Gold-Catalyzed, Iodine(III)-Mediated Direct Acyloxylation of the Unactivated C(sp3)–H Bonds of Methyl Sulfides

Article abstract of DOI:10.1002/ejoc.201600632

The gold-catalyzed, iodine(III)-mediated direct oxidative acyloxylation of the C(sp³)–H bonds of methyl sulfides for the synthesis of various α-thioaryl and α-thioalkyl ester derivatives was discovered. Bis(acyloxy)iodobenzene proved to be an efficient reagent to activate the sulfur atom as an in situ directing group for α-C(sp³)–H functionalization. The attractive features of this protocol include short reaction times, low catalyst loading, and in situ activation of adjacent C(sp³)–H bonds of the sulfur atom.

Full text of DOI:10.1002/ejoc.201600632

DOI: 10.1002/ejoc.201600632
Communication
Acyloxylation
Gold-Catalyzed, Iodine(III)-Mediated Direct Acyloxylation of the
3
Unactivated C(sp )–H Bonds of Methyl Sulfides
Sheng-rong Guo, Pailla Santhosh Kumar, Yan-qin Yuan,* and Ming-hua Yang*
[a]
[a]
[a]
[a]
3
Abstract: The gold-catalyzed, iodine(III)-mediated direct oxid- ing group for α-C(sp )–H functionalization. The attractive fea-
3
ative acyloxylation of the C(sp )–H bonds of methyl sulfides for tures of this protocol include short reaction times, low catalyst
3
the synthesis of various α-thioaryl and α-thioalkyl ester deriva- loading, and in situ activation of adjacent C(sp )–H bonds of
tives was discovered. Bis(acyloxy)iodobenzene proved to be an the sulfur atom.
efficient reagent to activate the sulfur atom as an in situ direct-
Introduction
zation of C–H bonds in the α-position to oxygen and nitrogen
[
15]
atoms is known, the oxidative activation of C–H bonds in the
α-position to a sulfur atom has not yet been reported. Encour-
aged by recent work by others on the hypervalent iodine(III)-
mediated formation of sulfides, especially work by Sanford re-
The transition-metal-catalyzed direct oxidative acyloxylation of
C–H bonds provides a straightforward strategy for C–O bond
[
1]
formation. In these acyloxylation methods, the catalyst is usu-
[
2]
[3]
[4]
ally palladium, rhodium, or copper, and (diacetoxyiodo)-
benzene is a typical acyloxylation reagent. In 2004, Sanford and
co-workers were the first to report the highly regioselective
acetoxylation of arene C–H bonds by using pyridine as a direct-
[
16a]
lated to C–S bond functionalization,
we decided to exploit
the oxidative functionalization of sulfides as substrates. To the
best of our knowledge, there are no reports on the direct α-
3
C(sp )–H acyloxylation of sulfides with hypervalent iodine(III)
IV
II
ing group and proposed a plausible Pd /Pd catalytic cycle for
the reaction mechanism. During the past decade, elegant
work on the acetoxylation of arene C–H bonds, including that
3
reagents. Thus, herein we report the direct C(sp )–H acyloxyl-
[
5]
ation of sulfides in the presence of PPh AuCl as a catalyst and
3
hypervalent iodine as an oxidant (Scheme 1).
[
6]
[7]
[8]
[9]
[10]
performed by Yu, Lei, Sahoo, Wang, and Liang,
has
addressed the critical role of the nitrogen-containing directing
group and the transition metal in this transformation. Because
3
of the relatively low reactivity of C(sp )–H bonds, the transition-
3
metal-catalyzed acetoxylation of unactivated C(sp )–H bonds
[
11]
has rarely been reported. Sanford and Neufeldt developed a
3
palladium-catalyzed method for the acetoxylation of C(sp )–H
[
11a]
bonds by using oximes as directing groups.
Other groups,
including those of Corey, Sahoo, and Zhang, independently dis-
covered the Pd(OAc) -catalyzed oxidative acetoxylation of
2
3
C(sp )–H bonds by utilizing a bidentate orientation strat-
egy.[11b–11e]
Scheme 1. Selective oxidative activation of sulfides mediated by hypervalent
iodine(III).
However, these transformations generally remain
limited as a result of the use of preactivated directing groups
and harsh reaction conditions.
Sulfide motifs serve as important functional groups in gen-
[
12]
eral organic synthesis and materials science,
methods have been developed for the construction of C–S
and numerous
Results and Discussion
[
13]
At the outset, we started with the model reaction of 4-
bonds. On the other hand, in recent years much progress in
transition-metal-catalyzed C–S bond-cleavage reactions has
also been achieved. Intriguingly, although direct functionali-
CH C H SCH (1a, 0.5 mmol) with PhI(OAc)2 (0.75 mmol,
3
6
4
3
[
14]
1.5 equiv.) without a metal catalyst or base in 1,2-dichloroeth-
ane (DCE) at 130 °C for 2 h (Table 1, entry 1). Unexpectedly
3
C(sp )–H bond acyloxylation of the sulfide was found, and the
[
a] Department of Chemistry, Lishui University,
23000, Lishui, P. R. China
3
reaction afforded product 3aa in 40 % yield without detecting
other byproducts such as sulfoxide or sulfone.
This positive outcome encouraged us to optimize the reac-
tion conditions. It was observed that the reaction was highly
sensitive to temperature. Methyl phenyl sulfoxide was isolated
E-mail: yuanyq5474@lsu.edu.cn-
mhyang@lsu.edu.cn
www.lsu.edu.cn
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201600632.
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1
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Communication
Table 1. Optimization of the reaction conditions.[a]
reaction did not proceed in the absence of a hypervalent iodine
reagent.
With the optimized reaction conditions in hand, we then ex-
amined the scope of various thioanisoles (Table 2, entries 1–
1
5). A variety of functional groups, both electron-donating and
-
withdrawing groups, including –CH , –OCH , –I, –CF , –CN,
3
3
3
Entry Catalyst (mol-%)
Temp. [°C ]
Solvent
Yield[b] [%]
–COCH , –CHO, and –CO CH , reacted with PhI(OAc) to give
3 2 3 2
the corresponding products in moderate to excellent yields
(Table 2, entries 1–15). Substituents in the para and meta posi-
tions of the thioanisole had only a small influence on the react-
ivity, and the corresponding products were obtained in good
to excellent yields (Table 2, entries 1–9). Substituents in the
ortho position, however, decreased the reactivity slightly and
gave the desired products in moderate to good yields (Table 2,
entries 10–15). Notably, if 2-methoxythioanisole was used as
the substrate it was the –SCH group and not the –OCH group
that was activated by the hypervalent iodine reagent (Table 2,
entry 10). This result indicates that between the sulfur and oxy-
gen atoms, only the sulfur atom could be activated by the
hypervalent iodine reagent to form the sulfonium salt. This
might be because of an empty d orbital of the sulfur atom in
this valency. Moreover, an alkenyl group was also tolerated un-
der the oxidative conditions, and the product was delivered in
a good yield (Table 2, entry 15). Disappointingly, no product
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
–
–
–
130
110
80
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
40
20
[
c]
n.r.
77
70
71
65
76
92
93
45
93
76
85
90
89
n.r.
n.r.
n.r.
n.r.
Pd(OAc)
Cu(OAc)
Ni(OAc)
AgOAc (2)
[Ir(cod)Cl]
AuCl(dms) (2)
PPh
PdCl
PPh
PPh
PPh
PPh
PPh
PPh
PPh
PPh
PPh
2
(2)
(2)
(2)
130
130
130
130
130
130
130
130
130
130
130
130
130
130
130
130
130
2
2
2
0
1
2
3
4
5
6
7
8
9
0
3
AuCl (2)
3
3
2
(2)
3
AuCl (0.5)
AuCl (0.5)
AuCl (0.5)
AuCl (0.5)
AuCl (0.5)
AuCl (0.5)
AuCl (0.5)
AuCl (0.5)
AuCl (0.5)
[
d]
3
3
3
3
3
3
3
3
[
e]
CH
CH
2
Cl
CN
2
3
[
[
[
[
f]
f]
f]
f]
DMSO
DMF
CH
3
OH
dioxane
[
(
a] Reaction conditions: sulfide (0.5 mmol), PhI(OAc)
2 mL), 130 °C, 30 min. [b] Yield of isolated product. [c] n.r.: no reaction; the
(0.5 mmol). [e] PhI(OAc) (1.0 mmol).
f] n.r.: no reaction; the product was not detected by GC–MS.
2
(0.75 mmol), solvent
Table 2. Substrate scope of the thioanisoles for acetoxylation.[a]
sulfoxide was isolated. [d] PhI(OAc)
[
2
2
in 60 % yield at 80 °C without the formation of the predicted
product, whereas only 20 % yield of product 3aa was detected
at 110 °C in the absence of a catalyst (Table 1, entries 2 and 3).
We then examined the influence of the metal catalyst, and a
number of transition-metal catalysts were screened and tested
in the model reaction, including Pd(OAc) , Cu(OAc) , Ni(OAc) ,
2
2
2
AgOAc, [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene), AuCl(dms)
dms = dimethyl sulfide), PPh AuCl, and PdCl . Interestingly, all
(
3
2
of these metal catalysts promoted the model reaction and de-
livered the product in moderate to good yields. The catalysts
Pd(OAc) , Cu(OAc) , Ni(OAc) , AgOAc, and [Ir(cod)Cl] afford 3aa
2
2
2
2
in moderate yields of 65–77 % (Table 1, entries 4–8), and 3aa
was obtained in near-quantitative yield in the presence of
2
.0 mol-% of AuCl(dms) or PPh AuCl as the catalyst (Table 1,
3
entries 9 and 10), whereas the heterogeneous catalyst PdCl2
gave only a 45 % yield of the desired product (Table 1, en-
try 11). Surprisingly, upon decreasing the loading of PPh AuCl
3
from 2 to 0.5 mol-% we found that there was no change in the
yield of the product (Table 1, entry 12). With respect to the
oxidant loading, 1.5 equivalents of PhI(OAc) was found to be
2
optimal for this reaction (Table 1, entries 12–14). Lastly, screen-
ing of the solvents revealed that DCE was the best solvent, and
other solvents such as 1,4-dioxane, DMF, and CH OH inhibited
3
the desired transformation (Table 1, entries 15–20). Notably, in
the absence of a hypervalent iodine reagent, the addition of a
carboxylic acid as a co-solvent in the presence of other oxid-
ants, such as K S O , 2,3-dichloro-5,6-dicyano-1,4-benzoquin-
2
2 8
[
(
a] Reaction conditions: sulfide (0.5 mmol), PhI(OAc)
0.5 mol-%), DCE (2 mL), 130 °C, 30 min, yields (based on 1) of isolated prod-
2 3
(0.75 mmol), PPh AuCl
one (DDQ), Oxone, and tert-butyl hydroperoxide (TBHP), hin-
dered this direct C–H bond acyloxylation reaction. However, the
ucts are given.
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Communication
was obtained under the optimized conditions in the presence
Table 3. Substrate scope of the thioanisole for acyloxylation.[a]
of the –OH, –COOH, and –NH functional groups on the thio-
2
anisole benzene ring.
Then we investigated the scope of different hypervalent iod-
ine coupling partners in this transformation. It was clear that
the acetate moiety in the product was from PhI(OAc) , so we
2
switched to using other hypervalent iodine reagents that could
be obtained by ligand metathesis. To our delight, the optimized
reaction conditions could also be applied to this change, al-
though a slightly longer time was required. As summarized in
Table 3, not only aliphatic acids such as butyric acid, cyclo-
propanecarboxylic acid, and acrylic acid but also aromatic acids
such as benzoic acid, m-nitrobenzoic acid, p-chlorobenzoic acid,
and p-toluic acid were compatible under the optimal condi-
tions, and they all provided the corresponding products in
good to excellent yields. For different substituted thioanisoles,
electron-donating groups such as –CH or electron-withdraw-
3
ing groups such as –CF , –COCH , –CN, –Br, and –I attached
3
3
to the aromatic ring were well tolerated during the reaction.
Moreover, commercially available dimethyl sulfide underwent
this acyloxylation reaction smoothly to give the product in ex-
cellent yield (Table 3, entries 15 and 16). Interestingly, the reac-
tion showed excellent regioselectivity in that the secondary C–
H bond of the sulfide showed higher reactivity than the primary
C–H bond of the sulfide, which indicated that C–H bond activa-
tion and cleavage might be the rate-limiting step in the reac-
tion (Table 3, entries 17 and 18).
To obtain some insight into this transformation, some control
experiments were performed. Previous research demonstrated
that an oxidative radical process might be involved in this C–H
a] Reaction conditions: sulfide (0.5 mmol), PhI(OCOR1)
2
(0.75 mmol),
[
[
16]
bond acyloxylation reaction.
Thus, we performed a control
PPh AuCl (0.5 mol-%), DCE (2 mL), 130 °C, 1–2 h, yields (based on 1) of
3
experiment by adding the radical scavenger 2,2,6,6-tetramethyl-
isolated products are given.
Scheme 2. Control experiments.
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Communication
Scheme 3. Proposed mechanism for the gold-catalyzed acyloxylation reactions with sulfides and hypervalent iodine(III).
piperidin-1-oxyl (TEMPO) under the standard reaction condi- Experimental Section
tions (Scheme 2, reaction a). The yield of product 3aa remained
General Procedure for the Gold-Catalyzed Direct Acyloxylation
of Sulfides: A mixture of sulfide 1 (0.5 mmol), hypervalent iodine
essentially the same, which indicated that a free-radical inter-
mediate might not be involved in the reaction. Further, we ex-
amined the reaction at a lower temperature expecting to obtain
2
(0.75 mmol), PPh AuCl (0.5 mol-%), and DCE (2 mL) was stirred at
3
130 °C in a sealed tube reactor for 30 min. Upon completion of
[
16a]
the sulfonium salt.
Unfortunately, however, we found that the reaction (monitored by TLC), the mixture was cooled to room
some other byproducts, such as the oxidized product of thio- temperature. The resulting crude product was purified directly by
anisole, and intermediate B along with the regular product column chromatography (silica gel; EtOAc/petroleum ether, 1:20) to
afford pure product 3.
were formed (Scheme 2, reaction b). Intermediate B, under the
optimal conditions, was rapidly converted into the product with
nearly 100 % conversion (Scheme 2, reaction c), and at the Acknowledgments
same time, the sulfoxide and sulfone failed to afford the acetox-
This work was supported by the Natural Science Foundation of
ylation product, which indicated that the sulfoxide and sulfone
Zhejiang Province, P. R. China (grant number Y16B020018) and
could not be activated by the hypervalent iodine(III) reagent to
the Public Welfare Technology Application Foundation of Lishui
form intermediate B (Scheme 2, reaction d). The above reac-
(
grant number 2014JYZB49).
tions clearly indicate that the reaction mechanism may not in-
volve a regular Pummerer rearrangement (Scheme 2, reac-
tion d). Lastly, we examined the reaction in the presence of
Keywords: Synthetic methods · C–H activation ·
Acyloxylation · Gold · Hypervalent compounds · Iodine
other nucleophiles such as CH OH, and to our delight, a meth-
3
oxylated product was observed in 16 % yield as a minor prod-
uct along with the acetoxylated product, which further sup-
ported the formation of intermediate B and our mechanistic
proposal (Scheme 2, reaction e).
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[
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a plausible reaction mecha-
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[
17d]
tions to the Pummerer rearrangement.
We presume that the
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[
19]
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3
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3
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of sulfides by hypervalent iodine(III) to give thioaryl acetates.
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Received: May 23, 2016
Published Online: ■
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Communication
Acyloxylation
An efficient reaction for the iodine(III)-
mediated acyloxylation of the unacti-
vated C(sp )–H bonds of methyl sulf-
ides is reported. This strategy utilizes
various hypervalent iodine reagents
and involves an ionic pathway to de-
liver the desired products in excellent
yields (DCE = 1,2-dichloroethane).
S.-r. Guo, P. Santhosh Kumar,
Y.-q. Yuan,* M.-h. Yang* ................... 1–6
3
Gold-Catalyzed, Iodine(III)-Mediated
Direct Acyloxylation of the Unacti-
3
vated C(sp )–H Bonds of Methyl
Sulfides
DOI: 10.1002/ejoc.201600632
Eur. J. Org. Chem. 0000, 0–0
www.eurjoc.org
6
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim