Nickel-Catalyzed Decarboxylative C–Si Bond Formation: A Regioselective Cross-Coupling Between Trialkyl Silanes and α,β-Unsaturated Carboxylic Acids

Article abstract of DOI:10.1002/aoc.5192

This report presents the first example of nickel-catalyzed mild decarboxylative cross-coupling reaction for the regioselective formation of C–Si bond. An easily accessible and significantly stable Ni (dmg)₂ owes the role of key promoter. This r

Full text of DOI:10.1002/aoc.5192

Received: 25 June 2019
DOI: 10.1002/aoc.5192
Revised: 24 July 2019
Accepted: 31 July 2019
C O M M U N I C A T I O N
Nickel‐Catalyzed Decarboxylative C–Si Bond Formation: A
Regioselective Cross‐Coupling Between Trialkyl Silanes and
α,β‐Unsaturated Carboxylic Acids
Bharat Kumar Allam* | Sadaf Azeez* | Jeyakumar Kandasamy
Department of Chemistry, Indian Institute
This report presents the first example of nickel‐catalyzed mild decarboxylative
of Technology (BHU), Varanasi 221
005Uttar Pradesh, India
cross‐coupling reaction for the regioselective formation of C–Si bond. An easily
accessible and significantly stable Ni (dmg) owes the role of key promoter.
2
Correspondence
This reaction is highly functional group tolerant and offers α,β‐unsaturated
silanes in synthetically useful yields. The reaction gives access to the successful
utilization of otherwise difficult trialkyl silanes as coupling partners and
operates at a moderate temperature, which is beneficial to deal with highly vol-
atile silanes.
Email: jeyakumar.chy@iitbhu.ac.in
KEYWORDS
carboxylic acids, decarboxylation, nickel, silicon, synthetic methods
1
| INTRODUCTION
problem since the fascinating chemistry was introduced
[
6]
by the landmark report of Friedel and Crafts. The for-
mation of C–Si bond has been reached to the extensive
levels of sophistication by the efforts of Grubbs and
[
1]
Silicon is the most abundant element in nature. It is
often a major constituent element in sand and found only
in traces in biological systems. Some living organisms can
engineer their shell structures by utilizing silica‐
precipitating proteins. Trypsin is reported to show pro-
miscuous activity in the metabolism of alkoxysilanes. The
family of silicate in enzymes from marine sponges is
unique for catalyzing the formation of organosiloxane
[
7]
[8]
[9]
[10]
[11]
Stolz, Hiyama, Hartwig, Oestreich,
Huang,
[
12]
and Arnold.
The alkenylsilanes are important synthons that are fre-
quently utilized in various synthetic transformations.
They are key coupling partners in Hiyama coupling,
Hiyama‐Denmark coupling, and silyl‐Heck reactions.
Stork described alkenylsilanes as carbonyl precursors in
annelation reactions.
[2]
[13]
[14]
[3]
structures.
Despite the limited availability of
[
15]
organosilicon compounds in living systems, synthetic
chemistry has provided us straightforward access. The
organic compounds containing silicon are important con-
stituents for molecules of chemistry and material science
interest. Silicon is a carbon isostere, the biocompatibil-
ity of silicon can be used to optimize and reconstituting of
The reported methods for the
synthesis of alkenylsilanes involves the reaction of
chlorotriorganosilanes
magnesium reagents,
with
organolithium/organo-
[
16]
silyl–Heck reaction of
[4]
[17]
halosilanes,
alkynes,
hydrosilylation and silylmetalation of
[
18]
[19]
and dehydrogenative silylation of alkenes.
[5]
the pharmacology of bioactive molecules. The silicon
supply in nature is more abundant, but the sustainable
methods for synthesizing organosilicon compounds are
limited. The affinity of silicon towards carbon to form a
carbon‐silicon (C–Si) bond is an interesting research
However, they require low temperatures, prolonged reac-
tion times, lack of regio‐ and stereoselectivity, require-
ment of precious transition metal catalysts, generation
of large quantity of halogenated waste, use of a huge
excess of activated olefins, formation of polymeric side
products, and moderate yields of trialkyl (alkenyl)silanes.
So, the development of highly regioselective methods for
*
Bharat Kumar Allam and Sadaf Azeez contributed equally to this work.
Appl Organometal Chem. 2019;e5192.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5192

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ALLAM ET AL.
1
3
the synthesis of trialkyl (alkenyl/alkynyl)silanes using
sustainable and economic starting materials are highly
valuable and in constant demand.
at 500 MHz, C NMR at 125 MHz). Chemical shifts for
protons are reported in parts per million downfield from
tetramethylsilane and are referenced to residual deute-
rium in the solvent ( H NMR: CDCl at 7.26 ppm). Chem-
ical shits for carbons are reported in parts per million
downfield from tetramethylsilane and are referenced to
the carbon resonances of the solvent peak ( C NMR:
1
Carboxylic acids are the naturally prevalent functional
groups found in organic molecules and serve as adaptable
synthetic building blocks. Through the extrusion of CO2,
carboxylic groups can act as traceless reactivity guiding
functionalities to construct simple to complex molecules.
Gooßen and MacMillan most extensively explored the
decarboxylative functionalizations for C–C bond forma-
3
13
CDCl at 77.0 ppm). NMR data are represented as fol-
3
lows: chemical shift, multiplicity (s = singlet, d = doublet
and m = multiplet), coupling constant (J) (Hz), and inte-
gration. HRMS was determined using Agilent 6530
Accurate–Mass Q–TOF instrument. Analytical thin layer
chromatography (TLC) was performed on Merck
Kieselgel 60 GF254 plates (thickness 0.25 mm). Visualiza-
tion was performed with a 254 nm UV lamp and by stain-
ing in I2 chamber. Organic solutions were concentrated
under reduced pressure using a Büchi rotary evaporator.
Purification of the crude products was carried out by col-
umn chromatography using silica gel 100–200 mesh. All
the reactions were carried out under an open atmosphere
using oven‐dried glassware. Yield refers to the isolated
analytically pure material (See Supporting Information).
[20]
tion. On the other hand, the decarboxylative C–X bond
[
21]
[22]
[23]
formation currently limited to the C–N, C–P, C–S,
[24]
[25]
[26]
C–F,
C–Br,
and C–I
bond creation. Particularly,
the formation of C–Si bond, an analogues bond to the C–
C bond, using decarboxylative functionalization has not
[27]
been studied well.
In this context, Liu et al. explored a
copper‐catalyzed decarboxylative C–Si bond formation
between unsaturated carboxylic acids and silanes, for the
27a
first time. In fact, it is the only method so far available
in the literature for C–Si bond formation between unsatu-
rated carboxylic acids and silanes. Hence, we believed that
there is enough room for the development of mild, selec-
tive, economical and high yielding methods for the C–Si
bond formation using sustainable and cheap silane feed
stocks. Nickel is an indispensable metal in organic synthe-
sis which is explored in many decarboxylative cross‐
2
.2 | General experimental procedure
Under air a mixture of α,β–unsaturated carboxylic acid
2 mmol), trialkyl silane (5 mmol), Ni (dmg) (20 mol%),
[28]
27b
coupling reactions.
In this context, Rueping et al.
(
27c
2
and Shi et al. have recently demonstrated a nickel pro-
moted decarbonylative silylation of aryl esters. However,
to best of knowledge, a decarboxylative C–Si bond forma-
tion between unsaturated acids and silanes is not explored
with nickel catalysts.
TBHP (6 mmol) were taken in a 10 ml glass vial contain
a Teflon coated magnetic stirr bar and the reaction mix-
ture was further heated up to 60 °C for 12 hr. After com-
pletion of the reaction (TLC) water was added. The
reaction mixture was filtered and partitioned in between
water and ethyl acetate. The organic layer was dried over
Na SO , evaporated by using a rotary evaporator. The res-
idue thus obtained was further subjected to silica gel col-
umn chromatography using a mixture of ethyl acetate
and hexane as an eluent (See supporting Information).
Given all the above facts, here we have developed a
nickel catalyzed decarboxylative silyl functionalization
strategy via the reaction of trialkyl silanes with (E)‐
cinnamic acids/alkynoic acids, to deliver trialkyl
2
4
(alkenyl/alkynyl)silanes (Scheme 1).
2
2
| EXPERIMENTAL SECTION
3 | RESULTS AND DISCUSSION
.1 | General experimental information
To establish optimized reaction conditions, we initially
screened a reaction between (E)‐cinnamic acid (1a) and
Proton and carbon magnetic resonance spectra were
recorded on a Bruker Avance 500 MHz NMR ( H NMR
triethylsilane (2a) using 10 mol% of Ni (dmg) , 100 mol%
of TBHP at 60 °C under solvent‐free conditions (Table 1).
2
1
SCHEME 1 Decarboxylative C–Si bond
formation.

ALLAM ET AL.
3 of 6
a
TABLE 1 Optimization of various parameters for decarboxylative silylation
b
S. No
Catalyst (mol%)
Accelerator (mol%)
T(°C)
Solvent
Yield (%)
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
.
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
Ni (dmg)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
(10)
(10)
(10)
(10)
(20)
(30)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
TBHP (100)
TBHP (200)
TBHP (300)
TBHP (400)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
TBHP (300)
60 °C
60 °C
60 °C
60 °C
60 °C
60 °C
40 °C
rt
–
–
–
–
–
–
–
–
–
45
.
53
.
60
.
40
c
.
87 (42)
.
82
.
50
.
trace
80
.
80 °C
60 °C
60 °C
60 °C
60 °C
60 °C
60 °C
60 °C
60 °C
60 °C
60 °C
0.
1.
2.
3.
4.
5.
6.
7.
8.
9.
CH
3
CN
55
t
BuOH
79
DCE
71
1,4‐dioxane
DMSO
DMF
65
50
32
THF
60
H
2
O
45
C
6
H
6
80
Toluene
57
a
1a (2 mmol), 2a (5 mmol), for 12 hr.
b
Isolated yield after column chromatography.
c
Reaction conducted with 70% TBHP (in water).
The reason behind the selection of nickel (II) dimethy-
further increase of catalyst mol% slightly diminished the
reaction yield (entry 6). Also, altering the reaction temper-
ature from 60 °C, delivered the desired product in dimin-
ished yield (entries 7 & 9). The reaction provided only a
lglyoxime complex as catalyst was that, Ni (dmg) is a
2
bench stable compound which is most commonly available
in research laboratories. Ni (dmg) is often used for elec-
2
trode surface modifications, as catalyst for oxygen reduc-
tion, and as an active site to promote hydrogen
trace of product at room temperature (entry 8). Various
t
polar and non‐polar solvents, Viz., CH CN, BuOH, DCE,
3
[29]
generation. However, Ni (dmg) is less explored as cata-
1,4‐dioxane, DMSO, DMF, THF, H O, C H , and toluene
2
2
6
6
[30]
lysts for synthetic organic transformations.
have initially assessed the catalytic efficiency of Ni
dmg) in C‐Si bond forming reaction. To our delight, we
Hence, we
were screened for their proficiency, and none match the
efficiency of solvent‐free conditions (entries 10–19). Vari-
ous salts of nickel, other metals, metal‐free conditions,
and accelerators were screened, and found that Ni (dmg)2
and TBHP combination is the best (See the supporting
information). It was interesting to mention here that
(
2
observed the formation of (E)–triethyl (styryl)silane (3a)
in 45% yield (entry 1). Later we raised the mol% of TBHP
to 300, which provided 53% yield of the product (entry 2).
But a further variation of TBHP concentration to
20 mol% BMIM[BF ] along with 300 mol% TBHP pro-
4
4
00 mol% did not provided a higher yield, surprisingly it
moted the reaction and delivered the product in 83% yield
diminished the product yield (entry 3). As an obvious alter-
(Cf. Supporting information).
native, we increased the Ni (dmg) to 20 mol%, which pro-
After all, the combination of Ni (dmg) and TBHP was
2
2
vided a maximum yield of 87% at 60 °C (entry 5). However
crucial and necessary for the decarboxylative silylation

4
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ALLAM ET AL.
reaction. The optimized reaction conditions [20 mol% Ni
dmg) , 3 equivalents of TBHP at 60 °C for 12 hr under
on lowering the reaction yield, perhaps, due to the steric
hindrance. For instance, the installation of methyl or
chloro substituent at ortho position of cinnamic acid lead
the formation of desired products in slightly lower yields
(Table 2, 3 h‐3j). It is worth noting that a highly sensitive
thiophene or furan containing α,β–unsaturated carboxylic
acids were also fruitfully utilized as coupling partners
(Table 2, 3 k‐3 l). Similar to cinnamic acids, a
decarboxylative coupling of naphthyl acrylic acid with
triethylsilane was successfully accomplished under opti-
mized condition in 73% yield. It is also interesting to note
that the hydroxyl group present on the substrate found to
be intact during the coupling reaction, which demon-
strate the mildness of the reaction conditions. Having
explored the substrate scope with different cinnamic
acids, coupling reactions were investigated with different
silanes. To our delight, similar to triethylsilane, tri‐
(
2
solvent‐free conditions], proved to apply to a wide range
of cinnamic/alkynoic acids in combination with trialky-
lsilanes having linear or branched alkyl chains (Table 2).
Initially, the reaction was tested between triethylsilane
and cinnamic acids bearing electron‐donating and with-
drawing groups under optimized conditions. It was
observed that cinnamic acids having electron‐donating
groups such as methyl and methoxy, gave the desired
products in excellent yields, i.e. 82–90% (Table 2, 3b‐3d).
Nevertheless, the electron‐withdrawing groups such as
nitro, fluoro and chloro functionalized cinnamic acids
were also participated in these coupling reactions with
similar reactivity and provided the desired products in
comparable yields (Table 2, 3e‐3 g). However, the ortho‐
substituent on the cinnamic acids has a profound effect
a,b
TABLE 2 The substrate scope for the decarboxylative C–Si bond formation
a
1
a (2 mmol), 2a (5 mmol), Ni (dmg)
2
(20 mol%), TBHP (decane) (6 mmol) heated up to 60 °C for 12 hr.
b
Isolated yield after column chromatography.

ALLAM ET AL.
5 of 6
isopropyl and dimethylphenyl silanes also participated in
the coupling reactions with different cinnamic acids pro-
viding the desired products 3n‐3v in 46–84% yields.
Similar to cinnamic acids, alkynoic acids also partook
as excellent coupling partners in the decarboxylative cou-
pling reactions with different linear and branched
trialkylsilanes under optimized conditions. These reac-
tions provided the desired products 3w‐3y in 65–85%
yields. To our surprise coupling of triphenylsilane with
cinnamic acids was resulted in no yield while with
in 75% yield suggesting that there is only a minimum
effect of oxygen in the reaction.
Based on the above control experiments and reported
27a, 31
literatures,
a plausible mechanistic pathway is
outlined in Scheme 2. We believe that the reaction pro-
ceeds through a Ni (III)Si complex (I) formed from the
reaction of Et SiH (2a) with Ni (dmg) in the presence
3
2
of TBHP. The Ni (III)Si complex efficiently delivers
trialkyl silyl radical, which undergo addition to cinnamic
acid double bond and provides the intermediate II. Fur-
ther, the intermediate (II) undergoes a decarboxylation
via intermediate (III) in the presence of hydroxyl ion to
3‐phenylpropiolic acid provided 65% yield. It was quite
unfortunate to report that all our efforts to utilize trialky-
lgermanes as coupling partners failed. Over all, under
optimized condition various functional groups, such as
nitro, ether, halo, and hydroxy were well tolerated in
these reactions.
27a
deliver the desired (E)‐trialkyl (alkenyl)silanes.
4
| CONCLUSIONS
Control experiments were conducted to further under-
stand and envision the reaction mechanism using
cinnamic acid (1a) and triethylsilane (2a) (See the
supporting information). The free radical trapping
reagents BHT and TEMPO have completely seized the
reaction indicating a radical type reaction mechanism.
A blank experiment was undertaken with triethylsilane
in the absence of cinnamic acid (1a) under standard reac-
tion conditions, and we did not find the formation of
In conclusion, we have a developed a nickel catalyzed
decarboxylative silylation strategy under mild conditions.
The application of dmg as a ligand tunes the Lewis acidity
of the nickel and safeguard the α,β‐unsaturated silanes
from further nickel catalyzed C–Si bond cleavage/
decomposition. The method efficiently used the otherwise
difficult and less reactive trialkyl silanes to deliver trialkyl
(
alkenyl/alkynyl)silanes. This method opens windows to
explore various transformations using aliphatic silanes.
Further studies to expand the scope of chemistry with
trialkylgermanes using various metal complexes are
underway in our laboratory.
1
,1,1,2,2,2‐hexaethyldisilane indicating the possibility of
forming a nickel (III)Si complex which efficiently trans-
fers the triethylsilyl group to the unsaturated carboxylic
acid. We have also conducted a reaction between
cinnamic acid and 1,1,1,2,2,2‐hexaethyldisilane under
standard reaction conditions, which only provided a trace
amount of product. To identify the role of light, the reac-
tion was investigated in dark and isolated the desired
product (3a) in 85% yield. It suggests that the light have
no significant effect on the reaction outcome/yield. Fur-
ther, we have investigated the reaction under inert (N2)
atmosphere. This reaction provides the desired product
ACKNOWLEDGMENTS
Dr. J. K. acknowledges Max‐Planck Society‐Germany and
DST‐India (DST/INT/MPG/P‐09/2016) for financial sup-
port through the Indo‐Max Planck partner group project.
J. K. also acknowledges DST‐SERB for the young scientist
start‐up research Grant (YSS/2014/000236). Dr. Bharat
Kumar Allam acknowledges Science and Engineering
Research Board (DST), New Delhi for the award of
National Post‐Doctoral Fellowship (Grant No. PDF/2016/
000068). Ms. Sadaf Azeez thanks CSIR, New Delhi for
the JRF.
ORCID
Jeyakumar Kandasamy https://orcid.org/0000-0003-3285-
971X
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SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of the
article.
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