Silver-promoted cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides by palladium catalysis

Article abstract of DOI:10.1016/j.tetlet.2018.11.026

A ligand-free Pd-catalyzed cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides enabled by silver salts was developed. This reaction delivered allylic arenes chemoselectively and regioselectively. The study suggested that the reaction might proceed through oxidative addition of ArI to Pd(0) followed by halide abstraction to give an electrophilic complex ArPdX, which further reacted with allyl(trimethyl)silanes via electrophilic addition/desilylation/reductive elimination to afford the allyl-aryl coupling products.

Full text of DOI:10.1016/j.tetlet.2018.11.026

Accepted Manuscript
Silver-Promoted Cross-Coupling of Substituted Allyl(trimethyl)silanes with
Aryl Iodides by Palladium Catalysis
Zhen-Lin Hou, Fan Yang, Zhibing Zhou, Yu-Fei Ao, Bo Yao
PII:
S0040-4039(18)31354-6
https://doi.org/10.1016/j.tetlet.2018.11.026
TETL 50411
DOI:
Reference:
Tetrahedron Letters
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Revised Date:
Accepted Date:
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8 November 2018
9 November 2018
Please cite this article as: Hou, Z-L., Yang, F., Zhou, Z., Ao, Y-F., Yao, B., Silver-Promoted Cross-Coupling of
Substituted Allyl(trimethyl)silanes with Aryl Iodides by Palladium Catalysis, Tetrahedron Letters (2018), doi:
https://doi.org/10.1016/j.tetlet.2018.11.026
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Zhen-Lin Hou,a Fan Yang,a Zhibing Zhou,a Yu-Fei Aob and Bo Yaoa,b,
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1
Tetrahedron Letters
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Silver-Promoted Cross-Coupling of Substituted Allyl(trimethyl)silanes with Aryl
Iodides by Palladium Catalysis
Zhen-Lin Hou,a Fan Yang,a Zhibing Zhou,a Yu-Fei Aob and Bo Yaoa,b,
*
aMOE Key Laboratory of Cluster Science, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical
Engineering, Beijing Institute of Technology, Beijing 102488, P. R. China.
bBeijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of
Sciences, Beijing 100190, P.R. China.
ARTICLE INFO
ABSTRACT
Article history:
Received
A ligand-free Pd-catalyzed cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides
enabled by silver salts was developed. This reaction delivered allylic arenes chemoselectively
and regioselectively. The study suggested that the reaction might proceed through oxidative
addition of ArI to Pd(0) followed by halide abstraction to give an electrophilic complex ArPdX,
Received in revised form
Accepted
Available online
which
further
reacted
with
allyl(trimethyl)silanes
via
addition/desilylation/reductive elimination to afford the allyl-aryl coupling products.
electrophilic
2009 Elsevier Ltd. All rights reserved.
Keywords:
Palladium catalysis
Cross-coupling
Allyl(trimethyl)silane
Silver salt
1. Introduction
(Scheme 1b).14 Despite high yield and excellent regioselectivity,
the use of fluoro- or oxygen-substituted silanes as substrates and
the need of fluoride anions for C-Si activation of some substrates
limited their application.
Allylic arenes represent an important structural component
found in many natural products, pharmaceuticals and synthetic
intermediates.1 Existing main approaches to allylic arenes include
Friedel-Crafts allylation of arenes,2 allylic C-H arylation,3 cross-
coupling of aryl (pseudo)halides with allylmetallic compounds,4
and cross-coupling of allylic electrophiles with arylmetallic
compounds.5 However, Friedel-Crafts allylation and allylic C-H
arylation often suffered from poor regioselectivity, while the
methods using organometallic compounds were often restricted
to substrates with non-sensitive functional groups. As a type of
mild nucleophilic allylation reagents, allylsilanes display unique
properties such as high stability, good solubility and controllable
reactivity. Therefore, the use of allylsilanes in the synthesis of
allylic arenes seemed to be an attractive surrogate for the existing
methods above.
Scheme 1. Cross-coupling reaction of activated allylsilanes
with aryl halides.
Being activated by electrophilic addition to the allylic double-
bond6 and/or nucleophilic attack at the Si atom,7 allylsilanes can
react with various activated electrophiles8-10 and free-radicals11 in
excellent regioselectivity and stereoselectivity. However, the
reaction with unactivated electrophilic reagents such as aryl
(pseudo)halides is less explored. Using allyl(trifluoro)silanes as
the substrates and TBAF as the activator, Hiyama and his co-
workers developed the first γ-regioselective cross-coupling of
allylsilanes with aryl iodides and triflates in. 1991 (Scheme 1a).12
They also disclosed ligand-controlled α-regioseletive cross-
coupling reaction in 1994.13 Furthermore, Denmark and his co-
workers reported a γ-regioselective cross-coupling of allylic
silanolate salts with aryl bromides catalyzed by Pd(dba)2 in 2008
Compared
with
other
types
of
allylsilanes,
allyl(trialkyl)silanes are more stable and therefore can be easily
prepared from various starting materials.15 Although an
intramolecular arylation of ally(trimethyl)silanes to allylic arenes
was successfully developed by Tietze in 1994,16 intermolecular
reactions often gave silyl-containing compounds as the major
products.17 In 2000, Jeffery reported an elegant method for the
cross-coupling of allyl(trimethyl)silane with aryl iodides to give
allylic arenes by a Pd(dba)2/PPh3/nBu4NOAc catalyst system (eq
1, Scheme 2a).18 More recently, Patil and his co-workers
developed an efficient cross-coupling of allyl(trialkyl)silanes
with aryl diazonium salts to allylic arenes via merged

2
Tetrahedron Letters
gold/photoredox catalysis (eq 2, Scheme 2a).19 However, the
were detected by NMR. Among these side-products, the double-
bond migration isomer 4 and the Heck-coupling product 5 were
the major and very difficult to be separated from 3aa by
chromatography. Surprisingly, further investigation of other Pd
catalysts showed that the use of Pd(OAc)2 as the catalyst without
a phosphine ligand led to only a trace amount of side-products,
though the yield of 3aa was also reduced (eq 1).
cross-coupling of substituted allyl(triakyl)silanes with aryl
(pseudo)halides to give allylarenes has not been investigated so
far. In this context and in connection with our interest in
organosilicon chemistry, we designed a Pd/Ag catalytic system
and realized the first cross-coupling of substituted
allyl(trimethyl)silanes with aryl iodides to furnish allylarenes
chemo-selectively (Scheme 2b). Furthermore, the reaction of β,γ-
disubstituted substrates gave the γ-arylation products in high
regio-selectivity.
On the basis of the preliminary results, we continued
extensive conditions optimization by screening solvents, silver
salts, Pd catalysts and ligands (Table S2-S4). It was found that
the reaction with 5 mol% Pd(OAc)2 as the catalyst and 1.0 equiv
Ag2CO3 as the additive in DCE at 80 °C under N2 gave the
optimal result (entry 1, Table 1). The reaction delivered 3aa in
79% yield and a bis-arylation product 7 in 8% yield. Both of the
two possible side-products 4 and 5 were not detected by NMR
and the protodesilylation product 6 was detected in less than 5%
Table 1. Conditions optimization for the cross-coupling
of allyl(trimethyl)silane 1a with methyl 4-iodobenzoate
2a
.
Scheme 2. Cross-coupling reaction of allyl(trialkyl)silanes
with aryl (pseudo)halides.
2. Results and discussion
2.1. Reaction design and conditions optimization
The Jeffery’s method realized the highly efficient and chemo-
Entry
Pd catalyst
Additive
(equiv)
Yield of
3aa b
79%
63%
79%
trace
trace
67%
57%
51%
trace
65%
72%
61%
39%
traceg
5%
Ratio of
3aa/4/5 c
selective
cross-coupling
between
non-substituted
allyl(trimethyl)silane and aryl iodides to produce allylic arenes.
However, the application of this method to the reaction of
substituted allyl(trimethyl)silane 1a with methyl 4-iodobenzoate
2a failed to afford the desired ally-aryl coupling product 3aa. In
addition, it was mentioned in the paper published by Patil that
substituted allyl(trialkyl)silanes were not compatible to the
gold/photoredox catalytic conditions probably due to steric
factors. In order to realize the cross-coupling of substituted
allyl(trialkyl)silanes with aryl iodides, we proposed a Pd/Ag
catalytic system according to the following considerations: (1)
oxidative addition of ArI to Pd(0) followed by halide abstraction
could generate a highly electrophilic intermediate [ArPdLn]+ A;
(2) this intermediate might undergo electrophilic addition
followed by desilylation to give an aryl-Pd-allyl complex C; (3)
reductive elimination from C would furnish the allyl-aryl
coupling product. In the reaction design, the high electrophilicity
of the complex A might be crucial to the success of the
investigated reaction.
1
Pd(OAc)2
PdCl2
Ag2CO3 (1.0)
Ag2CO3 (1.0)
Ag2CO3 (1.0)
Ag2CO3 (1.0)
Ag2CO3 (1.0)
Ag2CO3 (1.0)
Ag2CO3 (1.0)
Ag2CO3 (1.0)
Ag2CO3 (1.0)
AgOAc (2.0)
Ag2O (1.0)
10/0/1
2
12/0/1
3
Pd(TFA)2
Pd(PPh3)4
10/0/1
4
-
d
5
Pd2(dba)3
-
6
Pd(OTf)2L4
PdL2Cl2
6/2/1
7
5/0.25/1
8e
9f
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
5/0/1
-
10
11
12
13
14
15
16
3/0/1
6/0/1
AgTFA (2.0)
AgNO3 (2.0)
AgOTf (2.0)
K2CO3 (1.0)
CuOAc (2.0)
5/1/1
-
-
-
-
To test the feasibility of our hypothesis in the reaction design,
we conducted the reaction between 1a and 2a with Pd(PPh3)4 as
the catalyst and AgOTf as the additive. The first reaction in
toluene at 60 °C under N2 atmosphere successfully delivered the
product 3aa in 2% yield. And the yield of 3aa was increased to
45% after a short survey of reaction parameters (Table S1). But
this reaction was highly sensitive to air, moisture and even the
addition sequence of reagents. Furthermore, a lot of side-products
12%
aConditions: 2a (0.2 mmol), 1a (0.3 mmol), Pd catalyst (5
mol%), additive (1.0 equiv), DCE (4 mL), 80 °C, N2, 12 h.
b
c
Isolated yield. The ratios were determined by H NMR. 2.5
d
1
mol% Pd2(dba)3. 10 mol% PPh3, 24 h. f20 mol% PPh3, 12 h. 6
was detected by GC in 99% yield. L = CH3CN.
e
g

3
yield. The study also led to several key observations: (1) Pd(II)
catalysts such as PdCl2 and Pd(TFA)2 were as effective as
Pd(OAc)2, while Pd2(dba)3 and Pd(PPh3)4 were not capable of
catalyzing the reaction (entries 2-5, Table 1). (2) Ligands such as
CH3CN and PPh3 were detrimental to the reaction. CH3CN led to
the formation of 4 (entries 6-7, Table 1), while PPh3 reduced the
yield and selectivity (entries 8-9, Table 1). (3) silver salts with
more basic counterions than OAc- were competent (entries 10-11,
Table 1), while those with less basic counterions were not
suitable for the reaction (entries 12-14, Table 1). Further study
with K2CO3 or CuOAc replacing Ag2CO3 (entries 15-16, Table 1)
proved that Ag2CO3 not only acted as a base, but also probably as
an activator for aryl iodides.
Secondly, allyl(trimethyl)silanes with substituted allyl
groups were investigated (Table 3). The study showed that β-aryl
substitution was key to the success of the reaction. Substrates
with β-aryl groups bearing either electron-withdrawing or
electron-donating substituents reacted with aryl iodide 2a well to
yield the products (3ba to 3ia) in 42-76% yield. Functional
groups like methyl (1b), halogen (1c-1e, 1h), CN (1f), CO2Me
(1g) and OMe (1i) were also compatible. Interestingly, the
conditions could also be applicable to β,γ-disubstitued
allylsilanes. The reaction of β-phenyl-γ-methyl substituted
allyl(trimethyl)silane 1k with 2a furnished 3ka in 34% yield and
high γ-regioselectivity (γ:α>10:1). Moreover, the cyclic substrate
1l was coupled with 2d and 2n regioselectively to give the γ-
arylation products 3ld and 3ln (γ:α>20:1). However, when 10
mol% Pd(TFA)2 was used as the catalyst, the two reactions of 1l
delivered the products in higher yield, but with reduced
regioselectivity (γ:α = 3:1 for 3ld, γ:α = 2.5:1 for 3ln).
2.2. Substrate scope
With the optimal conditions in hand, the substrate scope was
next examined (Table 2). Firstly, aryl iodides with various
substituents at para-, meta-, and ortho-positions were tested.
Tolerated functional groups included CO2Me (2a), acyl (2b),
amido (2c), NO2 (2d), CN (2n), CF3 (2e), F (2f), Ph (2h), Me (2i),
OMe (2j), OTf (2k) and OTs (2l). Particularly, the reaction of
OTf and OTs-substituted aryl iodides delivered the OTf and OTs-
containing products in 45% (3ak) and 73% yield (3al)
respectively. The installation of these functional groups in the
products provided opportunities for further transformations.
Electronic properties and steric hindrance of substituents affected
the reaction outcome strongly. Aryl iodides with electron-
withdrawing substituents (2a-2f) reacted with 1a faster and
delivered the products in higher yield than aryl iodides with
electron-donating substituents (2h-2j). In addition, ortho- and
meta-substituted aryl iodides provided higher yield of products
than para-substituted aryl iodides (2d vs 2m, 2i vs 2o).
Combining the two effects, the reaction of 1a with 3-
iodobenzonitrile 2n and 2-iodobenzonitrile 2q provided the
highest yield among all examples (84% for both 3an and 3aq).
Surprisingly, heteroaryl iodides such as 2-iodobenzofuran (2r)
and 3-iodothiophene (2s) could also be coupled with 1a to deliver
the desired products 3ar and 3as in 30% and 36% yield.
However, 3-iodopyridine failed to furnish any coupling products
in the reaction with 1a, probably due to the strong coordination
between nitrogen and palladium.
Table 3. Scope of allyl(trimethyl)silanes 1.
Entry
Silane (1)
SiMe3
ArI (2)
Yield of 3
X
1
2
3
4
5
6
7
8
1b (X = 4-Me)
1c (X = 4-Br)
1d (X = 4-Cl)
1e (X = 4-F)
2a
3ba, 66%
2a
2a
2a
2a
2a
2a
2a
3ca, 42%
3da, 66%
3ea, 72%
3fa, 62%
3ga, 60%
3ha, 76%
3ia, 52%
1f (X = 4-CN)
1g (X = 4-CO2Me)
1h (X = 3-Cl)
1i (X = 3-OMe)
9
1j
2a
2a
3ja, 58%
Table 2. Scope of aryl iodides 2.
10
1k (Z:E = 1:3.6)
3ka, 34% (γ:α >10:1)
SiMe3
Entry
1
ArI (2)
2a (Ar = 4-CO2MeC6H4)
2b (Ar = 4-AcC6H4)
2c (Ar = 4-CONHPhC6H4)
2d (Ar = 4-NO2C6H4)
2e (Ar = 4-CF3C6H4)
2f (Ar = 4-FC6H4)
Yield of 3
3aa, 79%
11
12
1l
1l
2d
2n
3ld, 28% (γ:α>20:1)
43% (γ:α= 3:1)a
2
3ab, 66%
3ac, 73%
3ad, 60%
3ae, 60%
3af, 57%
3ag, 48%
3ah, 41%
3ai, 35%
3aj, 45%
3ak, 45%
3al, 73%
3am, 80%
3an, 84%
3ao, 49%
3ap, 35%
3aq, 84%
3ar, 30%
3as, 36%
3at, 0%
3
3ln, 32% (γ:α>20:1)
4
43% (γ:α= 2.5:1)a
5
a Pd(TFA)2 (10 mol%) instead of Pd(OAc)2 (5 mol%)
6
7
2g (Ar = C6H5)
After developing the allyl-aryl coupling reaction, we
continued to examine other coupling partners. First, the triethyl
and dimethylphenyl counterparts of 1f were applied in the
reaction with 2a. It was found that the reaction of the
triethylsilane (1m) delivered the desired product 3fa in 31% yield,
while the dimethylphenylsilane (1n) exhibited excellent
reactivity (eq 2). The low reactivity of 1m might be explained by
the larger steric bulk and more electron-donating properties of
the ethyl group. Although the dimethylphenylsilane 1n gave
better result, we still preferred to trimethylsilanes considering the
easy accessibility and low cost. Then, we also applied the
8
2h (Ar = 4-PhC6H4)
2i (Ar = 4-MeC6H4)
2j (Ar = 4-OMeC6H4)
2k (Ar = 4-OTfC6H4)
2l (Ar = 4-OTsC6H4)
2m (Ar = 3-NO2C6H4)
2n (Ar = 3-CNC6H4)
2o (Ar = 3-MeC6H4)
2p (Ar = 3-OMeC6H4)
2q (Ar = 2-CNC6H4)
2r (Ar = benzofuran-2-yl)
2s (Ar = thiophen-3-yl)
2t (Ar = pyridine-3-yl)
9
10
11
12
13
14
15
16
17
18
19
20
conditions
to
the
cross-coupling
of
substituted

4
Tetrahedron Letters
allyl(trimethyl)silanes with alkenyl iodides. Unfortunately, the
minor process to produce 3 as the Heck-product 5 from β-H
elimination was not detected under the optimal conditions.
reaction between (E)-β-iodostyrene and 1a under the above
optimal conditions failed to afford the desired coupling product.
In addition, a three-component reaction between 1a, 2a and 1,2-
diphenylenthyne did not give any product. Gratifyingly, a
cascade reaction between 1a with an alkynamide 8 successfully
yielded the desired cyclization-allylation product 9 in 22% yield.
After modification of the reaction conditions, the yield of 9 was
increased to 60% (eq 3).
Figure 1. Plausible mechanism
3. Conclusion
In conclusion, a phosphine ligand-free Pd-catalyzed cross-
coupling of substituted allyl(trimethyl)silanes with aryl iodides
was developed. This reaction delivered allylarenes
chemoselectively and regioselectively. The study suggested that
the reaction might follow a Pd(0)/Pd(II) catalytic cycle, which
included Ag(I)-mediated oxidative addition of ArI to Pd(0) to
produce an electrophilic intermediate ArPdX, electrophilic
addition/desilylation to give ArPd(allyl) complexes, and final
reductive elimination to furnish the products 3. The detailed
mechanistic study and synthetic application in organic synthesis
is underway in our lab.
2.3. Mechanistic discussion
To gain more information about reaction mechanism, several
control experiments were conducted and the results were
summarized as below: (1) the reaction between 6 and 2a under
the optimal conditions delivered 3aa and 4 in 70% total yield and
1:1 ratio (eq 4), while 4 was not detected in the reaction between
1a and 2a; (2) heating the Heck-product 5 under the optimal
conditions did not give 3aa (eq 5). The results of these
experiments indicated that neither 5 nor 6 was the intermediate in
the cross-coupling reaction, and further ruled out both of the
Acknowledgments
All authors have given approval for the final version of the
manuscript. The authors declare no competing financial interest.
We thank the National Natural Science Foundation of China
(21502006), Beijing National Laboratory for Molecular Sciences
and Beijing Institute of Technology for financial support.
protodesilylation/coupling the
coupling/protodesilylation pathway as possible mechanisms.
pathway
and
Heck-
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16382-16393.
15. Selected referenes: (a) Guo, L.; Leiendecker, M.; Hsiao, C. C.;
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(b) Cai, G.; Zhou, Z.; Wu, W.; Yao, B.; Zhang, S.; Li, X. Org.
Biomol. Chem. 2016, 14, 8702-8706. (c) Selander, N.; Paasch, J.
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6, 597-598.
17. (a) Karabelas, K.; Westerlund, C.; Hallberg, A.; J. Org. Chem.
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19. Akram, M. O.; Mali, P. S.; Patil, N. T. Org. Lett. 2017, 19, 3075-
3078.
20. A recent report on Pd-catalyzed oxidative cross-coupling of
ally(trimethyl)silanes with aryl boronic acids to form allylarenes,
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Supplementary Material
Electronic Supplementary Information (ESI) available:
1
Experimental details, compound characterization, copies of H
NMR and 13C NMR spectra. See DOI: 10.1039/x0xx00000x

6
Tetrahedron Letters
substituted
Highlights
•
•
•
•
The
first
cross-coupling
of
allyl(trimethyl)silanes with aryl iodides was realized
by palladium catalysis.
The
reaction
of
β-aryl
substituted
allyl(trimethyl)silanes delivered 2,3-diarylpropenes in
good yield and high chemoselectivity.
The
reaction
of
β,γ-disubstituted
allyl(trimethyl)silanes afforded the γ-arylation
products in high regioselectivity.
A cascade reaction involving the cyclization-allylation
sequence was realized to synthesize substituted
indolin-2-one.