Silylcarboxylic Acids as Bifunctional Reagents: Application in Palladium-Catalyzed External-CO-Free Carbonylative Cross-Coupling Reactions

Article abstract of DOI:10.1002/adsc.202000586

A palladium-catalyzed external-CO-free carbonylative Hiyama-Denmark cross-coupling reaction is presented. The introduction of silylcarboxylic acids as bifunctional reagents (CO and nucleophile source) avoids the need for external gaseous CO and a silylarene coupling partner. The transformation features high functional group tolerance and it is successful with electron-rich, -neutral, and -poor aryl iodides. Stoichiometric studies and control experiments provide insight into the reaction mechanism and support the hypothesized dual role of silylcarboxylic acids. (Figure presented.).

Full text of DOI:10.1002/adsc.202000586

Title: Silylcarboxylic Acids as Bifunctional Reagents: Application in
Palladium-Catalyzed External-CO-Free Carbonylative Cross-
Coupling Reactions
Authors: Xiong Li, Jie Xu, Yue Li, Soren Kramer, Troels Skrydstrup,
and Zhong Lian
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000586
Link to VoR: https://doi.org/10.1002/adsc.202000586

10.1002/adsc.202000586
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.202((will be filled in by the editorial staff))
Silylcarboxylic Acids as Bifunctional Reagents: Application in
Palladium-Catalyzed External-CO-Free Carbonylative Cross-
Coupling Reactions
XiongLi,+a JieXu,+a Yue Li,a SørenKramer,b Troels Skrydstrup,c Zhong Liana,*
a
Department of Dermatology, State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, and West
China School of Pharmacy, Sichuan University, Chengdu 610041, China
E-mail: lianzhong@scu.edu.cn
Department of Chemistry, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark
b
c
Carbon Dioxide Activation Center, Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry,
Aarhus University, Gustav WiedsVej 14, 8000 Aarhus C, Denmark
+
These authors contributed equally.
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
been used for various carbonylation reactions.[12] All
Abstract:
A
palladium-catalyzed external-CO-free
carbonylative Hiyama-Denmark cross-coupling reaction
is presented. The introduction of silylcarboxylic acids as
bifunctional reagents (CO and nucleophile source)
avoids the need for external gaseous CO and a silylarene
coupling partner. The transformation features high
functional group tolerance and it is successful with
electron-rich, -neutral, and -poor aryl iodides.
Stoichiometric studies and control experiments provide
insight into the reaction mechanism and support the
hypothesized dual role of silylcarboxylic acids.
the above-mentioned CO sources have their own
merits, but they play only one role: providing CO for
carbonylation, while the byproducts are treated as
waste.
In 2016, we developed a palladium-catalyzed
carbonylative
Hiyama-Denmark
cross-coupling
reaction, in which CO2 is initially reduced by a
disilane forming CO and a disiloxane byproduct.
Importantly, instead of being discarded as waste, the
generated disiloxane takes part in the carbonylative
cross-coupling with aryl iodides producing
diarylketones (Scheme 1b).[13] This transformation
combines the CO2 reduction with the carbonylative
Hiyama-Denmark coupling reaction efficiently, but
the handling is inconvenient due to the requirement
of a two-step operation and the need for external
gaseous CO2.
Keywords:Carbonylation; Cross-coupling; Hiyama-
Denmark; Palladium-catalysis
Transition-metal-catalyzed
carbonylative
cross-
coupling reactions are considered to be one of the
most efficient methods for synthesizing a diverse
array of carbonyl compounds. Such carbonylations
are widely utilized in pharmaceutical synthesis,[1]
total synthesis of natural products[2], and valuable
chemical manufacturing in industry[3]. Carbonyl
group installation can be realized by employing
carbon monoxide (CO), an economical one-carbon
building block. However, the toxic nature of CO and
the inconvenience of high-pressure storage limit its
practical use. In the past decades, CO surrogates such
as chloroform,[4] aldehyde,[5] transition-metal
carbonyl complexes,[6] N-formylsaccharin,[7] oxalyl
chloride,[8] and others[9] have been developed
(Scheme 1a). Additionally, our group invented two
As a continuation of our interest in streamlining
carbonylation reactions, we envisioned that it might
be possible to combine the CO source and
transmetallating agent into one molecule. By using
this approach, the addition of a single, bifunctional
reagent could facilitate carbonylative cross-coupling
reactions and eliminate any need for external gas
supply during the reactions. Notably, we have
previously developed the silylcarboxylic acid,
silaCOgen, as
a
solid CO precursor, and
demonstrated the potential as an ex-situ CO
source.[11a] Silylcarboxylic acids are easily prepared
on
a
multigram-scale from CO2. Subsequent
liberation of CO is promoted by fluoride sources
leading to a silanol byproduct. However, based on
our previous experience and the previous work by
others[14], we hypothesized that, instead of being
new CO precursors, Cogen[10] and SilaCOgen[11]
which combined with a two-chamber reactor, have
,
1
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10.1002/adsc.202000586
Advanced Synthesis & Catalysis
wasted, the silanol could serve as an in-situ generated
nucleophile for carbonylative Hiyama-Denmark
cross-coupling reactions. Thus, the silylcarboxylic
acid would play a dual role as both CO source and
precursor for the nucleophilic cross-coupling partner.
Previously, phenyl formate and DMF have been
utilized for formal alkoxy- and aminocarbonylations,
but these reactions do not involve release of CO
(Scheme 1c).[15,16] To date, our previous report
involving external gaseous CO2 is the only example
of catalytic ketone formation employing a dual role
CO precursor.
entry ‘Pd’
co-cat. Ligand Solvent Yield(3a)b)
1
2
Pd(dba)2
-
Pd(OAc)2 -
Pd(TFA)2 -
Pd(acac)2 -
-
-
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
12%
7%
3
4
-
-
-
-
15%
20%
20%
22%
5
6
7
8
PdCl2
PdBr2
PdI2
PdI2
PdI2
PdI2
PdI2
PdI2
PdI2
PdI2
PdI2
PdI2
PdI2
PdI2
PdI2
-
-
-
-
-
27%
L1-L4
L5-L13 DMF
5%-10%[c]
8%-40%[c]
50%
9
-
10
11
12
13
14
15
16
17
18
19
CuI
Cu-1
Cu-2
Cu-2
Cu-2
Cu-2
Cu-2
Cu-2
Cu-2
Cu-2
Cu-2
Cu-2
Cu-2
L6
L6
L6
L6
L6
L6
L6
L6
L6
L6
L6
L6
L6
DMF
DMF
DMF
DMA
NMP
DMSO 60%
toluene trace
dioxane 0%
THF
CH3CN trace
NMP
NMP
NMP
62%
74%
55%
91%
0%
20[d] PdI2
21
22[e] PdI2
75%
0%
0%
-
Scheme 1. Overview of Single and Dual Role CO-
precursors.
The optimization of this transformation was
initiated with 1-iodo-4-methoxybenzene 1a and
methyl diphenylsilanecarboxylic acid 2a, using
Pd(dba)2 as catalyst, CsF as promotor, and DMF as
solvent at 110 °C. After 1 h, the desired product (4-
methoxyphenyl)(phenyl)methanone (3a) was formed
in 12% yield (Table 1, entry 1). A subsequent
screening of palladium sources led to identification of
PdI2 as the best-performing palladium source (Table
1, entries 2-7). Interestingly, the addition of
phosphine ligands inhibited the reaction (Table 1,
entry 8). In contrast, the use of nitrogen ligands
generally led to improved yields (Table 1, entry 9).
Among them, bipyridine and phenanthroline-based
ligands (L5-L10) performed well, especially L6,
while bidentate amine ligand (L11-L13) led to lower
yields. Addition of copper co-catalysts further
improved the yield of 3a (Table 1, entries 10-12).
Among the various solvents tested, NMP showed the
best performance (Table 1, entries 13-19). Employing
dimethyl(phenyl) silanecarboxylic acid 4 instead of
2a retarded the transformation (Table 1, entry 20).
[a]Reactions in this table were performed under an Ar
atmosphere at 0.2 mmol scale.
[b]Yields were determined by GC using dodecane as an
internal standard.
[c]See individual yields by the ligand structures below the
table.
[d]Using 4 instead of 2a.
[e]Using PhBr or PhCl instead of 1a.
A control experiment revealed that the palladium
catalyst is essential for the reaction to take place
(Table 1, entry 21). Unfortunately, We found that
bromobenzene and chlorobenzene failed to proceed
this carbonylation. (Table 1, entry 22). Finally, the
optimized reaction conditions for this carbonylative
Table 1. Optimization of Reaction Conditions for the
CarbonylativeHiyama-Denmark Cross-Coupling Reaction
with a Silylcarboxylic Acid[a]
2
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10.1002/adsc.202000586
Advanced Synthesis & Catalysis
cross-coupling utilizes 5 mol % PdI2, 10 mol % Cu-2,
and 5 mol % L6 as catalyst precursors, 1.8 equiv2a as
CO source, 2.7 equivCsF as additive, and NMP as
solvent at 110 °C for 1 h (Table 1, entry 14).
substituents, such as acetyl (3o), trifluoromethyl (3p),
and cyano (3q) also successfully underwent the
carbonylative cross-coupling reaction. Aryl iodides
containing a 3-methoxy group and an ester afforded
the diarylketone products in moderate to good yields
(3r–s). Even a 5-iodo-isatin, which contains a highly
reactive carbonyl group, led to a synthetically useful
yield of the desired ketone (3t). Several heterocyclic
aryl iodides were well-tolerated such as indole (3u),
thiophene (3v), 2-, 3-, and 4-pyridine (3w–y),
pyrazole (3z), and quinoline (3aa). Finally, different
aryl silylcarboxylic acids containing methyl
substituents on the benzene ring were examined.
Pleasingly, no influence of the positioning of the
methyl group was observed as ortho-, meta-, and
para-methyl-substituted aryl silylcarboxylic acids all
provided comparable yields for the carbonylative
Hiyama-Denmark cross-coupling reaction (3ab–ad).
Moreover, tert-butyl-substituted aryl silylcarboxylic
acid could react with 4-iodobenzonitrile to give the
corresponding ketone (3ae) in a moderate yield.
Lastly, on a 5.0 mmol scale, ketone 3a was formed in
61% yield from the corresponding Aryl iodide.
Scheme 2. Substrate Scope Investigation for both Aryl
Iodides and Silylcarboxylic Acids. Unless Otherwise noted,
reactions in this scheme were performed at 0.2 mmol scale.
[a]Reaction was performed at 5.0 mmol.
With satisfactory reaction conditions established,
we next evaluated the scope of this carbonylative
Hiyama-Denmark cross-coupling reaction. First,
electron-rich aryl iodides were investigated. We
found that methyl-substituted iodobenzenes produced
the corresponding ketones in excellent yields, even
when the methyl group imposes sterical hindrance in
the ortho-position (3b–c). Other electron-donating
substituents such as amine (3d), pyrrole (3e),and
dihydrobenzofuran (3f) were well-tolerated. The use
of electron-neutral aryl iodides also led to high yields
of the desired carbonylative cross-coupling products.
This is demonstrated with the successful coupling of
iodobenzene as well as substrates bearing phenyl,
alkenyl, and naphthyl substituents (3g–k). Next, the
reactivity of electron-deficient aryl iodides was
studied. Notably, this methodology proved to be
highly efficient in the presence of other aryl halides
(3l–3n) which can serve as useful handles for further
functionalization by other cross-coupling reactions.[17]
Substrates bearing strongly electron-withdrawing
Scheme 3. Investigation of the Reaction Mechanism.
To gain more insight into the reaction mechanism
of the transformation, a few experiments were carried
out (Scheme 3). By heating a THF solution of 1-iodo-
4-methoxybenzene (1a) and stoichiometric amounts
of Pd(dba)2 and L6 to 50 °C for 5 h, the oxidative
addition complex I was isolated in 19% yield.[18] The
structure of
I
was confirmed by X-ray
crystallography.[19] Under a CO atmosphere (THF,
50 °C), palladium complex I was cleanly transformed
into the CO insertion complex II, which was isolated
in 90% yield. Under the standard catalytic conditions,
the use of palladium complex I instead of PdI2 led to
80% yield of 3a. Furthermore, the treatment of
3
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10.1002/adsc.202000586
Advanced Synthesis & Catalysis
Experimental Section
palladium complex II with methyldiphenylsilanol in
the presence of 2.0 equiv Cu-2 and 2.7 equivCsF in
NMP led to the formation of compound 3a in 50%
yield, thus clearly indicating the potential of the
silanolbyproduct as transmetallating agent.
General procedure: In the glovebox, aryl iodide 1 (0.2
mmol, 1.0 equiv), silacarboxylic acid 2 (3.6 mmol, 1.8
equiv), PdI2 (0.01 mmol, 5 mol %), Phenanthroline (0.01
mmol, 5 mol %), CuTc (0.02 mmol, 10 mol %), and CsF
(0.54 mmol, 2.7 equiv) were added into an oven-dried 15
mL vial with a magnetic stirring bar, followed by addition
of NMP (1.0 mL). The vial was sealed and heated to
various temperature. After 1 h, the vial was cooled to room
temperature. The residue was purified by flash column
chromatography to give the desired product.
Based on the results shown above, a plausible
mechanism is proposed (Figure 1). First,
silylcarboxylic acid (2a) is promoted by CsF to
release
CO
and
silanolate.
Meanwhile,
phenanthroline-ligated Pd(0) can undergo oxidative
addition into 1-iodo-4-methoxybenzene (1a) forming
palladium complex I. This complex can evolve into
palladium complex II by addition of the CO released
from the silylcarboxylic acid. Next, silanolate III
enter the cycle via ligand exchange. The formed Cu–
silanolate IV proceed the transmetallation with
complex II to furnish a Pd(II) complex V,[13,20]
followed by ß-Ph elimination to generate complex VI.
Finally, reductive elimination of product 3a closes
the catalytic cycle.
Acknowledgements
This work is supported by funding from National Natural Science
Foundation (Nos. 21901168), and start-up funding from Sichuan
University. S.K. thank the Lundbeck Foundation (Grant No.
R250-2017-1292) and the Technical University of Denmark for
generous financial support. T.S. is highly appreciative of funding
from the Danish National Research Foundation (grant no.
DNRF118), NordForsk (grant. no. 85378) and Aarhus University.
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In summary, we have developed
a novel
methodology where the CO precursor serves a dual
purpose: 1) providing CO for the carbonylation and
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carbonylative
reaction. This transformation provides
Hiyama-Denmark
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new
a
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10.1002/adsc.202000586
Advanced Synthesis & Catalysis
J. Am. Chem. Soc.2015, 137, 19, 6192–6199
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Advanced Synthesis & Catalysis
COMMUNICATION
Silylcarboxylic Acids asBifunctional Reagents:
Application in Palladium-Catalyzed External-CO-
Free Carbonylative Cross-Coupling Reactions
Adv. Synth. Catal.Year, Volume, Page – Page
+
+
Xiong Li, Jie Xu, Yue Li, Søren Kramer, Troels
Skrydstrup, Zhong Lian*
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