Sulfoxide synthesis from sulfinate esters under Pummerer-like conditions

Article abstract of DOI:10.1039/d0cc02253e

A facile synthetic method for the preparation of allyl sulfoxides byS-allylation of sulfinate esters proceeds through sulfonium intermediates without [3,3]-sigmatropic rearrangement and further Pummerer-type reactions of the resulting allyl sulfoxides. On the basis of the plausible reaction mechanism involving sulfonium salt intermediates,S-alkynylation andS-arylation were also accomplished.

Full text of DOI:10.1039/d0cc02253e

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Sulfoxide synthesis from sulfinate esters under Pummerer-like
conditions†
Akihiro Kobayashi, Tsubasa Matsuzawa, Takamitsu Hosoya and Suguru Yoshida*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A facile synthetic method for the preparation of allyl sulfoxides by further Pummerer-type reactions of the resulting allyl sulfoxides
S-allylation of sulfinate esters proceeds through sulfonium (Figure 1D).
intermediates without [3,3]-sigmatropic rearrangement and
A
further Pummerer-type reactions of the resulting allyl sulfoxides.
Br
CsF
O
FG’
On the basis of the plausible reaction mechanism involving
sulfonium salt intermediates, S-alkynylation and S-arylation were
also accomplished.
cat. Pd
I
OEt
OTf
SiMe3
FG’
I
O
S
FG’
FG’
O
O
S
OEt
Organosulfur compounds have gained attention in a broad range
of research fields such as pharmaceutical sciences,
agrochemistry, and materials science.1,2 The recent remarkable
successes of synthetic chemistry using sulfoxides have enhanced
the accessibility of highly functionalized compounds by virtue of
the significant transformability of sulfoxides.3–8 For example, the
preparations of diverse compounds 2–5 were achieved by a
variety of transformations of allyl aryl sulfoxides 1 through C–S
bond cleavage (Figure 1A).6,7,8h,8j In particular, multisubstituted
aromatic sulfides 4 and 5 were synthesized from sulfoxides 1 by
a reaction with aryne intermediate I in the presence of
electrophiles and the [3,3]-sigmatropic rearrangement of allyl
sulfonium intermediate II, respectively.6,7 Similar interrupted
4
FG
FG’
2
O
FG
S
1
FG’
FG’
FG
R
R
N
N
OSiMe3
FG’
R
LDA;
5
S
S
R
3
then,
O
N
–OTf
FG
FG
II
Tf2O
R
SiMe3
B
SiMe3
Tf2O
O
S
S
S
S
S
S
CF3
–OTf
CF3
CF3
III
6
7
Pummerer reactions of sulfoxides
6
and
8
with
C
D
SiMe3
Tf2O
R
O
trifluoromethanesulfonic anhydride (Tf2O) in the presence of
allyltrimethylsilane were also accomplished through the [3,3]-
sigmatropic rearrangement, showing the notable reactivity of
allyl sulfonium intermediates III and IV (Figures 1B and
1C).4b,4d,4e,4n Herein, we describe an efficient synthesis of various
allyl sulfoxides by allylation of sulfinate esters9 using
allyltrimethylsilane under the Pummerer-like conditions4
through sulfonium intermediate V having a methoxy group,
enabling to avoid the [3,3]-sigmatropic rearrangement and
–OTf
S
S
S
R
R
FG
FG
FG
8
9
IV
This work
SiMe3
Tf2O
–OTf
OMe
O
S
O
S
S
OMe
V
FG
FG
FG
Fig. 1 Transformations through the Pummerer-type activation of sulfoxides and sulfinate
esters. (A) Versatile transformations using allyl sulfoxides 1. (B) Interrupted Pummerer
reaction of ketene dithioacetal monoxide 6. (C) Interrupted Pummerer reaction of
aromatic sulfoxide 8. (D) This work.
a. Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering,
Tokyo Medical and Dental University (TMDU), 2-3-10 Kanda-Surugadai,
Chiyoda-ku, Tokyo 101-0062, Japan. E-mail: s-yoshida.cb@tmd.ac.jp
† Electronic Supplementary Information (ESI) available: Experimental procedures,
characterization for new compounds including NMR spectra. For ESI see DOI:
10.1039/x0xx00000x
Sulfinate esters hitherto have served in the sulfoxide
synthesis with Grignard reagents.9a Recently, Lewis acid-
mediated Friedel–Crafts-type sulfinylation of electron-rich
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Chem. Commun., 20XX, 00, 1-4 | 1
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R’
A
substituted sulfinate esters also took place smoothly to provide
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SiMe3
11
DOI: 10.1039/D0CC02253E
sulfoxides 12h–12j.
(3.0 equiv)
Tf2O
(1.5 equiv)
R’
Various functionalized allylsilanes 11 participated in the S-
–OTf
OMe
O
S
O
S
R’
allylation of sulfinate ester 10a (Figures 2A and 2C).13
Sulfoxides 12k and 12l were efficiently synthesized by 2-
methyl- and 2-phenylallylation, respectively. It is worth noting
that the C–S bond formation enabled to prepare allyl chloride
12m, allyl acetate 12n, ester 12o, and bromoalkene 12p leaving
highly electrophilic functional groups untouched, while it is not
easy to synthesize sulfoxides having electrophilic moieties by the
conventional allyl sulfoxide synthesis via allylation of thiols and
subsequent oxidation. Moreover, transformable sulfoxides 12q
and 12r possessing a silyl and boryl groups were obtained in
moderate to good yields without damaging these reactive
functional groups.
S
OMe
R
R
CH2Cl2
rt, 1 h;
then, aq. NaHCO3
R
V’
10
12
Products by allylation using 11a
(R’ = H)
B
SiMe3
11a
O
O
O
S
S
S
Me
MeO
12a
89%
12b
89%
12c
80%
O
S
Br
O
S
O
S
O2N
Cl
12d
88%
12e
63%
12f
87%
Me
O
S
O
S
O
O
S
SiMe3
11a
A
S
Ph
n-Pen
(3.0 equiv)
Tf2O
(1.5 equiv)
Me
12g
O
S
18O
S
12h
12i
12j
56%
72%
81%
88%
OMe
CH2Cl2
rt, 1 h;
then, NaHCO3, [18O]H2O
10a
12a’
Products by allylation of PhS(O)OMe (10a)
C
Cl
OAc
O
S
Me
O
S
Ph
O
S
O
S
10a
B
11a
(3.0 equiv)
Tf2O
(1.5 equiv)
12k
81%
12l
79%
12m
76%
12n
80%
O
S
NaHCO3
rt, 5 min
aq. NaHCO3
O
S
CO2Et
O
S
Br
O
S
SiMe3
O
Bpin
CH2Cl2, rt, 1 h;
–OTf
12a
94%a
CH2Cl2
rt, 10 min
S
S
12o
12p
12q
46%
12r
76%
OMe
31%
60%
13
quant.
NaBH4
S
Fig. 2 Allyl sulfoxide synthesis from sulfinate esters 10 and allylsilanes 11. (A) General
scheme. (B) Results using various sulfinate esters 10 with 11a. (C) Results using
allylsilanes 11 with 10a.
14
80%a
MeOH
0 °C to rt, 2 h
TfO
O
C
S
CF3
O
O
arenes using sulfinate esters was developed.9b Taking the
sulfinate ester chemistry into account, we envisioned that the
Pummerer-type activation of sulfinate esters 10 in the presence
of allylsilanes 11 and stability of methoxy sulfonium
intermediates10 would allow for the facile synthesis of allyl
sulfoxides 12, considering that the hydrolysis of methoxy
sulfonium intermediates V’ can afford sulfoxides (Figure 2A).
As a result of screening the reaction conditions, we found that
treatment of methyl benzenesulfinate (10a) with Tf2O in the
presence of allyltrimethylsilane (11a) followed by addition of
aqueous sodium bicarbonate provided allyl phenyl sulfoxide
(12a) in high yield (Figures 2A and 2B). Examinations using a
variety of acid anhydrides or Lewis acids showed the remarkable
TfO
–OTf
–OTf
SiMe3
S
S
S
OMe
OMe
OMe
12a
VI
13
Me3SiOTf
Fig. 3 Control experiments. (A) Reaction using [18O]H2O. (B) Isolation of sulfonium salt
13, hydrolysis of 13, and reduction of 13. (C) Plausible reaction mechanism. 1H NMR
a
yield.
To gain insight into the reaction mechanism of the
S-
allylation of sulfinate esters under the Pummerer-like conditions,
we then examined control experiments (Figure 3). Firstly, the
reaction using [18O]H2O in the hydrolysis using aqueous sodium
bicarbonate was conducted to clarify the origin of the oxygen
atom of sulfoxide 12a (Figure 3A). The result showed that 18O-
incorporated 12a’ was obtained selectively, indicating that the
sulfoxide oxygen was derived from water in the hydrolysis. We
then attempted to isolate sulfonium intermediate 13 (Figure 3B).
As a result, after sulfinate ester 10a was treated with Tf2O in the
presence of allylsilane 11a, an addition of solid sodium
bicarbonate, filtration of the resulting mixture, removal of the
solvent of the filtrate, and washing with diethyl ether afforded
sulfonium salt 13 quantitatively. Hydrolysis of sulfonium salt 13
with aqueous sodium bicarbonate underwent uneventfully to
give sulfoxide 12a. In addition, reduction of sulfonium salt 13
with sodium borohydride successfully provided allyl phenyl
reactivity of Tf2O in the S A
-allylation of sulfinate ester 10a.11,12
wide range of allyl sulfoxides 12b–12j were prepared by the S-
allylation under the Pummerer-like conditions, where
C-
allylation products through the [3,3]-sigmatropic rearrangement
were not obtained. Indeed, not only electron-rich aromatic
sulfinate esters bearing methyl and methoxy groups but also
electron-deficient substrates with chloro and nitro groups were
efficiently allylated to furnish sulfoxides 12b–12e. Sulfoxides
12f and 12g were obtained uneventfully by the reactions of bulky
2-bromo- and 2,6-dimethyl-substituted benzenesulfinate esters.
Furthermore, S-allylations of 2-naphtyl-, benzyl-, and n-pentyl-
2 | Chem. Commun., 20XX, 00, 1-4
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sulfide (14) in good yield.10c On the basis of these results, we cyclization of the resulting phenol 20a and subsequent
View Article Online
16
proposed a reaction mechanism of the S
-allylation (Figure 3C). elimination with a base successfully furnDisOhIe: d10b.1e0n39z/oDf0uCraCn022215.3E
The Pummerer-type activation of sulfinate ester by virtue of the Methallylation of sulfinate ester 10d followed by the aryne
remarkable reactivity of Tf2O,14 and following
-allylation of the trifunctionalization led to the synthesis of highly functionalized
S
resulting sulfonium intermediate VI would furnish sulfonium phenol 20b (Figure 5B). Furthermore, tetrasubstituted indole 23
intermediate 13 along with trimethylsilyl triflate. Then, was prepared through 2-bromoallylation of sulfinate ester 10c
hydrolysis of sulfonium salt 13 with aqueous sodium bicarbonate and following 2,3-difunctionalization of indole 22 according to
involving the nucleophilic attack of external water to the sulfur the reports by Procter and coworkers7 (Figure 5C).
atom leads to sulfoxide 12a. Although the role of methoxy group Functionalized allyl aryl sulfoxide 12t and indole 22 bearing o-
is still unclear, the stability of sulfonium salt 13 would achieve silylaryl triflate moiety17 for the aryne generation participated in
the sulfoxide synthesis without [3,3]-sigmatropic rearrangement the 2,3-disubstituted indole synthesis leaving the reactive
or the Pummerer-type reactions of allyl sulfoxide 12a and further functional groups intact. Thus, a wide variety of indoles would
Pummerer-type reactions of the resulting allyl sulfoxides.15
Our attention then directed toward novel transformations through
the cationic intermediates generated by the Pummerer-type activation
of sulfinate esters with Tf2O (Figure 4). In this context, we have
developed a facile synthetic method of alkynyl sulfoxides 16 using
alkynyl silanes 15 (Figure 4A). Indeed, treatment of sulfinate ester
10a dissolved in nitromethane with Tf2O in the presence of
ethynylsilanes 15 at –20 °C furnished alkynyl sulfoxides 16 in
moderate to high yields. This novel transformation enabled the
preparation of alkynyl sulfoxides 16a–16c having a methyl, phenyl,
and 4-anisyl group. Since alkynyl sulfoxides serve in a variety of
reactions including carbometallation, [2+2] cycloaddition, and
cyclopropanation, the alkynyl sulfoxide synthesis developed in this
study would allow for the preparation of a range of organosulfur
compounds.4j,13 In addition, Friedel–Crafts-type arylation of sulfinate
ester 10a also took place smoothly to afford a regioisomeric mixture
of diaryl sulfoxides 18 and 18’ in good yield (Figure 4B).9b
be synthesized by
difunctionalization of indoles, and further transformations
through indolyne intermediates with
arynophiles.18,19
S-allylation of sulfinate esters, 2,3-
a
number of
A
MeO
OTf
SiMe3
19
KF, 18-crown-6
Me
O
1. I2
MeO
Ph
12a
MeO
Ph
OH
21
42%
2. DBU
S
1,4-dioxane
110 °C
20a
52%
S
Me
Me
B
SiMe
3 11b
19
KF, 18-crown-6
Tf2O
O
Me
O
S
S
MeO
OH
Ar
Ar
OMe
1,4-dioxane
80 °C
CH2Cl2
rt, 1 h;
then,
S
10d
12s
80%
Ar = 4-ClC6H4
20b
32%
aq. NaHCO3
Cl
H
N
C
Br
15
R
Me3Si
(3.0 equiv)
Tf2O
TfO
A
22
SiMe3
SiMe3
NH
11g
(CF3CO)2O
NaHCO3
TfO
Me3Si
O
S
(1.5 equiv)
Tf2O
O
S
O
S
O
Br
S
OMe
MeNO2
–20 °C, 1 h;
then, NaHCO3, H2O
S
Br
Ar
OMe
Ar
CH2Cl2
rt, 1 h;
then,
CH2Cl2
–78 °C to rt
R
10c
Ar = 4-MeOC6H4
10a
16
12t
53%
MeO
aq. NaHCO3
O
S
O
23
84%
O
S
S
Fig. 5 Transformations of allyl sulfoxides. (A) Benzofuran synthesis. (B) Trisubstituted
phenol synthesis. (C) Multisubstituted indole synthesis.
Me
16a
75%
16b
70%
16c
45%
OMe
OMe
PhOMe 17
(3.0 equiv)
Tf2O
B
In summary, we have developed a facile synthetic method of
O
S
O
S
(1.5 equiv)
allyl sulfoxides by
S-allylation of sulfinate esters through
10a
+
sulfonium intermediates
without [3,3]-sigmatropic
MeNO2
–20 °C, 1 h;
then, NaHCO3, H2O
OMe
81%
(18:18’ = 88:12)
rearrangement and further Pummerer-type reactions of the
resulting allyl sulfoxides. On the basis of the plausible reaction
18
18’
Fig.
4
Alkynylation and arylation of sulfinate ester 10a. (A) Alkynylation with
mechanism,
S
-alkynylation and
S-arylation were also
alkynylsilanes 15. (B) Arylation with anisole (17).
accomplished. Further studies to expand the scope of these
transformations using sulfinate esters under the Pummerer-like
conditions, chiral sulfoxide synthesis, and the applications to the
synthesis of bioactive compounds are now in progress.
The authors thank Dr. Yuki Sakata at Tokyo Medical and
Dental University for HRMS analyses. This work was supported
by JSPS KAKENHI Grant Numbers JP19K05451 (C; S.Y.),
JP18H02104 (B; T.H.), JP18H04386 (Middle Molecular
Strategy; T.H.), and 19J14128 (JSPS Research Fellow; T.M.);
the Naito Foundation (S.Y.); the Japan Agency for Medical
Research and Development (AMED) under Grant Number
JP19am0101098 (Platform Project for Supporting Drug
Wide transformability of allyl aryl sulfoxides synthesized
from sulfinate esters was showcased by the syntheses of
multisubstituted aromatic compounds (Figure 5). Modifying the
conditions for the trifunctionalization of aryne intermediates
reported by Li and coworkers6 (Figure 1A, 1 to 4), we found that
2,3,6-trisubstituted phenol 20a was obtained in moderate yield
with avoiding further arylation between phenol 20a and 3-
methoxybenzyne when the aryne trifunctionalization was
performed in hot 1,4-dioxane5d in the absence of electrophiles
such as ethyl bromoacetate (Figure 5A). Iodine-mediated
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Conflicts of interest
There are no conflicts to declare.
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where [3,3]-sigmatropic rearrangement did not proceed.
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4 | Chem. Commun., 20XX, 00, 1-4
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ChemComm
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Journal Name
COMMUNICATION
Graphical abstract for the contents page
View Article Online
DOI: 10.1039/D0CC02253E
xxx
Sulfoxide synthesis from sulfinate esters under
Pummerer-like conditions
Akihiro Kobayashi, Tsubasa Matsuzawa,Takamitsu
Hosoya and Suguru Yoshida*
A facile synthetic method of allyl sulfoxides by S-allylation of
sulfinate esters through sulfonium intermediates has been
developed without [3,3]-sigmatropic rearrangement and further
Pummerer-type reactions of the resulting allyl sulfoxides. On the
basis of the plausible reaction mechanism involving sulfonium salt
intermediates, S-alkynylation and S-arylation were also
accomplished.
This journal is © The Royal Society of Chemistry 20xx
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