 (s, 1H), 2.39-2.35 (m, 2H), 1.87-1.83 (m, 1H), 1.62-1.57 (m, 1H), 1.46-1.40 (m, 2H),
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1.38-1.34 (m, 1H), 1.32 (d, J = 10.0 Hz, 1H), 0.37 (s, 9H), -0.33 (s, 9H). C{1H} NMR
(125 MHz, CDCl3, δ ppm) 147.0, 145.0, 133.5, 133.0, 132.9, 126.7, 53.3, 45.1, 41.2, 40.1,
+
38.9, 33.3, 32.4, 1.8, -0.7. HRMS (EI) m/z calcd for C19H31ClSi2 (M)+ 350.1653, found
350.1652.
trimethyl(3-(trifluoromethyl)-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)p
henyl)silane (2h) (62.2 mg, 81%) was prepared according to the typical procedure
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(petroleum ether) as a colorless oil. H NMR (400 MHz, CDCl3, δ ppm) 7.71 (d, J = 7.6
Hz, 2H), 7.26 (t, J = 7.6 Hz, 1H), 3.66 (d, J = 11.2 Hz, 1H), 2.37 (s, 1H), 2.89 (s, 1H),
1.99 (d, J = 10.0 Hz, 1H), 1.82 (d, J = 11.6 Hz, 1H), 1.62-1.58 (m, 1H), 1.52 (d, J = 11.6
Hz, 1H), 1.48-1.43 (m, 1H), 1.39-1.34 (m, 1H), 1.25 (d, J = 10.0 Hz, 1H), 0.41 (s, 9H),
-0.41 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 150.0, 146.0, 139.1, 128.6 (q, J =
7.4 Hz), 127.8 (d, J = 30.2 Hz), 125.2, 124.7 (q, J = 271.0 Hz), 54.4, 44.9, 41.5 (q, J =
5.0 Hz), 39.3, 38.9 (q, J = 15.6 Hz), 34.3, 31.7, 2.4, -0.8. HRMS (EI) m/z calcd for
+
C20H31F3Si2 (M)+ 384.1916, found. 384.1917.
trimethyl(4-methyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)si
lane (2i) (41 mg, 62%) was prepared according to the typical procedure (petroleum ether)
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as a white solid. mp: 86.8-93.0 °C. H NMR (500 MHz, CDCl3, δ ppm) 7.32 (d, J = 7.5
Hz, 1H), 7.22 (s, 1H), 6.99 (d, J = 7.5 Hz, 1H), 3.16 (d, J = 10.5 Hz, 1H), 2.37-2.34 (m,
5H), 2.02 (d, J = 10.0 Hz, 1H), 1.80-1.76 (m, 1H), 1.64-1.59 (m, 1H), 1.46-1.36 (m, 3H),
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1.28 (d, J = 10.0 Hz, 1H), 0.33 (s, 9H), -0.35 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3,
δ ppm) 152.8, 138.8, 135.6, 134.3, 127.7, 125.9, 51.0, 44.9, 43.6, 39.0, 38.5, 32.8, 32.2,
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+
21.4, 1.0, -0.8. HRMS (EI) m/z calcd for C20H34Si2 (M)+ 330.2199, found 330.2195
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lane (2j) (41.6 mg, 63%) was prepared according to the typical procedure (petroleum
ether) as a colorless oil. 1H NMR (500 MHz, CDCl3，δ ppm) 7.30 (d, J = 8.0 Hz, 1H), 7.21
(s, 1H), 7.12 (d, J = 7.5 Hz, 1H), 3.14 (d, J = 10.0 Hz, 1H), 2.36-2.32 (m, 5H), 1.98 (d, J
= 9.5 Hz, 1H), 1.79-1.74 (m, 1H), 1.63-1.57 (m, 1H), 1.45-1.40 (m, 1H), 1.37-1.35 (m,
2H), 1.27-1.25 (m, 1H), 0.34 (s, 9H), -0.34 (s, 9H). 13C{1H} NMR (125 MHz，CDCl3，δ
ppm)149.7, 138.7, 134.8, 134.1, 130.0, 126.5, 50.7, 45.0, 43.5, 38.8, 38.5, 32.8, 32.1,
+
21.1, 1.0, -0.7. HRMS (EI) m/z calcd for C20H34Si2 (M)+ 330.2199, found 330.2196.
(5-fluoro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethylsil
ane (2k) (34 mg, 51%) was prepared according to the typical procedure (petroleum ether)
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as a colorless oil. H NMR (500 MHz, CDCl3,δ ppm) 7.36-7.34 (m, 1H), 7.08-7.07 (m,
1H), 6.98-6.95 (m, 1H), 3.13 (d, J = 10.5 Hz, 1H), 2.36 (s, 1H), 2.28 (s, 1H), 1.93 (d, J =
10.0 Hz, 1H), 1.78-1.73 (m, 1H), 1.63-1.58 (m, 1H), 1.43-1.26 (m, 4H), 0.33 (s, 9H),
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-0.35 (s, 9H). C{1H} NMR (125 MHz, CDCl3,δ ppm) δ 160.7 (d, J = 244.3 Hz), 148.4
(d, J = 2.8 Hz), 141.9 (d, J= 2.8 Hz), 128.0 (d, J = 6.3 Hz), 120.2 (d, J = 17.9 Hz), 115.6
(d, J = 21.1 Hz), 50.4, 45.0, 43.5, 38.7, 38.6, 32.7, 32.1, 0.7, -0.7. HRMS (ESI) m/z calcd
+
for C19H31FSi2 (M)+ 334.1948, found 334.1950.
(3,4-dimethyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimeth
ylsilane (2l) (58.6 mg, 85%) was prepared according to the typical procedure (petroleum
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ether) as a colorless oil. H NMR (400 MHz, CDCl3, δ ppm) 7.27 (d, J = 7.2 Hz, 1H),
7.03 (d, J = 7.2 Hz, 1H), 3.52 (d, J = 10.8 Hz, 1H), 2.74 (s, 1H), 2.40 (s, 4H), 2.28 (s, 3H),
2.05 (d, J = 9.6 Hz, 1H), 1.87 (t, J = 11.6 Hz, 1H), 1.62-1.61 (m, 1H), 1.55-1.50 (m, 1H),
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1.7-1.39 (m, 3H), 0.37 (s, 9H), -0.39 (s, 9H). C{1H} NMR (100 MHz, CDCl3, δ ppm)
148.5, 139.7, 139.6, 134.4, 132.8, 127.3, 54.1, 45.1, 42.0, 40.1, 38.9, 33.6, 32.3, 21.4,
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17.7, 2.1, -0.7. HRMS (EI) m/z calcd for C21H36Si2 (M)+ 344.2356, found 344.2357.
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(3,5-dimethyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimet
hylsilane (2m) (61.3 mg, 89%) was prepared according to the typical procedure
(petroleum ether) as a colorless oil. 1H NMR (400 MHz, CDCl3, δ ppm) 7.11 (s, 1H), 6.88
(s, 1H), 3.43-3.41 (d, J = 10.8 Hz, 1H), 2.63 (s, 1H), 2.44 (s, 3H), 2.33 (s, 1H), 2.24 (s,
3H), 1.95 (d, J = 10.0 Hz, 1H), 1.83-1.77 (m, 1H), 1.59-1.53 (m, 1H), 1.48-1.43 (m, 1H),
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1.40 (d, J = 11.2 Hz, 1H), 1.35-1.28 (m, 2H), 0.32 (s, 9H), -0.40 (s, 9H). C{1H} NMR
(100 MHz, CDCl3, δ ppm) 145.4, 141.9, 134.9, 134.8, 134.3, 133.8, 53.3, 44.9, 41.1, 39.7,
+
38.8, 33.5, 32.2, 23.0, 20.7, 2.1, 0.6. HRMS (EI) m/z calcd for C21H36Si2 (M)+ 344.2356,
found 344.2356.
((1R,2S,3S,4S)-3-(4-fluoro-2-methyl-6-(trimethylsilyl)phenyl)bicyclo[2.2.1]heptan-2-yl)tr
imethylsilane (2n) (57.9 mg, 83%) was prepared according to the typical procedure
1
(petroleum ether) as a colorless oil. H NMR (500 MHz, CDCl3, δ ppm) 7.03 (d, J = 9.0
Hz, 1H), 6.79 (d, J = 9.0 Hz, 1H), 3.45 (d, J = 11.0 Hz, 1H), 2.65 (s, 1H), 2.50 (s, 3H),
2.37 (s, 1H), 1.96 (d, J = 9.5 Hz, 1H), 1.86-1.82 (m, 1H), 1.61-1.57 (m, 1H), 1.48-1.46
(m, 1H), 1.42 (d, J = 11.0 Hz, 1H), 1.35-1.34 (m, 2H), 0.36 (s, 9H), -0.35 (s, 9H).
13C{1H} NMR (125 MHz, CDCl3, δ ppm) 160.6 (d, J = 244.5 Hz), 145.1 (d, J = 2.6 Hz),
144.2 (d, J = 2.6 Hz), 137.6 (d, J = 2.5 Hz), 119.8 (d, J = 19.8 Hz), 119.1 (d, J = 18.1 Hz),
53.1, 45.0, 41.1, 39.8, 38.9, 33.5, 32.2, 23.1, 1.8, -0.6. HRMS (EI) m/z calcd for
+
C20H33FSi2 (M+H)+ 348.2105, found 348.2101.
((1R,2S,3S,4S)-3-(4-chloro-2-fluoro-6-(trimethylsilyl)phenyl)bicyclo[2.2.1]heptan-2-yl)tr
imethylsilane (2o) (44.5 mg, 60%) was prepared according to the typical procedure
1
(petroleum ether) as a colorless oil. H NMR (500 MHz, CDCl3, δ ppm) 7.18 (d, J = 2.0
Hz, 1H), 7.02 (dd, J = 1.5 Hz, 11.5 Hz, 1H), 3.16 (d, J = 11.0 Hz, 1H), 2.43-2.37 (m,
2H), 2.09 (d, J = 9.5 Hz, 1H), 1.81-1.77 (m, 1H), 1.62-1.57 (m, 1H), 1.41-1.37 (m, 1H),
13
1.33-1.26 (m, 2H), 1.22 (d, J = 10.0 Hz, 1H), 0.35 (s, 9H), -0.32 (s, 9H). C{1H} NMR
(125 MHz, CDCl3, δ ppm) 161.0 (d, J = 250.9 Hz), 145.5 (d, J = 3.8 Hz),, 135.6 (d, J =
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12.7 Hz), 131.9 (d, J = 9.0 Hz), 130.0 (d, J= 2.6 Hz), 117.8 (d, J = 28.1 Hz), 49.7 (d, J =
1.5Hz), 44.0, 42.7 (d, J = 1.4 Hz), 39.2, 38.2 (d, J = 14.2 Hz), 33.0, 32.4, 1.0, -0.9.
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HRMS (EI) m/z calcd for C19H30ClFSi2 (M)+ 368.1559, found 368.1550.
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trimethyl(1-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)naphthalen-2-yl)si
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lane (2p) (1p: 41.8 mg, 57%; 3p: 35,2 mg, 48%) was prepared according to the typical
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procedure (petroleum ether) as a white solid. mp: 77.2-79.5 °C. H NMR (500 MHz,
CDCl3, δ ppm) 8.65 (d, J = 7.5 Hz, 1H), 7.82 (d, J = 7.0 Hz, 1H), 7.70 (d, J = 8.0 Hz, 1H),
7.59 (d, J = 8.0 Hz, 1H), 7.45-7.44 (m, 2H), 3.85 (d, J = 11.0 Hz, 1H), 3.10 (s, 1H), 2.48
(s, 1H), 2.37 (d, J = 9.0 Hz, 1H), 1.98-1.93 (m, 1H), 1.73-1.72 (m, 1H), 1.64-1.62 (m,
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1H),. 1.60-1.58 (m, 1H), 1.49-1.47 (m, 2H), 0.46 (s 9H), -0.68 (s, 9H), C{1H} NMR
(125 MHz, CDCl3, δ ppm) 148.4, 139.0, 135.3, 132.4, 131.4, 128.6, 126.7, 126.1, 125.5,
124.4, 54.2, 45.7, 42.7, 40.4, 39.3, 34.0, 32.2, 2.1, -1.0. HRMS (EI) m/z calcd for
+
C23H34Si2 (M)+ 366.2199, found 366.2196.
trimethyl(3-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)naphthalen-2-yl)si
lane (2q) (27.8 mg, 38%) was prepared according to the typical procedure (petroleum
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ether) as a colorless oil. H NMR (500 MHz, CDCl3, δ ppm) 7.94 (s, 1H), 7.8 (s, 1H),
7.80 (d, J = 8.0 Hz, 1H), 7.76 (d, J = 8..0 Hz, 1H), 7.48-7.40 (m, 2H), 3.30 (d, J = 10.0
Hz, 1H), 2.47 (dd, J = 3.0 Hz, 11.0 Hz, 2H), 2.20 (d, J = 10.0 Hz, 1H), 1.84-1.79 (m, 1H),
1.70-1.64 (m, 1H), 1.52-1.46 (m, 2H), 1.43-1-1.40 (m, 1H), 1.38 (dd, J = 2.0 Hz, 10.5 Hz,
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1H), 0.44 (s, 9H), -0.39 (s, 9H). C{1H} NMR (125 MHz, CDCl3, δ ppm) 149.7, 138.8,
134.7, 133.9, 131.3, 127.8, 127.1, 126.3, 125.0, 124.7, 51.0, 45.5, 44.0, 39.0, 38.7, 32.8,
+
32.2, 1.0, -0.7. HRMS (EI) m/z calcd for C23H34Si2 (M)+ 366.2199, found 366.2194.
trimethyl(2-((1S,2R,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)thiophen-3-yl)sila
ne (2r) (1r: 33.0 mg, 51%; 3r: 25.8 mg, 40%) was prepared according to the typical
1
procedure (petroleum ether) as a colorless oil. H NMR (500 MHz, CDCl3, δ ppm) 7.11
(d, J = 5.0 Hz, 1H), 6.90 (d, J = 4.5 Hz, 1H), 3.50 (d, J = 10.0 Hz, 1H), 2.31 (d, J = 19.0
Hz, 2H), 1.90 (d, J = 9.5 Hz, 1H), 1.71-1.69 (m, 1H), 1.66-1.63 (m, 1H), 1.38-1.33 (m,
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3H), 1.20 (d, J = 10.0 Hz, 1H), 0.29 (s, 9H), -0.23 (s, 9H). 13C{1H} NMR (125MHz,
CDCl3, δ ppm) 157.9, 135.7, 131.4, 121.9, 48.3, 46.1, 41.9, 39.0, 37.6, 32.7, 31.2, 0.5,
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-1.1. HRMS (ESI-TOF) m/z calcd for C17H31SSi2 (M+H)+ 323.1680, found 323.1684.
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trimethyl(3-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)thiophen-2-yl)sila
ne (2s) (44.5 mg, 69%) was prepared according to the typical procedure (petroleum ether)
as a colorless oil. 1H NMR (400 MHz, CDCl3, δ ppm) 7.46 (d, J = 4.4 Hz, 1H), 7.19 (d, J
= 4.4 Hz, 1H), 3.23 (d, J = 10.0 Hz, 1H), 2.36 (s, 1H), 2.25 (s, 1H), 1.89 (d, J = 9.6 Hz,
1H), 1.75-1.72 (m, 1H), 1.66-1.63 (m, 1H), 1.39-1.31 (m, 3H), 1.19 (d, J = 10.4 Hz, 1H),
0.36 (s, 9H), -0.28 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 154.1, 133.2, 129.7,
128.5, 47.4, 44.2, 41.7, 38.8, 37.8, 32.9, 31.7, 0.7, -0.9. HRMS (ESI-TOF) m/z calcd for
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C17H31SSi2 (M+H)+ 323.1680, found 323.1681.
6-(trimethylsilyl)-5-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)quinoline
(2t) (44.2 mg, 56%) was prepared according to the typical procedure (petroleum
ether/ethyl acetate = 5:1) as a yellow solid. mp: 99.0-101 °C. 1H NMR (500 MHz, CDCl3,
δ ppm) 8.98 (d, J = 8.5 Hz, 1H), 8.86 (dd, J = 1.5 Hz, 4 Hz, 1H), 7.95 (d, J = 8.5 Hz, 1H),
7.80 (d, J = 8.5 Hz, 1H), 7.34-7.31 (m, 1H), 3.83 (d, J = 11.0 Hz, 1H), 3.00 (s, 1H), 2.47
(d, J = 4.0 Hz, 1H), 2.22 (d, J = 9.5 Hz, 1H), 1.96-1.89 (m, 1H), 1.73-1.67 (m, 1H),
13
1.62-1.56 (m, 2H), 1.48-1.42 (m, 2H), 0.43 (s, 9H), -0.71 (s, 9H). C{1H} NMR (125
MHz, CDCl3, δ ppm) 149.8, 149.7, 140.0, 135.0, 134.8, 127.3, 127.1, 119.2, 53.8, 45.6,
+
42.8, 40.4, 39.4, 33.9, 32.1, 1.9, -1.0. HRMS (ESI-TOF) m/z calcd for C22H34NSi2
(M+H)+ 368.2224, found 368.2227.
(5-methoxy-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethyl
silane (2u) (48.5 mg, 70%) was prepared according to the typical procedure (petroleum
ether/ethyl acetate = 100:1) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.33 (d,
J = 9.0 Hz, 1H), 6.97 (d, J = 3.0 Hz, 1H), 6.85 (dd, J = 3.0 Hz, 9.0 Hz, 1H), 3.80 (s, 3H ),
3.13 (d, J = 10.5 Hz, 1H), 2.37 (d, J = 3.5 Hz, 1H), 2.29 (d, J = 2.5 Hz, 1H), 1.96 (d, J =
9.5 Hz, 1H), 1.79-1.73 (m, 1H), 1.64-1.58 (m, 1H), 1.44-1.40 (m, 1H), 1.37-1.32 (m, 2H),
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1.26 (dd, J = 1.5 Hz, 10.5 Hz, 1H), 0.34 (s, 9H), -0.33 (s, 9H). 13C{1H} NMR (125 MHz,
CDCl3, δ ppm) 156.9, 145.0, 140.5, 127.6, 119.9, 113.8, 55.1, 50.3, 45.1, 43.5, 38.7, 38.6,
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32.8, 32.1, 0.9, -0.7. HRMS (EI) m/z calcd for C20H34OSi2 (M)+ 346.2148, found
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346.2151.
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trimethyl(5-nitro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)sila
ne (2v) (36.2 mg, 50%) was prepared according to the typical procedure (petroleum
ether/ethyl acetate = 200:1) as a yellow solid. mp: 107.4-112.1 °C.1H NMR (400 MHz,
CDCl3, δ ppm) 8.25 (s, 1H), 8.13 (d, J = 8.8 Hz, 1H), 7.54 (d, J = 8.4 Hz, 1H), 3.25 (d, J
= 10.4 Hz, 1H), 2.40 (s, 1H), 2.32 (s, 1H), 1.95 (d, J = 10.0 Hz, 1H), 1.82-1.76 (m, 1H),
1.67-1.64 (m, 1H), 1.44-1.36 (m, 3H), 1.31 (d, J = 10.4 Hz, 1H), 0.39 (s, 9H), -0.35 (s,
13
9H). C{1H} NMR (100MHz, CDCl3, δ ppm) 160.7, 145.5, 141.7, 128.8, 127.4, 124.1,
51.4, 45.0, 43.5, 38.9, 38.6, 32.6, 32.1, 0.6, -0.7. HRMS (ESI-TOF) m/z calcd for
C19H31NO2Si2Na+ (M+Na)+ 384.1786, found 384.1783.
trimethyl((1R,2S,3S,4S)-3-(2'-(trimethylsilyl)-[1,1'-biphenyl]-2-yl)bicyclo[2.2.1]heptan-2
-yl)silane
trimethyl((1R,2S,3S,4S)-3-(3-(trimethylsilyl)-[1,1'-biphenyl]-2-yl)bicyclo[2.2.1]heptan-2-
yl)silane (5a) (4a: 54.2 mg, 69%; 6a: 62.0 mg, 79%) ) was prepared according to the
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typical procedure (petroleum ether) as a white solid. mp: 87.9-91.0 °C. H NMR (500
MHz, CDCl3, δ ppm) 7.51 (d, J = 7.0 Hz, 1H), 7.42 (d, J = 7.0 Hz, 1H), 7.38-7.30 (m,
3H), 7.28-7.26 (m, 1H), 7.17-7.14 (m, 1H), 7.03 (d, J = 7.0 Hz, 1H), 3.58 (d, J = 11.0 Hz,
1H), 2.65 (s, 1H), 2.00 (s, 1H), 1.63-1.58 (m, 1H), 1.49-1.44 (m, 1H), 1.35 (d, J = 11.0
Hz, 1H), 1.30-1.23 (m, 2H), 0.54 (d, J = 9.5 Hz, 1H), 0.42, (s, 9H), 0.35 (d, J = 9.0 Hz,
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1H), -0.37 (s, 9H). C{1H} NMR (125MHz, CDCl3, δ ppm) 148.4, 144.4, 142.6, 141.3,
134.9, 134.5, 131.8, 129.8, 127.4, 126.6, 126.4, 124.4, 55.1, 43.8, 43.3, 38.7, 37.8, 33.0,
+
32.8, 2.1, -0.5. HRMS (EI) m/z calcd for C25H36Si2 (M)+ 392.2356, found 392.2355.
trimethyl(5-methyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1'-bip
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henyl]-3-yl)silane (5b) (4b: 65.0 mg, 80%; 6b: 65,0 mg, 80%) was prepared according to
the typical procedure (petroleum ether) as a white solid. mp: 66.5-73.4 °C. 1H NMR (500
MHz, CDCl3, δ ppm) 7.42 (d, J = 8.0 Hz, 1H), 7.39-7.27 (m, 5H), 6.87 (d, J = 1.5 Hz,
1H), 3.55 (d, J = 11.0 Hz, 1H), 2.64 (d, J = 3.0 Hz, 1H), 2.31 (s, 3H), 2.02 (d, J = 3.5 Hz,
1H), 1.64-1.58 (m, 1H), 1.48-1.44 (m, 1H), 1.36-1.34 (m, 1H), 1.31-1.29 (m, 1H),
1.26-1.21 (m, 1H), 0.54 (d, J = 10.0 Hz, 1H), 0.42 (s, 9H), 0.35 (d, J = 10.0 Hz, 1H),
-0.35 (s, 9H). 13C{1H} NMR (125MHz, CDCl3, δ ppm) 145.5, 144.5, 142.4, 141.1, 135.5,
135.2, 133.4, 131.8, 129.8, 127.4, 126.5, 126.1, 54.6, 43.8, 43.4, 38.7, 37.8, 33.1, 32.8,
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20.7, 2.1, -0.5. HRMS (EI) m/z calcd for C26H38Si2 (M)+ 406.2512, found 406.2503.
(5-fluoro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1'-biphenyl]-3-
yl)trimethylsilane (5c) (4c: 68.2 mg, 83%; 6c: 59.9 mg, 73%) was prepared according to
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the typical procedure (petroleum ether) as a white solid. mp: 110.0-113.0 °C. H NMR
(500 MHz, CDCl3, δ ppm) 7.38-7.37 (m, 2H), 7.31 (s, 2H), 7.28-7.26 (m, 1H), 7.20-7.19
(m, 1H), 6.74-6.71 (m, 1H), 3.53 (d, J = 11.0 Hz, 1H), 2.60 (s, 1H), 2.00 (s, 1H),
1.62-1.59 (m, 1H), 1.48-1.43 (m, 1H), 1.33-1.28 (m, 2H), 1.22-1.21 (s, 1H), 0.53 (d, J =
9.0 Hz, 1H), 0.41 (s, 9H), 0.30 (d, J = 9.5 Hz, 1H), -0.34 (s, 9H). 13C{1H} NMR
(125MHz, CDCl3, δ ppm) 159.6 (d, J = 246.3 Hz), 145.8 (d, J = 2.8 Hz), 144.4 (d, J = 2.7
Hz), 143.1, 143.0, 131.6, 129.6, 127.6, 127.0, 126.3, 120.8 (d, J = 7.2 Hz), 120.6 (d, J =
5.3 Hz), 54.4, 43.9, 43.4, 38.7, 37.7, 33.0, 32.8, 1.9, -0.4. HRMS (EI) m/z calcd for
+
C25H35FSi2 (M)+ 410.2261, found 410.2260.
(5'-chloro-2'-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1'-biphenyl]-
2-yl)trimethylsilane
(5-chloro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1'-biphenyl]-3
-yl)trimethylsilane (5d) (66.6 mg, 78%) was prepared according to the typical procedure
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(petroleum ether) as a white solid. mp: 113.0-116.7°C. H NMR (500 MHz, CDCl3, δ
ppm) 7.44 (d, J = 2.0 Hz, 1H), 7.42-7.36 (m, 2H), 7.34-7.30 (m, 2H), 7.29-7.26 (m, 1H),
7.04 (d, J = 2.0 Hz, 1H), 3.53 (d, J = 11.0 Hz, 1H), 2.61 (d, J = 3.5 Hz, 1H), 2.02 (d, J =
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3.5 Hz, 1H), 1.64-1.57 (m, 1H), 1.49-1.43 (m, 1H), 1.34 (d, J = 11.0 Hz, 1H), 1.29-1.26
(m, 1H), 1.24-1.20 (m, 1H), 0.54 (d, J = 10.0 Hz, 1H), 0.42 (s, 9H), 0.33 (d, J = 10.0 Hz,
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1H), -0.33 (s, 9H). C{1H} NMR (125MHz, CDCl3, δ ppm) 147.1, 145.5, 143.0, 142.9,
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32.8, 1.9, -0.4. HRMS (EI) m/z calcd for C25H35ClSi2 (M)+ 426.1966, found 426.1967.
trimethyl(2'-methyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1'-bi
phenyl]-3-yl)silane (5e) (62.3 mg, 79%) was prepared according to the typical procedure
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(petroleum ether) as a colorless oil. H NMR (500 MHz, CDCl3, δ ppm) 7.49 (d, J = 6.5
Hz, 1H), 7.41 (d, J = 6.0 Hz, 1H), 7.23-7.20 (m, 2H), 7.15-7.14 (m, 2H), 6.88 (d, J = 6.5
Hz, 1H), 3.52 (d, J = 11.0 Hz, 1H), 2.20 (s, 1H), 2.07 (s, 1H), 1.94 (s, 3H), 1.59-1.57 (m,
1H), 1.49 (d, J = 11.0 Hz, 2H ), 1.23 (s, 2H), 0.80 (d, J = 9.0 Hz, 1H), 0.55 (d, J = 9.0 Hz,
1H), 0.40 (s, 9H), -0.31 (s, 9H). C{1H} NMR (125MHz, CDCl3, δ ppm) 148.3, 144.5,
13
142.2, 139.3, 137.1, 134.4, 129.5, 129.0, 127.0, 124.9, 124.8, 54.7, 44.1, 39.9, 38.9, 38.4,
33.0, 32.8, 20.7, 2.1, -0.1. HRMS (EI) m/z calcd for C26H38Si2 (M)+ 406.2512, found
+
406.2501.
(4'-methoxy-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1'-biphenyl]
-3-yl)trimethylsilane (5f) (4f: 68.5 mg, 81%; 6f: 68.4 mg, 81%) was prepared according
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to the typical procedure (petroleum ether) as a white solid. mp: 55.5-65.7 °C. H NMR
(500 MHz, CDCl3, δ ppm) 7.48 (d, J = 6.5 Hz, 1H), 7.32-7.30 (d, J = 8.0 Hz, 1H), 7.24 (d,
J = 8.5 Hz, 1H), 7.14-7.12 (m, 1H), 7.02 (d, J = 7.0 Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H),
6.82 (d, J = 8.0 Hz, 1H), 3.86 (s, 3H), 3.56 (d, J = 11.0 Hz, 1H), 2.64 (s, 1H), 2.01 (s, 1H),
1.61-1.59 (m, 1H), 1.49-1.45 (m, 1H), 1.35-1.28 (m, 3H), 0.61 (d, J = 9.5 Hz, 1H),
0.43-0.40 (m, 10H), -0.38 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 158.4, 148.8,
142.5, 141.0, 136.9, 135.3, 134.3, 132.8, 130.8, 124.4, 112.5, 111.8, 55.3, 55.1, 43.8, 43.4,
38.7, 37.9, 33.1, 32.8, 2.1, -0.5. HRMS (EI) m/z calcd for C26H38OSi2 (M)+ 422.2461,
+
found 422.2463.
(4'-chloro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1'-biphenyl]-3
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-yl)trimethylsilane (5g) (4g: 51.3 mg, 60%; 6g: 21.3 mg, 25%) was prepared according to
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6
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the typical procedure (petroleum ether) as a white solid. mp: 94.3-101.6 °C. H NMR
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8
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(400 MHz, CDCl3, δ ppm) 7.41 (d, J = 7.6 Hz, 1H), 7.26 (s, 2H), 7.18 (s, 2H), 7.05 (t, J =
7.2 Hz, 1H), 6.88 (d, J = 7.6 Hz, 1H), 3.48 (d, J = 11.2 Hz, 1H), 2.49 (s, 1H), 1.94 (s, 1H),
1.53 (t, J = 11.2 Hz, 1H), 1.39 (t, J = 11.6 Hz, 1H), 1.26-1.14 (m, 3H), 0.54 (d, J = 9.6 Hz,
1H), 0.31 (s, 10H), -0.48 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 148.5, 142.9,
142.8, 140.0, 134.8, 134.7, 133.2, 132.6, 131.0, 127.5, 126.4, 124.5, 55.0, 43.8, 43.2, 38.7,
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+
38.0, 33.0, 32.8, 2.1, -0.5. HRMS (EI) m/z calcd for C25H35ClSi2 (M)+ 426.1966, found
426.1967.
methyl
3'-(trimethylsilyl)-2'-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1'-bip
henyl]-4-carboxylate (5h) (31.6 mg, 35%) was prepared according to the typical
1
procedure (petroleum ether/ethyl acetate = 30:1) as a colorless oil. H NMR (400 MHz,
CDCl3, δ ppm) 7.97 (d, J = 8.0 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.42 (s, 2H), 7.32 (d, J
= 8.0 Hz, 1H), 7.07 (t, J = 7.2 Hz, 1H), 6.88 (d, J = 7.2 Hz, 1H), 3.86 (s, 3H), 3.49 (d, J =
11.2 Hz, 1H), 2.50 (s, 1H), 1.91 (s, 1H), 1.53-1.47 (m, 1H), 1.39-1.33 (m, 1H), 1.23-1.20
(m, 1H), 1.18-1.13 (m, 2H), 0.45 (d, J = 10 Hz, 1H), 0.31 (s, 9H), 0.24 (d, J = 10 Hz, 1H),
-0.47 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 167.1, 149.4, 148.2, 142.9, 140.2,
134.9, 134.3, 132.0, 129.8, 128.9, 128.4, 127.4, 124.5, 55.0, 52.0, 43.8, 43.1, 38.7, 37.9,
+
33.0, 32.7, 2.1, -0.6. HRMS (ESI) m/z calcd for C27H38O2Si2 (M + Na)+ 473.2410, found
473.2412.
(3'-fluoro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1'-biphenyl]-3
-yl)trimethylsilane (5i) (56.7 mg, 69%, 1:1) was prepared according to the typical
procedure (petroleum ether) as a white solid. 1H NMR (400 MHz, CDCl3, δ ppm) 7.53 (d,
J = 7.2 Hz, 2H), 7.34 (q, J = 6.8 Hz, 1H), 7.25-7.21 (m, 2H), 7.18-7.13 (m, 4H),
7.08-7.00 (m, 1H), 3.60 (d, J = 11.2 Hz, 2H), 2.64 (s, 2H), 2.06 (s, 2H), 1.64 (t, J = 12.0
Hz, 2H), 1.52-1.45 (m, 2H), 1.39-1.25 (m, 6H), 0.64 (t, J = 10.4 Hz, 2H), 0.43 (s, 20H),
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-0.35 (d, J = 6.4 Hz, 18H). 13C{1H} NMR(100MHz, CDCl3, δ ppm) 162.7 (d, J = 89.1 Hz)
160.3 (d, J = 88.0 Hz), 148.3 (d, J = 5.1 Hz), 146.6 (d, J = 7.3 Hz),146.5 (d, J = 6.8 Hz),
142.8 (d, J = 2.5 Hz), 140.0, 134.8, 134.5, 128.8 (d, J = 8.7 Hz), 127.8 (d, J = 8.8 Hz),
127.7 (d, J = 8.8 Hz), 125.7 (d, J = 3.1 Hz), 124.5 (d, J = 1.8 Hz), 118.8 (d, J = 21.5 Hz),
117.0 (d, J = 21.1 Hz), 113.6 (d, J = 21.2 Hz), 113.3 (d, J = 20.5 Hz), 55.1, 55.0, 43.8,
43.7, 43.3, 43.2, 38.8, 38.7, 38.0, 37.8, 33.0, 32.9, 32.8, 32.8, 2.1, -0.5, -0.6. HRMS (EI)
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+
m/z calcd for C25H35FSi2 (M)+ 410.2261, found 410.2261.
4-(3-(trimethylsilyl)-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)
pyridine (5j) (44.9 mg, 57%) was prepared according to the typical procedure
1
(petroleum ether/ethyl acetate = 3:1) as a yellow solid. mp: 118.2-120.0 °C. H NMR
(500 MHz, CDCl3, δ ppm) 8.60 (s, 1H), 8.49 (s, 1H), 7.52 (d, J = 7.0 Hz, 1H), 7.37 (s,
1H), 7.26 (s, 1H), 7.17-7.15 (m, 1H), 6.92 (d, J = 7.0 Hz, 1H), 3.57 (d, J = 11.0 Hz, 1H),
2.57 (s, 1H), 2.03 (s, 1H), 1.60-1.58 (m, 1H), 1.49-1.44 (m, 1H), 1.33-1.27 (m, 2H), 1.21
(s, 1H), 0.60 (d, J = 9.5 Hz, 1H), 0.39 (s, 10H), -0.40 (s, 9H). 13C{1H} NMR (125 MHz,
CDCl3, δ ppm) 152.6, 149.2, 147.9, 147.6, 143.2 138.5, 135.2, 134.0, 127.0, 124.9, 124.7,
54.9, 43.8, 43.1, 38.7, 38.2, 32.9, 32.7, 2.0, -0.5. HRMS (ESI-TOF) m/z calcd for
+
C24H36NSi2 (M+H)+ 394.2381, found 394.2384.
2-bromo-5-fluoro-1,1'-biphenyl (6c) (125.5 mg, 50%) was prepared according to the
typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm)
7.62 (q, J = 5.5 Hz, 8.5 Hz 1H), 7.46-7.39 (m, 5H), 7.07 (dd, J = 3.0 Hz, 9.0 Hz 1H), 6.94
(td, J = 3.0 Hz, 8.5Hz, 1H), 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 161.7 (d, J = 245.7
Hz), 144.3 (d, J = 8.0 Hz), 140.1, 134.3 (d, J = 8.3 Hz) 129.2, 128.1, 128.0, 118.2 (d, J =
22.6 Hz), 116.8 (d, J = 3.4 Hz), 115.8 (d, J = 21.9 Hz). HRMS (ESI) m/z calcd for
C12H9I+ (M+H)+ 250.9793, found 250.9791.
((1R,2S,3S,4S)-3-(2-iodophenyl)bicyclo[2.2.1]heptan-2-yl)trimethylsilane (7) (68.9 mg,
1
93%) was prepared according to the literature14 (petroleum ether) as a colorless oil. H
NMR (400 MHz, CDCl3, δ ppm) 7.77 (d, J = 7.6 Hz, 1H), 7.34 (d, J = 7.6 Hz, 1H), 7.26 (t,
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J = 7.2 Hz, 1H), 6.83 (t, J = 7.2 Hz, 1H), 3.24 (d, J = 10.4 Hz, 1H), 2.37 (s, 2H), 1.84 (d,
J = 9.6 Hz, 1H), 1.77-1.71 (m, 1H), 1.64-1.58 (m, 1H), 1.47-1.37 (m, 4H), -0.30 (s, 9H).
13C{1H} NMR (100 MHz, CDCl3, δ ppm) 148.4, 139.1, 128.1, 127.5, 127.3, 105.2, 55.5,
44.0, 40.2, 38.9, 38.4, 32.3, 32.2, -0.4. HRMS (ESI) m/z calcd for C16H24ISi+ (M+H)+
371.0686, found 371.0682.
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((1R,2S,3S,4S)-3-(3-iodo-[1,1'-biphenyl]-2-yl)bicyclo[2.2.1]heptan-2-yl)trimethylsilane
(8) (85.7 mg, 96%) was prepared according to the literature14 (petroleum ether) as a
colorless oil. Colorless oil (85.7 mg, 96%). 1H NMR (400 MHz, CDCl3, δ ppm) 7.92 (d, J
= 8.0 Hz, 1H), 7.33 (d, J = 11.2 Hz, 5H), 6.97 (d, J = 7.6 Hz, 1H), 6.78 (t, J = 7.6 Hz, 1H),
3.62 (d, J = 10.8 Hz, 1H), 2.47 (s, 1H), 2.09 (s, 1H), 1.82 (d, J = 10.8 Hz, 1H), 1.61-1.56
(m, 1H), 1.40-1.37 (m, 1H), 1.31-1.26 (m, 2H), 0.65 (q, J = 9.6 Hz, 2H), -0.21 (s, 9H).
13C{1H} NMR (100 MHz, CDCl3, δ ppm) 144.4, 143.0, 141.5, 139.8, 133.5, 131.0, 129.5,
127.3, 126.5, 126.1, 109.0, 60.0, 42.0, 40.2, 38.7, 38.3, 33.3, 32.5, 0.0. HRMS (ESI-TOF)
m/z calcd for C22H28ISi+ (M+H)+ 447.0999, found 447.0996.
 ASSOCIATED CONTENT
 AUTHOR INFORMATION
Corresponding Author
* E-mail: yliang@hunnu.edu.cn.
* E-mail: yangyuan071@126.com.
ORCID
Guobo Deng: 0000-0002-5470-5706
Yun Liang: 0000-0002-2550-9220
Yuan Yang: 0000-0002-9061-1758
Notes
The authors declare no competing financial interest.

Supporting Information
The Supporting Information is available free of charge on the ACS Publications website
at DOI: 10.1021/acs.joc.
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1H NMR and 13C{1H} NMR spectra of new compounds 2 and 5 and X-ray
single-crystal diffraction analysis for compound 5d (PDF)
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 ACKNOWLEDGMENT
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This work was supported by the National Natural Science Foundation of China
(21572051 and 21602057), the Opening Fund of Key Laboratory of Chemical Biology
and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan
Normal University (KLCBTCMR201707 and KLCBTCMR201708), and Science and
Technology Planning Project of Hunan Province (2018TP1017).
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 References
(1) For reviews see: (a) Della Ca’, N.; Fontana, M.; Motti, E.; Catellani, M. Pd/Norbornene: A
Winning Combination for Selective Aromatic Functionalization via C-H Bond Activation. Acc.
Chem. Res. 2016, 49, 1389-1400. (b) Catellani, M.; Motti, E.; Della Ca’, N.; Catalytic sequential
reactions involving palladacycle-directed aryl coupling steps. Acc. Chem. Res. 2008, 41,
1512-1522.
(c) Ye, J.; Lautens, M. Palladium-catalysed norbornene-mediated C-H
functionalization of arenes. Nat. Chem. 2015, 7, 863-870. (d) Martins, A.; Mariampillai, B.;
Lautens, M. Synthesis in the Key of Catellani: Norbornene-Mediated ortho C-H
Functionalization. Top. Curr. Chem. 2010, 292, 1-33. (e) Lautens, M.; Alberico, D.; Bressy, C.;
Fang, Y.-Q.; Mariampillai, B.; Wilhelm, T. Palladium-catalyzed ring-forming reactions: Methods
and applications. Pure Appl. Chem. 2006, 78, 351-361. (f) Kim, D.-S.; Park, W.-J.; Jun, C-H.
Metal-Organic Cooperative Catalysis in C-H and C-C Bond Activation. Chem. Rev. 2017, 117,
8977-9015.
(2) Catellani, M.; Frignani, F.; Rangoni, A. A complex catalytic cycle leading to a regioselective
synthesis of o,oʹ-disubstituted vinylarenes. Angew. Chem., Int. Ed. Engl. 1997, 36, 119-122.
(3) For selected excellent studies, see: (a) Cheng, H.-G.; Wu, C.; Chen, H.; Chen, R.; Qian, G.; Geng,
Z.; Wei, Q.; Xia, Y.; Zhang, J.; Zhang, Y.; Zhou, Q. Epoxides as Alkylating Reagents for the
Catellani Reaction. Angew. Chem., Int. Ed. 2018, 57, 3444-3448. (b) Li, R.; Dong, G. Direct
Annulation between Aryl Iodides and Epoxides through Palladium/Norbornene Cooperative
Catalysis. Angew. Chem., Int. Ed. 2018, 57, 1697-1701. (c) Shi, G.; Shao, C.; Ma, X.; Gu, Y.;
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2
3
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5
6
7
8
9
Zhang, Y. Pd(II)-Catalyzed Catellani-Type Domino Reaction Utilizing Arylboronic Acids as
Substrates. ACS Catal. 2018, 8, 3775-3779. (d) Sun, F.; Li, M.; He, C.; Wang, B.; Li, B.; Sui,
X.; Gu, Z. Cleavage of the C(O)-S Bond of Thioesters by Palladium/ Norbornene/Copper
Cooperative Catalysis: An Efficient Synthesis of 2-(Arylthio)aryl Ketones. J. Am. Chem. Soc.
2016, 138, 7456-7459. (e) Wang, J.; Zhang, L.; Dong, Z.; Dong, G. Reagent-Enabled
ortho-Alkoxycarbonylation of Aryl Iodides via Palladium/Norbornene Catalysis. Chem. 2016, 1,
581-591. (f) Shi, H.; Babinski, D. J.; Ritter. T. Modular C-H Functionalization Cascade of Aryl
Iodides. J. Am. Chem. Soc. 2015, 137, 3775-3778. (g) Dong, Z.; Wang, J.; Ren, Z.; Dong, G.
Angew. Chem., Int. Ed. 2015, 54, 12664-12668.
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43
44
45
46
47
48
49
50
51
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53
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55
56
57
58
59
60
(4) For selected excellent studies, see: (a) Casnati, A.; Gemoets, H. P. L.; Motti, E.; Ca’, N. D.; Noël,
T. Homogeneous and Gas-Liquid Catellani-type Reaction Enabled by Continuous-Flow
Chemistry. Chem.-Eur. J. 2018, 24, 14079-14083. (b) Chen, S.; Liu, Z.-S.; Yang, T.; Hua, Y.;
Zhou, Z.; Cheng, H.-G.; Zhou, Q. The Discovery of a Palladium(II)-Initiated Borono-Catellani
Reaction. Angew. Chem., Int. Ed. 2018, 57, 7161-7165. (c) Dong, Z.; Lu, G.; Wang, J.; Liu, P.;,
Dong, G. Modular ipso/ortho Difunctionalization of Aryl Bromides via Palladium/Norbornene
Cooperative Catalysis. J. Am. Chem. Soc. 2018, 140, 8551-8562. (d) Wang, J.; Li, W.; Dong, Z.;
Liu, P.; Dong, G. Complementary site-selectivity in arene functionalization enabled by
overcoming the ortho constraint in palladium/norbornene catalysis. Nature Chemistry 2018, 10,
866-872.
(5) (a) Della Ca’, M.; Maestri, G.; Malacria, M.; Derat, E.; Catellani, M. Palladium-Catalyzed
Reaction of Aryl Iodides with ortho-Bromoanilines and Norbornene/Norbornadiene: Unexpected
Formation of Dibenzoazepine Derivatives. Angew. Chem. Int. Ed. 2011, 50, 12257-12261. (b)
Zhou, H.; Chen, W.; Chen, Z. Pd/Norbornene Collaborative Catalysis on the Divergent
Preparation of Heterocyclic Sulfoximine Frameworks. Org. Lett. 2018, 20, 2590-2594. (c)
Zheng, H.; Zhu, Y.; Shi, Y. Palladium(0)-Catalyzed Heck Reaction/C-H Activation/Amination
Sequence with Diaziridinone: A Facile Approach to Indolines. Angew. Chem., Int. Ed. 2014, 53,
11280-11284. (d) Jafarpour, F.; Jalalimanesh, N.; Teimouri, M.; Shamsianpour, M.
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Palladium/norbornene chemistry: an unexpected route to methanocarbazole derivatives via three
Csp3-Csp2/Csp3-N/Csp2-N bond formations in a single synthetic sequence. Chem. Commun.
2015, 51, 225-228.
9
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53
54
55
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(6) (a) Thansandote, P.; Hulcoop, D. G.; Langer, M.; Lautens, M. Palladium-Catalyzed Annulation of
Haloanilines and Halobenzamides Using Norbornadiene as an Acetylene Synthon: A Route to
Functionalized Indolines, Isoquinolinones, and Indoles. J. Org. Chem. 2009, 74, 1673-1678. (b)
Casnati, A.; Fontana, M.; Coruzzi, G.; Aresta, B. M.; Corriero, N.; Maggi, R.; Maestri, G.; Motti,
E.; Ca’, N. D. Enhancing Reactivity and Selectivity of Aryl Bromides: A Complementary
Approach
to
Dibenzo[b,f]azepine
Derivatives.
ChemCatChem.
2018,
DOI:
10.1002/cctc.201800940.
(7) (a) Hao, T.; Liang, H.; Ou-Yang, Y.; Yin, C.; Zheng, X.; Yuan, M.; Li, R.; Fu, H.; Chen, H.
Palladium-Catalyzed Domino Reaction for Stereoselective Synthesis of Multisubstituted Olefins:
Construction of Blue Luminogens. J. Org. Chem. 2018, 83, 4441-4454. (b) Fu, W. C.; Wang, Z.;
Chan, W. T. K.; Lin, Z.; Kwong, F. Y. Regioselective Synthesis of Polycyclic and
Heptagon-embedded Aromatic Compounds through a Versatile p-Extension of Aryl Halides.
Angew. Chem., Int. Ed. 2017, 56, 7166-7170. (c) Cheng, M.; Yan, J.; Hu, F.; Chen, H.; Hu, Y.
Palladium-catalyzed cascade reactions of 3-iodochromones with aryl iodides and norbornadiene
leading to annulated xanthones. Chem. Sci. 2013, 4, 526-530. (d) Larraufie, M.-H.; Maestri, G.;
Beaume, A.; Derat, É.; Ollivier, C.; Fensterbank, L.; Courillon, C.; Lacôte, E.; Catellani, M.;
Malacria, M. Exception to the ortho Effect in Palladium/Norbornene Catalysis. Angew. Chem.,
Int. Ed. 2011, 50, 12253-12256. (e) Maestri, G.; Motti, E.; Della Ca’, N.; Malacria, M.; Derat, E.;
Catellani, M. Of the Ortho Effect in Palladium/Norbornene-Catalyzed Reactions: A Theoretical
Investigation. J. Am. Chem. Soc. 2011, 133, 8574-8585.
(8) (a) Gericke, K. M.; Chai, D. I.; Bieler, N.; Lautens, M. The Norbornene Shuttle: Multicomponent
Domino Synthesis of Tetrasubstituted Helical Alkenes through Multiple C-H Functionalization.
Angew. Chem., Int. Ed. 2009, 48, 1447-1451. (b) Chai, D. I.; Thansandote, P.; Lautens, M.
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Mechanistic Studies of Pd-Catalyzed Regioselective Aryl C-H Bond Functionalization with
Strained Alkenes: Origin of Regioselectivity. Chem. Eur. J. 2011, 17, 8175-8188. (c) Hulcoop,
D. G.; Lautens, M. Palladium-Catalyzed Annulation of Aryl Heterocycles with Strained Alkenes.
Org. Lett. 2007, 9, 1761-1764.
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(9) (a) Lv, W.; Wen, S.; Yu, J.; Cheng, G. Palladium-Catalyzed Ortho-Silylation of Aryl Iodides with
Concomitant Arylsilylation of Oxanorbornadiene: Accessing Functionalized (Z)-β-Substituted
Vinylsilanes and Their Analogues. Org. Lett. 2018, 20, 4984-4987. During article submission, a
similar work was reported: (b) Lv, W.; Yu, J.; Ge, B.; Wen, S.; Cheng, G. Palladium-Catalyzed
Catellani-Type Bis-silylation and Bisgermanylation of Aryl Iodides and Norbornenes. J. Org.
Chem. 2018. DOI: 10.1021/acs.joc.8b02018.
(10) (a) Nakao, Y.; Sahoo, A. K.; Imanaka, H.; Yada, A.; Hiyama, T. Alkenyl- and
aryl[2-(hydroxymethyl)phenyl]dimethylsilanes:
Tetraorganosilanes
for
the
practical
cross-coupling reaction. Pure Appl. Chem. 2006, 78, 435-440. (b) Suzawa, K.; Ueno, M.;
Wheatley, A. E. H.; Kondo, Y. Phosphazene base-promoted functionalization of
aryltrimethylsilanes. Chem. Commun. 2006, 42, 4850-4852. (c) Pierrat, P.; Gros, P.; Fort, Y.
Hiyama Cross-Coupling of Chloro-, Fluoro-, and Methoxypyridyltrimethylsilanes:
Room-Temperature Novel Access to Functional Bi(het)aryl. Org. Lett. 2005, 7, 697-700. (d) S.
E. Denmark and R. F. Sweis in Metal-Catalyzed Cross-Coupling Reactions, Vol. 1, 2nd ed.
(Eds.: A. De Meijere, F. Diederich), Wiley-VCH, Weinheim, 2004. (e) Abele, E.; Lukevics,E.
Recent Advances in the Synthesis and Transformations of Heterocycles Mediated by Fluoride
Ion Activated Organosilicon Compounds. Heterocycles 2002, 57, 361-401. (f) Langkopf, E.;
Schinzer, D. Chem. Rev. 1995, 95, 1375-1408.
(11) (a) Yang, Y.; Song, R.-J.; Ouyang, X.-H.; Wang, C.-Y.; Li, J.-H.; Luo, S. Iron-Catalyzed
Intermolecular 1,2-Difunctionalization of Styrenes and Conjugated Alkenes with Silanes and
Nucleophiles. Angew. Chem., Int. Ed. 2017, 56, 7916-7919. (b) Franz, A. K.; Wilson, S. O.
Organosilicon Molecules with Medicinal Applications. J. Med. Chem. 2013, 56, 388-405. (c)
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