Direct Access to 1,1-Dicarbonyl Sulfoxonium Ylides from Aryl Halides or Triflates: Palladium-Catalyzed Carbonylation

Article abstract of DOI:10.1021/acs.orglett.9b01926

The synthesis of 1,1-dicarbonyl sulfoxonium ylides by palladium-catalyzed carbonylation of aryl halides or triflates with α-carbonyl sulfoxonium ylides has been developed for the first time. This method provides a general approach to synthetically useful 1,1-dicarbonyl sulfoxonium ylides in high efficiency. The protocol displays a wide substrate scope, showing that the resulting 1,1-dicarbonyl sulfoxonium ylides have been converted into the corresponding 1,3-dicarbonyl compounds.

Full text of DOI:10.1021/acs.orglett.9b01926

Letter
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
pubs.acs.org/OrgLett
Direct Access to 1,1-Dicarbonyl Sulfoxonium Ylides from Aryl
Halides or Triflates: Palladium-Catalyzed Carbonylation
Yang Yuan and Xiao-Feng Wu*
̈
Leibniz-Institut fur Katalyse e.V., Universitat Rostock, Albert-Einstein-Straße 29a, 18059 Rostock, Germany
̈
*
S Supporting Information
ABSTRACT: The synthesis of 1,1-dicarbonyl sulfoxonium
ylides by palladium-catalyzed carbonylation of aryl halides or
triflates with α-carbonyl sulfoxonium ylides has been
developed for the first time. This method provides a general
approach to synthetically useful 1,1-dicarbonyl sulfoxonium
ylides in high efficiency. The protocol displays a wide substrate scope, showing that the resulting 1,1-dicarbonyl sulfoxonium
ylides have been converted into the corresponding 1,3-dicarbonyl compounds.
16b
he transition-metal-catalyzed carbonylation reaction has
now emerged as one of the most powerful methods for
(Figure 1, eq 1), and intramolecular transformations using
rhodium catalysts were studied by the research group of
T
the synthesis of carbonyl-containing compounds, and a variety
of value-added bulk and fine chemicals are available by this
1
transformation. Since the pioneering work of Heck and
coworkers in 1974, palladium-catalyzed carbonylative coupling
reactions of aromatic halides have undergone rapid develop-
2
ment during the recent years. Palladium-catalyzed carbon-
ylations of aryl halides, followed by the attack of different types
of nucleophiles such as alcohols, amines, and water, are known
as alkoxycarbonylation, aminocarbonylation, and hydroxycar-
3
bonylation. In particular, they have been used for the
4
5
synthesis of a wide range of valuable esters, amides,
6
7
8
9
carboxylic acids, aldehydes, ketones, and heterocycles.
10
Sulfur (sulfonium and sulfoxonium) ylides have served as
significant synthetic precursors in many organic trans-
formations, such as aziridinations, epoxidations, cyclopropana-
11
tions, olefinations, and rearrangements. Their synthetic
potential was demonstrated in the synthesis of various natural
12
products, pharmaceuticals, and chemical materials as well. In
13
addition, sulfoxonium ylides were used as versatile carbenoid
14
precursors in X−H (X = C, N, O, S) insertion reactions, and
transition-metal-catalyzed C−H functionalization has been
Figure 1. Synthesis of 1,1-dicarbonyl sulfoxonium ylides.
1
5
well developed. Consequently, it would be desirable to
develop general protocols for the preparation of sulfoxonium
17
̈
Moody. In 2017, Vaitla and coworkers demonstrated the
direct synthesis of 1,1-dicarbonyl sulfoxonium ylides from
malonates and sulfoxides via an iodonium ylide generated in
ylides. Here it is important to mention that Aissa and
coworkers developed an interesting palladium-catalyzed
procedure for the synthesis of bis-substituted sulfoxonium
18
1
1g
suit (Figure 1, eq 2). The groups of Nemykin and Zhdankin
developed a highly soluble iodonium ylide, which could be
transformed into sulfoxonium ylides with DMSO by using
ylides in 2018. By directly cross-coupling aryl halides and
aryl triflates with α-ester sulfoxonium ylides, good yields of the
desired ylides can be obtained. In 1964, Ko
reported their work on the acylation of trimethylsulfoxonium
̈
nig and Metzger
19
Rh (OAc) as the catalyst. On the basis of our continuous
2
4
1
6a
interest in carbonylations, and to the best of our knowledge,
sulfoxonium ylides as the nucleophiles in the carbonylative
reactions have not been reported until recently. Herein, we
think a complementary practical approach to this interesting
ylide with benzoic anhydride.
However, methods to
synthesize 1,1-dicarbonyl sulfoxonium ylides were still limited.
In general, these ylides can be prepared from the generation of
carbenoids by transition-metal-catalyzed decomposition of
diazo compounds or iodonium ylides. In 1970, Dost and
Gosselck reported the decomposition of diazo compounds to
provide sulfoxonium ylides by using copper and silver salts
Received: June 4, 2019
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.9b01926
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
,1-dicarbonyl sulfoxonium ylides can be achieved by the
Letter
1
DPEphos (10 mol %), and Cs CO (1.1 equiv) in CH CN at
2
3
3
carbonylation of aryl halides with sulfoxonium ylides.
100 °C under CO (10 bar) for 20 h.
To verify our hypothesis, we initially chose α-estersulfoxo-
nium ylide (2a) and iodobenzene (1a) as the model substrates,
with Pd(PPh ) as the catalyst. We discovered that the desired
We then explored the substrate scope of aryl halides with
sulfoxonium 2a (Scheme 1). A variety of aryl iodides bearing
electron-donating substituents at the para positions were
successfully converted to the desired products 3a−3g and 3p
3
4
product 3a was formed in 72% yield using Cs CO (2 equiv)
2
3
as the base in CH CN under 10 bar of CO gas pressure at 100
3
°
C (Table 1, entry 1). The yield of 3a could be increased to
Scheme 1. Substrate Scope of Various Aryl Halides and
Triflates
a
a
Table 1. Screening of Reaction Conditions
entry
X
[Pd]
ligand (mol %)
yield (%)
72
80
48
28
33
65
trace
48
63
1
2
3
4
5
6
7
8
9
I
I
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd (dba)
b
Br
OTf
I
I
I
I
PPh (10)
2
3
3
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
PPh (10)
3
PCy (10)
3
BUPAd (10)
2
T
I
Bu P·HF (10)
3
4
10
11
12
13
14
15
16
17
I
I
I
I
DPPE
<5
69
Xantphos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
78
88
c
c
c
c
c
,
,
,
,
d
d
d
d
I
89
80
81
86
Br
OTf
I
,
e
a
Reaction conditions: 2a (0.2 mmol), 1 (0.3 mmol), [Pd] (2.5 mol
), ligand (5.0 mol % or 10 mol %), CH CN (1.0 mL), Cs CO (2.0
%
3
2
3
b
equiv), CO (10 bar), 100 °C, 20 h, isolated yield. Pd(PPh ) (5.0
mol %). Pd(OAc) (5.0 mol %), DPEphos (10 mol %). Cs CO
3
4
c
d
2
2
3
e
(
1.1 equiv). 80 °C.
8
0% with 5 mol % Pd(PPh ) (Table 1, entry 2). Gratifyingly,
3 4
the reaction could also give 3a in 48% yield and 28% yield
when the bromobenzene or phenyl triflate was used as the
substrate (Table 1, entries 3 and 4). However, product 3a was
always mixed with small amounts of triphenylphosphine oxide,
even after two applications of flash chromatography. Therefore,
we decided to identify alternative conditions to avoid the
impurity. We thus evaluated different palladium precursors in
the presence of PPh ligand, and Pd(OAc) proved to be more
3
2
efficient than Pd (dba)3 (Table 1, entries 5 and 6).
2
Subsequently, the screening of various monodentate and
bidentate phosphine ligands showed that DPEphos was the
optimal ligand for this transformation (Table 1, entries 7−12).
An increase in the catalyst loading to 5 mol % Pd(OAc) and
2
1
0 mol % DPEphos gave 3a in 88% yield (Table 1, entry 13).
Reducing the base Cs CO to 1.1 equiv furnished the product
2
3
3
a in 89% isolated without any impurity (Table 1, entry 14).
Further exploration of the bases resulted only in a significant
decrease in the yield of 3a (Table S1). In particular,
bromobenzene and phenyl triflate were also well applicable
to this transformation to give the desired product 3a in high
yield (Table 1, entries 15 and 16). Therefore, the optimal
a
Reaction conditions: 2a (0.2 mmol), 1 (0.3 mmol), Pd(OAc) (5
2
mol %), DPEphos (10 mol %), CH CN (1.0 mL), Cs CO (1.1
3
2
3
equiv), CO (10 bar), 100 °C, 20 h, isolated yield. [a] Use aryl
triflates. [b] Use aryl bromides. [c] Use 5 mol % Pd(PPh3)4 as
catalyst. [d] Use vinyl triflate.
reaction conditions were defined as Pd(OAc) (5 mol %),
2
B
DOI: 10.1021/acs.orglett.9b01926
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
a
in good to excellent yield. The structure of 3a was confirmed
Scheme 3. Carbonylation of β-Ketosulfoxonium Ylides
2
0
by X-ray crystallography. Various electron-withdrawing
substituents such as fluoro, chloro, and trifluoromethyl, esters,
as well as ketones at the para positions of aryl iodides were all
well tolerated and afforded the corresponding substituted
products 3h−3o in 70−92% yield. Ortho- or meta-substituted
aryl halides were able to give the corresponding products in
moderate yield as well (3q−3t). Moreover, disubstituted aryl
iodides and bromonaphthalenes also reacted smoothly to
furnish the desired products 3u−3z in 60−86% yield.
Fortunately, benzodioxole- and quinoline- containing sub-
strates were successfully compatible under the reaction
conditions (3aa, 3ab, 71−93% yields). Importantly, hetero-
iodides such as 2-iodothiophene and 3-iodopyridine also
worked well, furnishing 3ac and 3ad in 74−78% yield. Vinyl
triflates were also well applicable in this transformation to give
the desired products 3ae−3ag in good yield, and these vinyl
triflates could be easily prepared from the corresponding
a
Reaction conditions: 1a (0.3 mmol), 2 (0.2 mmol), Pd(OAc) (2.5
2
mol %), DPEphos (5 mol %), CH CN (1.0 mL), Cs CO (1.1 equiv),
CO (10 bar), 80 °C, 20 h.
2
1
3
2
3
carbonyl compounds.
To demonstrate the potential
applications, the late-stage modification of natural products
and pharmaceutical derivatives was investigated. Camphor-,
estrone-, menthol-, and glucose-derived 3ah−3ak were all
isolated in good yield (68−90% yield, Scheme 1).
Under the optimized conditions, the scope of different α-
estersulfoxonium ylides 2 was subsequently examined (Scheme
in 41−85% yield. Interestingly, intramolecular reactions could
also smoothly proceed to form 3ax in 56% yield.
The practicability of the presented methodology was
demonstrated with a 4 mmol scale of reaction in the presence
of 2.5 mol % palladium catalyst, and the desired products 3a
and 3an were obtained in 91 and 90% yields, respectively
2
). The sulfoxonium ylides bearing an alkyl group gave the
(
Scheme 4, eq 1). As an application of the ylides, some of them
a
Scheme 2. Substrates Scope of α-Estersulfoxonium Ylides
Scheme 4. Gram-Scale Synthesis and Synthetic
a
Transformations
a
Reaction conditions: 1a (0.3 mmol), 2 (0.2 mmol), Pd(OAc) (5
2
mol %), DPEphos (10 mol %), CH CN (1.0 mL), Cs CO (1.1
3
2
3
equiv), CO (10 bar), 100 °C, 20 h, isolated yield.
a
(
a) Raney nickel, IPA, reflux, 2 h. (b) Aniline, [Ir(COD)Cl] (2 mol
2
expected products (3al−3ao) in excellent yield. However,
sulfoxonium ylide with an aryl group provided only the
corresponding product 3ap in 41% isolated yield.
%
), toluene, 150 °C. (c) Acetamide, [Ir(COD)Cl]2 (2 mol %),
toluene, 150 °C. (d) LiCl, MsOH, THF, 50 °C.
Meanwhile, we were wondering if this catalytic system could
be extended to the β-ketosulfoxonium ylides. To our delight, in
the reactions of iodobenzene 1a with β-ketosulfoxonium ylide
were subjected to a desulfurization reaction using Raney nickel
2
g under the above reaction conditions, the reaction could
in refluxing 2-propanol and provided respective 1,3-dicarbonyl
2
2
furnish the target product 3aq in moderate yield. Unfortu-
nately, although a detailed exploration of reaction parameters,
such as catalysts, bases, temperature, ligands, and solvents, was
carried out (Tables S2−S5), the yield of 3aq was only achieved
with up to 52% NMR yield and isolated in 41% yield. Then,
the substrate scope of β-ketosulfoxonium ylide (2g−2n) was
examined (Scheme 3). The β-ketosulfoxonium ylides bearing
an alkyl or aryl group gave the expected products (3aq−3aw)
compounds in good yield (72−78%, Scheme 4, eq 2a).
Furthermore, some known transformations were performed,
2
3
such as N−H and Cl−H insertions (Scheme 4, eqs 2b−d).
The treatment of sulfoxonium yield 3 with aniline or acetamide
in the presence of [Ir(COD)Cl] (1 mol %) in toluene at 150
2
°C afforded N−H insertion products 5 or 6 successfully.
Likewise, the treatment of 3a with LiCl and MsOH in THF at
50 °C gave the Cl−H insertion product 7 in 56% isolated yield.
C
DOI: 10.1021/acs.orglett.9b01926
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
In conclusion, we have developed the first palladium-
catalyzed carbonylation of α-estersulfoxonium ylides or β-
ketosulfoxonium ylides for the synthesis of 1,1-dicarbonyl
sulfoxonium ylides from easily available aryl halides and
triflates. This method provides a general approach to a variety
of synthetically useful 1,1-dicarbonyl sulfoxonium ylides in
good yield with ease of scale up. Additionally, the
desulfurization of representative sulfoxonium ylides success-
fully afforded the corresponding 1,3-dicarbonyl compounds.
Moreover, we also demonstrated that these ylides can be
readily diversified to other important dicarbonyl compounds of
choice.
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ASSOCIATED CONTENT
■
*
S
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.or-
glett.9b01926.
5
, 4269−4272.
(
7) Klaus, S.; Neumann, H.; Zapf, A.; Strubing, D.; Hubner, S.;
̈
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General comments, general procedure, optimization
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Rossen, K.; Beller, M. A General and Efficient Method for the
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CCDC 1900497 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
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data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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AUTHOR INFORMATION
■
*
Corresponding Author
E-mail: xiao-feng.wu@catalysis.de.
ORCID
(
9) (a) Larksarp, C.; Alper, H. Palladium-Catalyzed Cyclo-
carbonylation of o-Iodophenols and 2-Hydroxy-3-iodopyridine with
Heterocumulenes: Regioselective Synthesis of Benzo[e]-1,3-oxazin-4-
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1999, 64, 9194−9200. (b) Lian, Z.; Friis, S. D.; Skrydstrup, T.
Palladium-Catalyzed Carbonylative α-Arylation of 2-Oxindoles with
Xiao-Feng Wu: 0000-0001-6622-3328
Notes
The authors declare no competing financial interest.
(
Hetero)aryl Bromides: Efficient and Complementary Approach to 3-
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DOI: 10.1021/acs.orglett.9b01926
Org. Lett. XXXX, XXX, XXX−XXX