Visible Light-Promoted Sulfoxonium Ylides Synthesis from Aryl Diazoacetates and Sulfoxides

Article abstract of DOI:10.1002/cjoc.202100064

A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported. The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives, affording the corresponding sulfoxonium ylides in moderate to good yields. The success of late-stage modification of natural isolates or drug candidates, scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.

Full text of DOI:10.1002/cjoc.202100064

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Title: Visible Light-Promoted Sulfoxonium Ylides Synthesis from Aryl Diazoacetates
and Sulfoxides
Authors: Juan Lu, Lei Li,* Xiang-Kui He, Guo-Yong Xu,* and Jun Xuan*
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Cite this paper: Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Visible Light-Promoted Sulfoxonium Ylides Synthesis from Aryl
Diazoacetates and Sulfoxides
Juan Lu,a Lei Li,*a Xiang-Kui He,a Guo-Yong Xu,*d and Jun Xuan*,a,b,c
a Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, College of Chemistry & Chemical En-
gineering, Anhui University, Hefei, Anhui 230601, People’s Republic of China.
b Key Laboratory of Structure and Functional Regulation of Hybrid Materials (Anhui University), Ministry of Education, Hefei, 230601, Peo-
ple’s Republic of China.
c Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, 18 Shilongshan
Road, Hangzhou 310024, Zhejiang Province, China
d Institute of Physical Science and Information Technology, Anhui University, Hefei 230601, People’s Republic of China.
Keywords
Sulfoxonium Ylides | Aryl Diazoacetates | Sulfoxides | Visible Light | Carbene
Main observation and conclusion
A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetic useful sulfoxonium
ylides was reported. The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives,
affording the corresponding sulfoxonium ylides in moderate to good yields. The success of late-stage modification of natural isolates or
drug candidates, scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach
valuable.
Comprehensive Graphic Content
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*E-mail:
llee2005@163.com;
gyxu@mail.ustc.edu.cn;
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Supporting Information
xuanjun@ahu.edu.cn
Chin. J. Chem. 2021, 39, XXX－XXX©
2021
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CAS,
Shanghai,
&
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Juan Lu et al.
Report
product. Transition-metals or additives are all not required to run
the process.
Background and Originality Content
Sulfoxonium ylides, one categories of sulfur ylides,[1] have been
investigated as one of the most important synthons in synthetic or-
ganic chemistry.[2] Generally, sulfoxonium ylides are considered as
alternative metal-carbene surrogates due to their operational
safety and synthetic convenience comparing with structural similar
diazo compounds. Till now, they have been used in numerous types
of important organic transformations, including X-H insertion, cy-
clopropanation, epoxidation, aziridination, dimerizations, Wolff re-
arrangements, Stevens rearrangements and others.[3] Moreover,
their synthetic potentials were also well illustrated in the facile syn-
thesis of many natural isolates, pharmaceuticals, and chemical ma-
terials.[4] Consequently, the development of general and robust
synthetic method for the synthesis of sulfoxonium ylides has at-
tracted considerable attention.
Results and Discussion
At the beginning, methyl 2-diazo-2-phenylacetate 1a and dime-
thyl sulfoxide (DMSO) was selected as model substrates to test the
reaction efficiency. Irradiating a solution of 1a in DMSO with 24 W
blue LED for 3 h afforded the desired sulfoxonium ylide 3aa in 86%
isolated yield (Table 1, entry 1). To simplify the work-up step, we
tried to use DMSO as reagent in other reaction solvents. It was
found that 3aa still could be isolated in 49% yield when the reaction
was performed in DCM with 2.0 equivalents of DMSO (Table 1, en-
try 2). To our delight, the yield raised to 93% by increasing DMSO
to 4.0 equivalents (Table 1, entry 3). Replacement of DCM to other
commonly used reaction solvents, such as EtOAc, 1,2-dichloro-
ethane (DCE), CH3CN, 1,4-dioxane and tetrahydrofuran (THF) did
not give better results (Table 1, entries 4-8). No desired product 3aa
was observed when H2O was used as reaction media (Table1, entry
9). Control experiment revealed that blue LED irradiation is essen-
tial for the formation of target product (Table 1 entry 10).
O
O
R1
R1
or
/heat
O
S
[M]
UV
+
R
R
R
R
(a)
irradiation
S
S
N2
O
O
O
O
S
O
O
R1
TMS
OTf
CsF,
MS
4Å
CH3CN, 65 o
+
+
R1
Table 1 Reaction Optimization between 1a and 2aa
(b)
(c)
C
H
H
O
N2
O
S
e e
S M
O
M
+
O
S
,
,
r
t
3
so ven
Cs CO
,
e
M
l
t
h
[Pd]
CH3CN, 80 o
2
3
Ph
CO2
e
M
e
M
Ar(Het)
e
M
(Het)Ar-X
R
Ph
CO2
aa
3
R
C
a
a
2
1
=
X
Br, OTf
S
I,
O
work:
This
visible
sulfoxonium
light-promoted
ylides synthesis
Entry
1c
2d
3e
4
Solvent
Yield (%)b
86
O
S
O
DMSO
DCM
R1
(d)
O
R1
R3
R2
O
R1
R
49
93
R
R3
R2
R
S
N2
O
DCM
N2
energy source
Transition-metal free
Clean
Late-stage modification
EtOAc
DCE
73
5
78
Scheme 1 Methods towards the synthesis of α-aryl carbonylsulfoxonium
ylides.
6
CH3CN
79
7
1,4-dioxane
THF
42
Recently, several methods have been developed for the synthe-
sis of α-aryl carbonylsulfoxonium ylides, a kind of pro-chiral ylides,
which permit potential applications in asymmetric reactions.
Among the synthetic routes developed, sulfoxide insertion reac-
tions of diazo compounds represented as one of the most com-
monly used methods for the synthesis of α-aryl carbonylsulfoxo-
nium ylides (Scheme 1a).[5] Note that, those reactions generally re-
quired transition-metals, e.g., [Ag], [Cu], [Rh], at heating reaction
conditions and the light-promoted transformation limited to utilize
UV. In 2018, Burtoloso et al. developed the coupling of α-hydrogen
carbonylsulfoxonium ylides with arynes, providing a new method
for the direct synthesis of pro-chiral α-aryl carbonylsulfoxonium
ylides with moderate to good yields (Scheme 1b).[6] However, the
aryne precursors required multistep synthesis with poor regiose-
lectivity in many cases. Shortly after this discovery, Aïssa group re-
ported an α-aryl carbonylsulfoxonium ylides synthesis through pal-
ladium-catalyzed C−H cross-coupling of α-hydrogen carbonylsulfox-
onium ylides with (hetero)aryl halogens or triflates (Scheme 1c).[7]
Despite those elegant progresses, continuously developing green
and sustainable synthetic method under transition-metals and ad-
ditives free conditions is still highly appealing and desirable.
8
41
9
10f
H2O
N.R.
N.R.
DCM
a Reaction condition: 1a (0.1 mmol), 2a (0.4 mmol), in the indicated solvent
(1.0 mL), irradiation by 24 W blue LED at room temperature for 3 h under
nitrogen atmosphere. b isolated yield. c DMSO (1 mL) as solvent. d 1a/2a=1:2.
d 1a/2a=1:4. f In dark.
With the optimized reaction conditions in hand (Table 1, entry
3), we started to investigate the substrate scope of this method. As
shown in Table 2, a wide range of diazo alkanes were efficiently
transformed to the corresponding sulfoxonium ylides moderate to
good yields. Notably, substrates 1a-1h bearing electron-neutral,
electron-donating (e.g., -Me), or electron-withdrawing substitu-
ents (e.g., halogens, nitro and ester group) at the para position of
aryl ring were tolerated well, affording sulfoxonium ylides 3aa-3ha
in moderate to good yield. Unfortunately, the reaction of sulfoxo-
nium ylide bearing a strong electron-donating group (4-OMe) could
not afford the target product 3ga. We further investigated the ef-
fects of halogen substituents at different positions of benzene ring.
When 2-Cl, 3-Cl, 3,4-dichloro substituted diazo alkanes were ap-
plied to the reaction, the corresponding products 3ia-ka were ob-
tained in 56-87% yields. In addition, methyl 2-diazo-2-(naphthalen-
2-yl)acetate 1k was also amenable substrate to give product 3la in
51% yield.
As our ongoing research interests on visible light promoted
chemical transformations,[8] we herein described a visible light-
prompted α-aryl carbonylsulfoxonium ylides synthesis via the cou-
pling of diazoalkanes with sulfoxides (Scheme 1d). Under blue LED
irradiation,[9] diazoalkanes could transfer to free carbene spe-
cies,[10][11] which subsequently trapped by sulfoxides to give the fi-
nal ylide products. Note that, the reaction was performed by using
visible light as clean energy source with the release of N2 as sole by-
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Chin. J. Chem. 2021, 39, XXX－XXX

Running title
Chin. J. Chem.
Table 2 Reaction Scope a,b
To further show the synthetic potential of this blue LED-pro-
moted sulfoxonium ylide synthesis protocol in pharmaceutical in-
dustry, we introduced some natural molecules (e.g. L-Menthol, Cit-
ronellol, Oleyl alcohol) and pharmaceutically relevant compounds
(e.g. Metronidazole), into the diazo alkane starting materials. To
our delight, all of those reactions reacted well to provide modified
sulfoxonium ylide 3ua-3xa in moderate to good yields (Table 3).
O
S
N2
O
R1
R2
+
S
,
r
M
t
,
R1 R2
r
e
A
D
,
h
CO2M
C
3
r
e
A
CO2M
1
2
3
,
=
=
=
=
=
=
O
S
a
3b
3
R
R
R
R
R
R
F
C
B
N
82%
6%
O
O
S
,
,
,
,
e
e
M
ca
a
M
l 7
r
e
M
e
M
e
e
S
M
M
3d
82%
e
CO2M
,
,
,
27
ea
3
3f
e
M
O2
e
%
e
CO2
CO2M
,
O
a
M
45
%
Ad
.
.
-
,
,
R
a
a
ram sca e eac on
e
,
86%
l
R
ti
3g
N R
G
O
M
a
3h
(
)
,
O
aa
3
93%
O
S
O
S
O
N2
O
S
O
e
e
M
O
S
M
+
e
M
e
e
M
e
M
M
S
,
,
22 h
e
e
M
r
e
M
S
e
e
Ph
.
DCM
t
CO2M
M
M
e
M
e
M
e
Ph
CO2M
e
e
CO2M
CO2M
a
a
2
aa
e
1
3
CO2M
e
CO2M
.
.
,
,
mmo
e
60% yi ld 0 81 g
6 0
l
1 06 g
Cl
Cl
Cl
Cl
3k
n
e
c
rans orma on o aa
ti
f 3
b
)
Sy th ti
T
f
(
,
,
,
,
a
3l
51%
a
3i
a
a
3
7
6 %
85%
56
%
C
l
j
O
S
O
S
O
O
e
CO2M
e
M
e
e
M
e
e
M
e
e
M
e
M
M
M
O
S
M
O
S
7
O
O
O
O
,
s
n
LiCl M OH
,
73
%
THF 65 o
C
O
O
,
,
=
=
=
ma
na
oa
n
3
3
3
H2N
H
S
1 81
%
,
,
,
,
,
ra
86%
O
a
3p
a
3q
n
n
4
%
89%
6 %
4
3
5 9
,
,
e
M
e
M
S
11 8
7
%
N
H
S
CN 25 o
89
C
,
e
O
O
S
O
S
O
S
r
CO2M
e
M
I
[
COD Cl
)
e
]
e
CO2M
(
2
CO2M
DCE 80 o
C
,
e
M
e
M
e
M
e
M
e
M
S
Ph
Ph
Ph
aa
%
3
4
93%
6
O
O
e
e
CO2M
CO2M
PTSA 130 o
C
56
,
%
O
,
O
CH3CN/H2O
,
,
,
ac
77
sa
3
a
3t
a
3 b
89%
18%
60%
3
%
OH
e
CO2M
a Reaction condition: 1 (0.1 mmol), 2 (0.4 mmol), in 1.0 mL DCM, irradiation
by 24 W blue LED at room temperature for 3 h under nitrogen atmosphere.
b isolated yield.
5
Scheme 2 Follow-up Chemistry.
Further investigation revealed that alkyl substituents on the es-
ter group of 1 have negligible effect on the reaction (3ma−3sa), and
a variety of groups including primary alkyl groups with different
chain length (3ma-oa), secondary alkyl group (3pa), cyclic alkyl
groups (3qa and 3ra), were all well-tolerated. It is important to
highlight that cyclic diazo compounds are also compatible with this
procedure to afford the desired products, albeit with relatively low
yield (3ta). Apart from DMSO, it structural analogous, including sul-
finyldibenzene 2b, (methylsulfinyl)benzene 2c reacted well under
standard reaction conditions, affording the final α-aryl carbonyl-
sulfoxonium ylide in 60% and 77% yield, respectively (3ab and 3ac).
To illustrate the preparative utility of this methodology, a gram-
scale reaction of 1a (6.0 mmol, 1.06 g) and 2a was performed
(Scheme 2a). The reaction proceeded smoothly to give sulfoxonium
ylide 3aa in 60% yield after 22 hours irradiation. More importantly,
the obtained sulfoxonium ylides also could serve as valuable
synthons for synthetic transformations. As shown in scheme 2b,
several structural transformations of 3aa were carried out.[6][12-14]
The corresponding N-H, O-H, S-H, Cl-H insertion products 4-7 could
be obtained in good to excellent yields, showing the potential ap-
plications of this kind of sulfoxonium ylides in the formation of new
useful chemical bonds.
Table 3 Reaction Scope a,b
a
a
ca ra
n
g
x
e
p
r m n
e
R di l T ppi
E
i
t
)
O
e
S
M
N2
O
S
O
S
s an ar
t
d
d
e
M
+
con ons
diti
e
e
M
,
,
3
M
+
,
7
r
a
1
a
2
e
M
e
M
Ph
t
h
CO2R
C
D M
aa
8 %
3
.
Ph
CO2R
e u v
q
i
)
TEMP
1
(
O
0
a
2
1
3
e
M
Ph
CO2
O
O
ar ene
a
ur n
i
x
e
e
r m n
i
t
b C
)
b
C pt
g E
p
e
e
e
M
e
M
S
M
S
M
N
N
O2
e
M
O
O
e
N
M
O2C
ue
s
bl LED
+
+
a
1
a
2
aa
3
+
Ph
e
e
M
O
M
O
,
r
M
t 3 h
,
Ph
D
Ph
e
M
C
,
,
,
56
%
8 12
%
ua
va
3
3
rom
7
8%
62%
rone
o
l
rom e ron azo e
id
f
Cit
ll
f
M
t
l
Scheme 3. Mechanism studies
O
S
e
e
M
M
e
e
Some primary mechanistic investigations were conducted in
scheme 3 to probe the reaction mechanism of this sulfoxonium
ylide formation protocol. It was found that almost similar yield of
3aa was obtained when 1.0 equivalent of free radical scavenger
TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) was added to the
model reaction, indicating the transformation might not involve a
radical intermediate (Scheme 3a). The competitive experiment be-
tween 2a and styrene was investigated under the optimal condi-
tions, producing the expected 3aa in 56% yield, together with 12 %
yield of cyclopropane 8. The results confirmed the formation of free
carbene species in current reaction system.
M
M
,
xa
3
4
%
9
O
rom
e a co o
Ol yl
l h l
f
O
S
e
M
e
O
,
M
O
e
M
wa
3
44
%
-
rom
en o
L M th l
f
O
a Reaction condition: 1 (0.1 mmol), 2a (0.4 mmol), in 1.0 mL DCM, irradiation
by 24 W blue LED at room temperature for 3 h under nitrogen atmosphere.
b isolated yield.
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
www.cjc.wiley-vch.de

Juan Lu et al.
Report
Chem. 2020, 18, 8793–8809.
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In conclusion, we have developed a visible light-promoted car-
bene-transfer reactions of donor/acceptor diazoalkanes with
DMSO. The reaction occurred under sole visible light irradiation
without the need of any transition-metals or additives, affording a
wide range of synthetic useful sulfoxonium ylides in moderate to
good yields. Note that, the strategy shows excellent functional
group tolerance and can be utilized to late-stage modification of
natural isolates and drug candidates. The success of scale-up reac-
tion and transformation of sulfoxonium ylides to other useful mol-
ecules further render the approach valuable.
Experimental
A flame-dried Schlenk-tube equipped with a magnetic stir bar
was charged with 1a (0.1 mmol, 1.0 equiv.), 2a (0.4 mmol, 4.0
equiv.) in 1.0 mL DCM. The resulting mixture was degassed via
‘freeze-pump-thaw’ procedure (3 times). The reaction mixture was
then stirred under the irradiation with 24 W blue LED for 3 h. After
that, the crude residue was purified by silica gel column chroma-
tography to afford pure product 3aa as a yellow solid in 93% yield.
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2021xxxxx.
Acknowledgement
We are grateful to the National Natural Science Foundation of
China (No. 21971001, 21702001), the Natural Science Foundation
of Anhui Province (No. 1808085MB47), the Open Fund for Disci-
pline Construction, Institute of Physical Science and Information
Technology, Anhui University, and the Start-up Grant from Anhui
University for financial support of this work.
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(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2021
Manuscript revised: XXXX, 2021
Manuscript accepted: XXXX, 2021
Accepted manuscript online: XXXX, 2021
Version of record online: XXXX, 2021
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Running title
Chin. J. Chem.
Entry for the Table of Contents
Visible Light-Promoted Sulfoxonium Ylides Synthesis from Aryl Diazoacetates and Sulfoxides
Jun Lu, Lei Li,* Xiang-Kui He, Guo-Yong Xu* and Jun Xuan*
Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
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A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetic useful sulfoxonium ylides is re-
ported. The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives, affording the corresponding
sulfoxonium ylides in moderate to good yields.
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
www.cjc.wiley-vch.de