I2-catalyzed oxidative C(sp3)-H/S-H coupling: Utilizing alkanes and mercaptans as the nucleophiles

Article abstract of DOI:10.1039/c4cc05661b

By using alkanes and mercaptans as the nucleophiles with di-tert-butyl peroxide (DTBP) as the oxidant, I₂-catalyzed oxidative C(sp³)-H/S-H coupling was achieved. This protocol provides a novel process to construct C(sp³)-S bonds from commercially available hydrocarbons and mercaptans.

Full text of DOI:10.1039/c4cc05661b

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Journal Name
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I2-Catalyzed Oxidative C(sp3)-H/S-H Coupling：
Utilizing Alkanes and Mercaptans as the
Nucleophiles
Cite this: DOI: 10.1039/x0xx00000x
Jiwen Yuan,a Xu Ma,a Hong Yi, a Chao Liu,a and Aiwen Lei*,a,b
Received 00th January 2014,
Accepted 00th January 2014
DOI: 10.1039/x0xx00000x
www.rsc.org/
By using alkanes and mercaptans as the nucleophiles, di-tert-
butyl peroxide (DTBP) as the oxidant, I2-catalyzed oxidative
C(sp3)-H/S-H coupling was achieved. This protocol provided
a novel process to construct C(sp3)-S bond from commercially
available hydrocarbons and mercaptans.
Scheme 1. New way for C(sp3)-S bond construction
C-S bonds are key structures of many nature products and
functional molecules which exhibit different biological
activities, hence much attention has been paid to the formation
of C-S bond through coupling reactions1. Classically, coupling
reactions of organic halides/organic boronic acid with
mercaptans in the presence of bases and catalysts was
employed to form C-S bonds2. Oxidative coupling betweenRH
and R’H, which shortens the synthesis route due to the
elimination of pre-activation of C-H or X-H bonds, has
attracted much attention during the past decades3. Although
In consequence of the strong coordination of the mercaptans
to the transition metals, and the use of metal limited the further
application of the protocols in industry and pharmacy. We
initiated the investigation with a metal-free protocol8. Recently,
iodide catalysts are gaining more attention among the oxidative
coupling reactions9. Moreover, compared with transition
metals, iodide catalysts might exhibit weaker interaction with
mercaptans. Thus, this serious of catalysts were picked out to
catalyze the oxidative C(sp3)-H/S-H coupling. To figure out the
best condition, 4-methyl thiophenol 2a was employed to react
with toluene 1a. After a series of condition optimization, I2 and
DTBP were selected to be the catalyst and the oxidant
respectively (see supporting information, Table S1). The
detailed condition was: 1a (4 mL), 2a (0.3 mmol), DTBP (1.5
mmol), I2 (0.045 mmol) at 120 oC for 20 h under N2. The
corresponding sulfide was obtained in the yield of 74% under
the optimized condition (Scheme 2, 3aa)10.
transition-metal-catalyzed
C(sp2)-H
and
C(sp)-H
functionalization were the major force in this field4, they were
seldom utilized to perform oxidative coupling with S-H bonds5
due to the strong poisoning effect of mercaptans. Moreover, up
to now, only isolated reports focus on oxidative C(sp3)-H/S-H
coupling6. Thus, it is still highly desirable to explore the C-S
bond formation utilizing C(sp3)-H bonds and mercaptans as the
nucleophiles.
C(sp3)-H bonds existed extensively in the nature, and most of
which were of alkanes. Thus it is a pivotal task to realize the
functionalization of the abundant C(sp3)-H bonds of alkanes.
However, they are difficult to be activated in reactions, which
may be ascribe to their nonpolarity, which weakened the
interaction between the bonds and other species such as
transition metals. Consequently, to date, only few reports have
described oxidative coupling utilizing simple alkanes in highly
selective manner7 although they are always easy accessible.
Therefore, it is still a crucial but challenging task to achieve the
oxidative coupling of the C(sp3)-H bonds of simple alkanes.
Moreover, there is no report focused on the oxidative C-H/S-H
coupling of C(sp3)-H bonds between simple alkanes and
mercaptans, so such topic of C(sp3)-H functionalization would
provide a new way to construct C(sp3)-S bonds (Scheme 1).
Then we began to investigate the substrate scope of the
reaction. First, various aryl mercaptans were examined to react
with toluene 1a under optimized condition. Electron-rich
thiophenols performed the benzylation smoothly and good
yields were obtained (Scheme 2, 3aa, 3af, 3ag). The electron-
deficient thiophenol, however, exhibited lower activity than the
electron-rich ones (Scheme 2, 3ae). The halo-substituted
thiophenols, which allowed further functionalization, were
tolerated (Scheme 2, 3ab
effect was not obvious in the reactions of thiophenols bearing
-Br and -Br group (Scheme 2, 3ad 3ah). It was noteworthy
, 3ac, 3ad, 3ah). The steric hindrance
o
p
,
that both electron-rich and electron-deficient heterocyclic
mercaptans were also suitable for this transformation (Scheme
2, 3ai
, 3aj). Moreover, 4-mercapto-phenyl sulfide 2k, a
substrate bearing two mercapto group, also react with toluene
with good selectivity that only dibenzylated product was
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DOI: 10.1039/C4CC05661B
obtained (Scheme 2, 3ak). Unfortunately, only trace amount of kcal/mol13, and as the result, acetone, the most simple ketone,
product were detected when aliphatic mercaptans were can also perform the C(sp3)-H/S-H coupling as predicted with
employed to couple with toluene, which might result from the lower yield (Scheme 4, 5bf). With the C-H bond of acetone
over-oxidation of the relatively unstable aliphatic mercaptans.
activated, acetylacetone reacted with 4-methoxy-thiophenol
smoothly and the yield rose to 90% (Scheme 4, 5cf).
I2 (15 mol%)
DTBP (5 equiv)
N2, 120 oC, 20 h
H
Bn
Ar
+ HS Ar
S
1a
2
3
F
Cl
Br
Bn
Bn
Bn
Bn
Bn
Bn
S
S
S
S
3ad
3aa
3ab
3ac
77%
74%
73%
69%
NO2
OMe
Bn
NHAc Br
Bn
Bn
Bn
Scheme 4. I2-promoted oxidative C(sp3)-H/S-H coupling of various various
S
S
S
S
C(sp3)-H source with 4-methoxy-thiophenol. Reaction conditions:
4 (4 mL), 2f
3ae 40%
3af 86%
3ag 60%
3ah 74%
(0.3 mmol), DTBP (1.5 mmol), I2 (0.045 mmol) at 120 oC for 20 h under N2.
Yields shown are of isolated products.
S
N
N
N
Bn
Bn
S
S
S
N
S
S
[a]
Furthermore, we wanted to gain some mechanistic insights of
this oxidative coupling of alkane C(sp3)-H bonds with aryl
mercaptans. Control experiments were carried out firstly. When
I2 was excluded from the system, the yield of sulfide lowered
slightly [Scheme 5, eq(1)]. Which indicated that I2 was involved
among the transformation. Then, benzyl iodide was employed
to react with 4-methylthiophenol (see supporting imformation,
Scheme S1) and only 30% of the aryl alkyl sulfide was
obtained. This result suggested that the iodization/substitution
procedure may not be the main access led to the formation of
product.
3ai
3aj
38%
70%
3ak
72%
Scheme 2. I2-promoted oxidative C(sp3)-H/S-H coupling of toluene with aryl
mercaptans. Reaction conditions: 1a (4 mL),
(0.045 mmol) at 120 oC for 20 h under N2. Yields shown are of isolated products.
2 (0.3 mmol), DTBP (1.5 mmol), I2
Bn = benzyl. [a] 2k (0.15 mmol).
Inspired by the encouraging results, the reactivity of methyl
arenes was further investigated. 4-methoxy-thiophenol 2f was
selected to react with various methyl arenes due to the easier
isolation of the products. The methyl arenes bearing multiple
methyls, which enriched the electron density of the arene
Then in situ IR was selected to monitor the reaction between
toluene and 4-methylthiophenol to figure out the role of I2. We
can see that 4-methyl-thiophenol consumed within 3 minutes
accompanying the generation of 4-methylphenyl disulfide (see
supporting information, Figure S1). The sampling experiment
revealed that the disulfide generated very fast with the yield of
79% (Figure 1, disulfide with I2), and the product did not form
until the fully consumption of mercaptans (Figure 1, product
with I2). Slower generation of the disulfide and lower yield of
the product were observed when I2 was taken away from the
system (Figure 1, disulfide and product without I2). Therefore,
we drew the inference that the disulfides may be the
intermediate of the reaction, and I2 may act as accelerator of the
generation of disulfide14. The accelerated dimerization might
prevent the side reactions of mercaptans, which may result to
the slight promotion of the yield. Another control experiment
showed that disulfide exhibited similar activity compared with
mercaptan [Scheme 5, eq(2)], which further confirmed the
deduction.
slightly, exhibited good activity (Scheme 3, 3bf, 3ff). However,
methyl arenes bearing electron-deficient group such as Cl and
Br group exhibited lower activity in the reaction (Scheme 3,
3cf, 3df, 3ef). Steric effect was also not observed since the o-Br
and
p
-Br toluenes showed similar activity (Scheme 3, 3df
,
3ef).
OMe
I2 (15 mol%)
HS
DTBP (5 equiv)
N2, 120 oC, 20 h
H
+
R
S
R
OMe
1
2f
3
OMe
OMe
OMe
S
S
S
Br
OMe
Cl
3df 66%
3bf 78%
3cf 68%
OMe
S
S
Br
In view of the previous reports employed methyl arenes as
the benzyl source and DTBP as the oxidant, a single electron
3ef 70%
3ff 79%
Scheme 3. I2-promoted oxidative C(sp3)-H/S-H coupling of various methyl arenes transfer (SET) process led to the generation of benzyl radical
might be one step among the reaction7d, 15. Therefore, a radical-
trapping experiment was carried out using butylated
hydroxytoluene (BHT) as the radical trapper. As predicted, the
coupling reaction was suppressed by BHT [Scheme 5, eq(3)].
Thus we believed that a radical process was involved among
the reaction.
Then, to further confirm our speculation, electron
paramagnetic resonance (EPR) experiments were carried out. A
complicated spectrum was recorded when 5,5-dimethyl-1-
pyrroline N-oxide (DMPO) was added to the reaction of
toluene and DTBP [Figure 2(a)]. Moreover, with I2 or both I2
with 4-methoxy-thiophenol. Reaction conditions:
1 (4 mL), 2f (0.3 mmol), DTBP
(1.5 mmol), I2 (0.045 mmol) at 120 oC for 20 h under N2. Yields shown are of
isolated products.
Since the bond dissociation energy (BDE) of toluene C(sp3)-
H bond (
89 Kcal/mol11) was low among the C(sp3)-H bonds,
cyclohexane, another alkane with relatively low C(sp3)-H bond
energy (96 kcal/mol12), was tested utilizing the standard
condition. To our delight, the corresponding phenyl alkyl
sulfide was obtained in the yield of 80% (Scheme 4, 5af).
Moreover, the BDE of C(sp3)-H bond of acetone was 95
2 | J. Name., 2012, 00, 1-3
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and 4-methylphenyl disulfide added to above system, similar
Furthermore, an intermolecular kinetic isotopic effect (KIE)
radical signal was recorded [Figure 2(b, c)]. This result experiment was carried out, and a noteworthy KIE was
excluded I2 and disulfide from the radical signal source. When observed with the kH/kD = 3.0 (Scheme 6). This result indicated
toluene was replaced by cyclohexane, a different signal was that the C(sp3)-H bond activation might be involved in the rate
recorded [Figure 2(d)], which indicated that the radical signal determining step.
was related to the C(sp3)-H bonds, and thus the C(sp3) radical
generated from the C(sp3)-H bonds may be the intermediate of
the reaction.
disulfide with I2
100
product with I2
disulfide without I2
80
product without I2
Scheme 6. KIE experiment
60
Based on the experiment results and literature precedent, a
40
plausible mechanism was proposed. Initially, an oxidative
dimerization of aryl mercaptans took place quickly to give
20
corresponding disulfide with the I2 as the catalyst and DTBP as
the oxidant. The homocoupling of the sulfur radical, which
0
generated from the S-H bond abstraction by tert-butoxy radical,
0
5
10
15
20
were believed to be the route14. The tert-butoxy radical could
also abstracted hydrogen from methyl arene to obtained benzyl
radical with a lower rate that it did not occur before the
completely consumption of the mercaptan. This step was also
considered to be the rate determining step (RDS). Afterward,
there are two possible pathways. Similar to organic peroxides,
the disulfide might act as a sulfur radical pool that it release the
sulfur radical slowly through homolysis16. And the sulfur
radical couple with the benzyl radical to afford the product.
Another possibility is that radical-substitution occurred between
benzyl radical and disulfide6b, 10, 17 to give the product and the
sulfur radical, which dimerized quickly to regenerate the
disulfide.
t / h
Figure 1. The sampling experiment of reaction mixture of 1a (4 mL), 2a (0.3
mmol), DTBP (1.5 mmol) at 120 oC with and without I2 respectively.
In summary, we have established an oxidative C(sp3)-H/S-H
coupling of alkanes with mercaptans to afford aryl alkyl
sulfides with the employment of cheap and nontoxic I2 and
DTBP in moderate to good yields. This proposal provided a
novel process to construct C(sp3)-S bond using alkanes and
mercaptans directly, which eliminate the pre-functionalization
of the starting materials and might encourage the further
application. The mechanism study suggested that the disulfides
were the intermediate and the C(sp3)-H bond cleavage was the
rate-determing step of the transformation.
Scheme 5. Control experiments and Radical trapping experiment
similar radical signal
(a)
DTBP + toluene
(b)
DTBP + toluene + I2
Acknowledgement
(c)
This work was supported by the 973 Program
(2011CB80860, 2012CB725302), the National Natural Science
Foundation of China (21390400, 21025206, 21272180 and
21302148), and the Research Fund for the Doctoral Program of
Higher Education of China (20120141130002) and the Program
for Changjiang Scholars and Innovative Research Team in
University (IRT1030). The Program of Introducing Talents of
Discipline to Universities of China (111 Program) is also
appreciated.
DTBP + toluene
+ I2 + disulfide
(d)
DTBP + cyclohexane
different radical signal
3325
3350
3375
3400
field / G
Figure 2. The electron paramagnetic resonance (EPR) spectra (X band, 9.4GHz,
RT) of (a) reaction mixture of DTBP (1.5 mmol) in toluene (2 mL) at 120 oC for 5
h with the addition of DMPO; (b) Reaction mixture of DTBP (1.5 mmol) and I2
(0.045 mmol) in toluene (2 mL) at 120 oC for 5 h with the addition of DMPO; (c)
Reaction mixture of DTBP (1.5 mmol), I2 (0.045 mmol) and 4-methylphenyl
disulfide (0.2 mmol) in toluene (2 mL) at 120 oC for 5 h with the addition of
DMPO; (d) Reaction mixture of DTBP in cyclohexane (2 mL) at 120 oC for 5 h
Notes and references
a
College of Chemistry and Molecular Sciences, Wuhan University,
Wuhan, Hubei 430072, P. R. China. Fax: (+86)-27-68754067; Tel:
(+86)-27-68754672; E-mail: aiwenlei@whu.edu.cn;
b
National Research Center for Carbohydrate Synthesis, Jiangxi Normal
with the addition of DMPO
.
University, Nanchang, Jiangxi, 330022, P. R. China.
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DOI: 10.1039/C4CC05661B
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See DOI:
10.1039/c000000x
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The C(sp3)-S bond formation was achieved utilizing C(sp3)-H and S-H as the nucleophiles. Methyl
arenes, cycloalkanes and aliphatic ketones exhibited reactivity for this transformation. Mechanism
study revealed that C(sp3) radical and disulfide were the intermediates of the reaction.