Direct α-acyloxylation of organic sulfides with the hypervalent (diacyloxyiodo)benzene/tetra-n-butylammonium bromide (TBAB) reagent combination

Article abstract of DOI:10.1039/c6ra01799a

A novel metal-free approach to directly synthesize α-acyloxy sulfides from readily available alkyl sulfides utilizing the hypervalent (diacyloxyiodo)benzene and TBAB reagent combination is reported. This transformation is characterized by its broad substrate scope in moderate to excellent yields, convenient operating conditions and outstanding functional group tolerance.

Full text of DOI:10.1039/c6ra01799a

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Direct α-Acyloxylation of Organic Sulfides with the Hypervalent
(Diacyloxyiodo)benzene/Tetra-n-Butylammonium Bromide (TBAB)
Reagent Combination
Received 00th January 20xx,
Accepted 00th January 20xx
Dan Zhu, a,b Denghu Chang, a,b Shaoyan Gan, a,b and Lei Shi* a,b,c
DOI: 10.1039/x0xx00000x
www.rsc.org/
N
A novel metal-free approach to directly synthesize α-acyloxy
sulfides from readily available alkyl sulfides utilizing hypervalent
(diacyloxyiodo)benzene and TBAB reagent combination is
reported. This transformation is characterized by its broad
substrate scope in moderate to excellent yields, convenient
operating condition and outstanding functional group tolerance.
S
O
O
O
SPh
OAc
N
N
N
HO
MeO2
C
MeO2C
H
NH2
Me
Lamivudine
HO
Me
the synthesis of Strychnine
by Philip Magnus
OH
O
O
OAc
Me
H
Sulfur-containing organic compounds have been attracting
more and more interest due to their essential role in the fields
of modern organic synthesis,1 drug design and discovery,2 food
chemistry3 and material science.4 Among common
organosulfur compounds, α-acyloxy sulfides5 and their further
oxidative derivatives (α-acyloxy sulfones)6 have been widely
employed as aldehyde or ketone synthons in organic synthesis.
Moreover, the ester parts of bifunctional α-acyloxy sulfides
can subsequently react with a large variety of external or
internal nucleophiles, which provide a convenient method for
regiospecific carbon-carbon bond formation.7c, 7f Therefore, α-
acyloxy sulfides are widely used as valuable synthetic
precursors and intermediates, especially in the construction of
biologically and industrially useful carbocycles and
heterocylces (naturally occurring or unnatural), such as
Lamivudine,8a Strychnine8b and Asteltoxin.8c
the synthesis of Asteltoxin
by Stuart L. Schreiber
SPh
Figure
1 Examples of α-acyloxy sulfides as valuable
intermediates in natural products.
(a) Previous work
O
Ac2O
R2
S
S
R2
OAc
R2(R3)
OR
S
R1
R1
R1
Pummerer rearrangement
R2
S
X
R1
or
Nucleophilic reaction
S
S
R2
OR
R1
R2
S
S
R2
R1
R1
anti-Markovnikov addition
OR
Rf
Rf
anodic oxidation
R1
Electrolytic reaction
H
Over the past decades, there were five general methods for
the preparation of α-acyloxy sulfides (Scheme 1): (1)
Pummerer-type rearrangement of alkyl sulfoxides;7 (2) the
nucleophilic reaction of α-substituted alkyl sulfides;9 (3) the
anti-Markovnikov addition of vinyl esters with arylthiols;10 (4)
addition of aryl disulfides with (acyloxymethyl)magnesium
chlorides;11 (5) the anodic oxidation of sulfides.12
OR
(b) This work
R2
S
R2
OAc
TBAB / PhI(OAc)2
DCM / r.t. / N2
S
R1
R1
H
Scheme 1 Exiting methods for synthesize the α-acyloxy sulfides.
Stoichiometric hypervalent (diacyloxyiodo)benzene has
been frequently used in the direct acyloxylation of C(sp3)
−H
bonds recently. In this regard, various directing groups, such as
picolinamide,13 pyridine,14 oxime,14,15 8-aminoquinoline,16 S-
methyl-S-2-pyridyl-sulfoximine,17
Boc-protected
N-
methylamine,18 N2-pyridine-1,2,3-triazole-4-carboxylic acid19
and 1-aminoanthraquinone,20 have been successfully utilized
for transition-metal-catalyzed chelate-directed oxidative
a.Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen 518055,
China. E-mail: lshi@hit.edu.cn
b.Institute of Organic Chemistry, The Academy of Fundamental and Interdisciplinary
Sciences, Harbin Institute of Technology, Harbin 150080, China
functionalization of C(sp3)
−H bonds in conjunction with
c. State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin
300071, China. Homepage: http://homepage.hit.edu.cn/pages/shilei
†Electronic Supplementary Information (ESI) available: Detailed synthetic
procedures and characterization of new compounds. See DOI: 10.1039/x0xx00000x
PhI(OAc)2, giving rise to acetoxylated products in excellent
yields and extremely high selectivities. In addition, the
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acyloxylation reactions of substrates with activated Csp3
bonds (benzylic position21 or α-position relative to an electron- absence of tetra-n-butyl ammonium bromide (Table 1, entry 2)
withdrawing group22) in presence of PhI(OAc)2 have also been was carried out and clearly showed that only trace amount of
emphasized in literatures. Despite the advances in this field, expected product 2a was formed. By adjusting the amount of
Journal Name
−H
in only 22% yield. Importantly, the controlled reaction in the
the ability of hypervalent (diacyloxyiodo)benzene to introduce TBAB (Table 1, entries 3-4) to
3 equivalents, the α-
an acyloxy group into organic sulfides has been virtually acyloxylation product 2a can be formed as the dominant
unexplored, which is probably because organic sulfides are product (60% yield; Table 1, entry 4). The excessive amounts of
easily oxidized to the corresponding sulfoxides.23 As
a
TBAB is necessary because of the competing oxidation of the
continuation of our research interest in the application of sulfur with the PhI(OAc)2. The increase of the amount of TBAB
hypervalent iodine reagents in the rapid and efficient is beneficial to the production of tetra-n-butylammonium
preparation of useful sulfur-containing compounds,24 this work [di(acyloxy)bromated (I)], which might be the critical
herein report a direct and selective acyloxylation of a variety of intermediate in this reaction. In stark contrast, the
sulfides
with
the
combination
of
hypervalent replacement of TBAB by other additives was completely
(diacyloxyiodo)benzene and tetra-n-butyl ammonium bromide unsuccessful and led to the formation of expected product 2a
(TBAB). It is noteworthy that sulfoxides as the traditional in less than 5% yield (Table 1, entries 5-9), confirming the
precursors of Pummerer reaction8 need not be synthesized, unique reactivity of the PhI(OAc)2/TBAB system. Subsequently,
whilst most of organic sulfides are commercially available or other solvents, including toluene and THF, were also surveyed
easily prepared. To the best of our knowledge, only relatively but substantially decreased the reaction efficiency (Table 1,
rare electrochemical approaches12 have been reported thus far entries 10-11). Finally, the amount of PhI(OAc)2 can be
to construct the high-value α-acyloxy sulfides from readily reduced to 1.75 equivalents, which led to improvement in
available sulfides.
Table 1 Optimization of the reaction conditionsa,b
both starting material consumption and product formation
providing a slightly higher yield of 66% (Table 1, entry 12).
Interestingly, it was found that the improper substrates ratio
between thioanisole 1a and PhI(OAc)2 had negative effects on
the reaction (Table 1, entries 13-17). Therefore, the condition
described in entry 12 in Table 1 was chosen as the standard
condition to verify the general applicability of the present
methodology. To our disappointment, methyl phenyl sulfone
or methyl phenyl sulfoxide failed to yield the corresponding α-
acyloxylated sulfone or sulfoxide under the optimized
condition, suggesting the requirement of two lone pairs on the
sulfur for the α-acyloxylation transformation.
entry PhI(OAc)2
(equiv)
additive (equiv)
solvent
yield
(%)b
1
2
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1.75
4.0
3.0
2.5
1.5
1.0
n-Bu4NBr (1.0)
--
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
toluene
THF
22
<5
<10
60
0
3
n-Bu4NBr (0.5)
n-Bu4NBr (3.0)
n-Bu4NF (3.0)
n-Bu4NCl (3.0)
n-Bu4NI (3.0)
n-Bu4NOAc (3.0)
NaBr (3.0)
4
Table 2 Scope of thioether derivativesa,b
5
6
0
7
<5
<5
0
8
9
10
11
12
13
14
15
16
17
n-Bu4NBr (3.0)
n-Bu4NBr (3.0)
n-Bu4NBr (3.0)
n-Bu4NBr (3.0)
n-Bu4NBr (3.0)
n-Bu4NBr (3.0)
n-Bu4NBr (3.0)
n-Bu4NBr (3.0)
36
0
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
66
<10
19
35
57
35
aReaction conditions: thioanisole (0.5 mmol), PhI(OAc)2,
additive, solvent (2.0 mL), room temperature. b Isolated yield.
We initiated our investigation by choosing thioanisole 1a
and 2 equivalents of PhI(OAc)2 as the model substrates for the
target α-acyloxylation reaction in the presence of 1 equivalent
of TBAB in CH2Cl2 at room temperature for 6 h (Table 1, entry
1). To our delight, the desired product 2a was isolated, albeit
aReaction conditions: thioether (0.5 mmol), TBAB (1.5 mmol),
PhI(OAc)2 (0.875 mmol), DCM (2.0 mL), room temperature. b
Isolated yield.
2 | J. Name., 2012, 00, 1-3
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With the optimized reaction condition in hand, we first products in good yields (Table 3). Higher yields obtained than
examined the scope of sulfide substrates (Table 2). Various PhI(OAc)2 implied that we can select the appropriate
alkyl phenyl sulfides (1a-1i) with different substituents on the hypervalent iodine reagents as the acylate source (e. g.,
phenyl ring, including electron-donating and electron- hypervalent (dipivaloxyiodo)benzene) to efficiently afford the
withdrawing groups, can react smoothly with the combination analogous α-acyloxy sulfide products, which might give a
of PhI(OAc)2 and TBAB to afford the corresponding α- handgrip for a variety of further transformations in organic
acyloxylation products in yields from 32% to 80%. Moreover, synthesis. Actually, the clearly improved yields were indeed
the introduction of the substituents in ortho, meta, and para observed as illustrated in Table 3 (3eb and 3fb).
positions of the phenyl group is in fact also tolerated under the
Although further studies may be still required to discover
standard reaction condition (1j, 1k and 1b). Remarkably, this and understand the mechanism in more detail, on the basis of
transformation is compatible with a variety of synthetically our present results and the previously reported literatures,27 a
valuable functional groups (1b-1o), including fluoro, chloro, plausible mechanism for this α-acyloxylation transformation,
bromo, methoxy, nitro, cyano, carbonyl, alkenyl and alkynyl, exemplified by the reaction of organic sulfides with
thus offering ample opportunities for further derivation. PhI(OAc)2/TBAB system, is proposed in Scheme 2. Initially, a
Among these, there are still several sulfide substrates highly
containing cyano (1e), nitro (1f) and carbonyl (1g), can get [di(acyloxy)bromated (I)], which might be really responsible for
corresponding -acyloxylation products with low yields, which the α-acyloxylation reactions, is generated by the interaction
is mainly because of the competing oxidation of the sulfur with of hypervalent (diacyloxyiodo)benzene with tetra-n-butyl
the PhI(OAc)2. In particular, sulfide 1p possessing the ammonium bromide. As a matter of fact, subjection of methyl
active
intermediate
tetra-n-butylammonium
α
,
important dibenzo[b,e]thiepin framework25 with a broad- phenyl sulfide 1a in the presence of other tetra-n-butyl
ranging pharmacological potential, can also provide the ammonium salts and NaBr (Table 1, entries 5-9) resulted in less
desired α-acyloxylation product 2p in 72% yield. Besides the than 5% of the desired product, which is likely a result of
benzene ring, naphthyl-substituted sulfide (1q) and heteroaryl- inexistence of tetra-n-butylammonium [di(acyloxy)bromated
substituted sulfide
(
1r
)
are also amenable to this (I)] and competitive undesired oxidation.28 Then, organic
transformation. Likewise, unsymmetrical alkyl methyl sulfides sulfides undergoes Br-activation by the nucleophilic attack at
also proved to be suitable substrates for this transformation. the electrophilic bromine centre to form an bromosulfonium
For n-decyl methyl sulfide 1s
,
excellent regioselectivity salt. Afterwards, deprotonation next to the positively charged
H bond was sulfur by the acetate anion would lead to the generation of
favoring functionalization of the less hindered C
−
observed and sole α-acyloxylation product 2s was achieved in acetic acid and a new thionium ion. The existence of acetic
32% yield. On the contrary, acetoxylation of 2-(methylthio)-1- acid has been confirmed by the in situ 1H and 13C NMR
phenylethan-1-one 1t took place only at the more sterically investigation. Finally, the nucleophilic addition of acetate
accessible position, which is mainly because of the further anion to the double C=S bond completes the formation of the
advantage in the formation of the more stable thionium ion, α-acyloxy sulfide products. The excess of TBAB for this α-
and a 58% isolated yield of α-acyloxylation product 2t was acyloxylation transformation would be indispensable and
obtained. Notably, α-acyloxy β-ketosulfide products 2o and 2t helpful to avoid the alternative and competing undesired
might be easily rearranged into α-acyloxy thioesters as oxidation.23
versatile building blocks via acyl migration in enolate form.26
Based on the results for the above different regioselectivities
between 2o and 3o C
−H bonds, we presumed that it perhaps
originated from the stability of the thioniumion intermediates.
Table 3 Scope of hypervalent iodine (III) reagents derivativesa,b
Scheme 2 Proposed mechanism for the reaction.
In summary, we have developed an unprecedented metal-
free α-acyloxylation process of a broad range of alkyl sulfides
with the combination of hypervalent (diacyloxyiodo)benzenes
and tetra-n-butyl ammonium bromide. The key features of the
present protocol are metal-free reaction condition,
operational simplicity, a wide ranging substrate scope and
tolerance of various synthetically useful functional groups. This
methodology could also potentially streamline the synthesis by
minimizing the unnecessary oxidation operation to organic
sulfoxides as the traditional precursors of Pummerer reaction8
aFollowing the general procedure. b Isolated yield.
Next, we evaluated α-acyloxylation between methyl phenyl
sulfide 1a and other hypervalent (diacyloxyiodo)benzenes with
the aid of tetra-n-butyl ammonium bromide. As expected, all
four
hypervalent
(diacyloxyiodo)benzenes
smoothly
participated in this transformation leading to the desired
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Journal Name
1995, 36
,
8493
−
8496. For anodic oxidation of α-
and reducing the number of steps. Preliminary studies have
shown that the success of this reaction might be mainly
attributed to the generation of the tetra-n-butylammonium
[di(acyloxy)bromated (I)]. Further investigations on
mechanistic details as well as other related transformation
events are currently underway in our laboratory.
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−
−
,
−
−
80.
The work was supported by the ‘‘Hundred Talents Program’’
of Harbin Institute of Technology (HIT), the “Fundamental
−
Research
Funds
for
the
Central
University”
(HIT.BRETIV.201502), the NSFC (21202027), the NCET (NCET-
12-0145), and the ‘‘Technology Foundation for Selected
Overseas Chinese Scholar” of Ministry of Human Resources
and Social Security of China (MOHRSS).
−
,
−
−
−
−
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Journal Name
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A novel metal-free approach to directly synthesize α-acyloxy sulfides from readily available alkyl
sulfides utilizing hypervalent (diacyloxyiodo)benzene and TBAB reagent combination was
developed.