Metal-free preparation of cycloalkyl aryl sulfides via di-tert-butyl peroxide-promoted oxidative C(sp3)-H bond thiolation of cycloalkanes

Article abstract of DOI:10.1002/adsc.201400032

A concise thiolation of the C(sp³)-H bond of cycloalkanes with diaryl disulfides in the presence of the oxidant di-tert-butyl peroxide (DTBP) has been developed. This reaction, without using any metal catalyst, tolerates varieties of disulfides and cycloalkanes substrates, giving good to excellent chemical yields, and thus provides a useful approach to cycloalkyl aryl sulfides from unactivated cycloalkanes.

Full text of DOI:10.1002/adsc.201400032

UPDATES
DOI: 10.1002/adsc.201400032
Metal-Free Preparation of Cycloalkyl Aryl Sulfides via Di-tert-
3
À
butyl Peroxide-Promoted Oxidative C
G
Cycloalkanes
Jincan Zhao,a Hong Fang,a Jianlin Han,a,b,* Yi Pan,a and Guigen Lib,c
a
School of Chemistry and Chemical Engineering, State of Key Laboratory of Coordination, Nanjing University, Nanjing
210093, Peopleꢀs Republic of China
Fax : (+86)-25-8368-6133, phone: (+86)-25-8368-6133; e-mail: hanjl@nju.edu.cn or yipan@nju.edu.cn
Institute for Chemistry & BioMedical Sciences, Nanjing University, Nanjing, 210093, Peopleꢀs Republic of China
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA
b
c
Received: January 9, 2014; Revised: April 1, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400032.
3
À
Abstract: A concise thiolation of the C
(sp ) H
lyst, has attracted considerable interest of organic
3
chemists in recent years.[5] However, C
A
À
bond of cycloalkanes with diaryl disulfides in the
presence of the oxidant di-tert-butyl peroxide
(DTBP) has been developed. This reaction, without
using any metal catalyst, tolerates varieties of disul-
fides and cycloalkanes substrates, giving good to ex-
cellent chemical yields, and thus provides a useful
approach to cycloalkyl aryl sulfides from unactivat-
ed cycloalkanes.
[6]
[7]
À
À
À
activation of cycloalkanes to form C C, C O,
N[8] bonds still has not been well reported because the
3
À
C
(sp ) H bond activation of cycloalkanes is more dif-
3
À
ficult than C
(sp ) H bond activation adjacent to het-
eroatoms, double bonds, phenyl or electron-withdraw-
ing groups. Li and others have done elegant work in
this field using a transition metal catalyst (such as Ru,
Sc, Fe, etc.) both for activating the C
(sp ) H bond of
3
cycloalkanes and subsequent coupling to form C Y
(Y=O, N, C) bonds.[9] Recently, our group also devel-
oped an Fe-catalyzed decarboxylative alkenylation of
cycloalkanes via a radical process.[10] The metal-free
À
Keywords:
CU
(sp ) H activation; cycloalkanes;
metal-free conditions; oxidative process; thiolation
3
À
C
C
N
ACHTUNGTRENNUNG(sp )
À
The formation of C S bonds represents an active re- alkanes promoted by DTBP has also been reported
search area in general organic chemistry, material sci-
ence as well as biological and pharmaceutical chemis-
try.[1] In the past decade, a number of methodologies
have been developed in this field. In particular, transi-
tion metal-catalyzed cross-coupling reactions of thiols
with aryl halides provided the most general strategies
[2]
À
for constructing C S bonds. Recently, metal-cata-
2
À
À
lyzed C S bond formation through C
(sp ) H bond
activation has become an alternative and intriguing
method for the preparation of sulfides due to its high
atom-economy and efficiency.[3] However, the cleav-
3
À
À
age of a C
(sp ) H bond leading to C S bond forma-
tion is less studied. Very recently, Xiang and co-work-
ers reported a novel thiolation of the C
3
À
N
adjacent to a nitrogen or oxygen atom (Scheme 1a
and b).[4] To date, thiolations of the C
(sp ) H bond of
3
À
unactivated alkanes still have not been developed.
(sp ) H transformation of alkanes,
which is a great challenge due to their low reactivity
3
À
The direct C
U
3
À
and the lack of a coordination site for the metal cata- Scheme 1. CACTHNUGRTNEUNG(sp ) H bond functionalization.
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Jincan Zhao et al.
Table 1. Optimization of reaction conditions.[a]
of the conditions showed that the reaction could not
proceed without the use of DTBP as oxidant (Table 1,
entry 12).
With the optimized reaction conditions in hand,
this approach was then applied to the coupling of cy-
clohexane to a variety of diaryl disulfides (Scheme 2).
As shown in Scheme 2, the process has a broad scope
and high compatibility with functional groups such as
methyl, methoxy, halo and nitro substituents. Also,
ortho-, meta- and para-substituted diaryl disulfides
were well tolerated, and the reactions gave the corre-
sponding products with good to excellent yields of
71–92% (3a–h). The lower yields observed in the case
of ortho-substituted diaryl disulfides compared to the
para- or meta- analogues, is possibly due to the steric
hindrance (3d–f). The reaction with para-methyl- and
para-methoxy-substituted diaryl disulfides afforded
the expected products with excellent yields (3b and
3c). However, when para-fluoro and para-nitro-substi-
tuted diaryl disulfides were used as the coupling part-
ner the product yields dropped (85% for 3d and 75%
Entry
Oxidant (equiv.)
T [oC]
Yield [%][b]
1
2
3
4
5
6
7
8
TBHP (4.0)
DTBP (4.0)
DDQ (4.0)
K2S2O8 (4.0)
H2O2 (4.0)
TBPB (4.0)
DTBP (2.0)
DTBP (4.0)
DTBP (6.0)
DTBP (4.0)
DTBP (4.0)
–
120
120
120
120
120
120
120
100
120
140
120
120
23[c]
88
N.D.
N.D.
trace[d]
18
75
69
86
9
10
11
12
87
79[e]
N.D.
[a]
Catalytic conditions: 1 (0.5 mmol), cyclohexane (2 mL),
oxidant, 24 h.
Isolated yields based on 1.
70% in water solution.
30% aqueous solution.
CuACHTUNGTRENNUNG(OAc)2 (0.05 mmol) was added.
[b]
[c]
[d]
[e]
(Scheme 1c).[11,12] To the best of our knowledge, no ex-
À
amples for the construction of a C S bond through
3
À
C
N
been described. Herein, we now report the first reali-
3
À
zation of the thiolation of C
alk
(sp ) H bonds of cyclo-
anes through DTBP-mediated oxidative C
bond functionalization without the aid of a transition
metal catalyst (Scheme 1d).
3
À
E
U
N
Initially, we conducted our investigation by reacting
1,2-diphenyldisulfane 1 (0.5 mmol) with cyclohexane
2a (2 mL) in the presence 4.0 equiv. of tert-butyl hy-
droperoxide (TBHP) at 1208C for 24 h. The reaction
did happen, and afforded the expected product of
cyclohexylACHTUNGTRENNUNG(phenyl)sulfane 3a in a poor yield (23%,
Table 1, entry 1). On replacing TBHP with DTBP, the
yield dramatically increased to 88% without the aid
of any metal catalyst or other additives (Table 1,
entry 2). The use of other oxidants such as DDQ,
K2S2O8, H2O2 (30% aqueous solution) or TBPB did
not provide any better results (Table 1, entries 3–6).
With a decrease in the loading of DTBP to 2.0 equiv.
or at a lower temperature of 1008C, lower yields were
obtained, 75% and 69%, respectively (Table 1, en-
tries 7 and 8). No significant effect on the yield of 3a
was found with use of 6.0 equiv. of DTBP or at
a higher temperature (Table 1, entries 9 and 10). Fur-
thermore, the addition of a metal catalyst, Cu
(10 mol%), did not result in any improvement of the
ACHTUNGERTN(NUNG OAc)2
Scheme 2. Thiolation of cyclohexane with disulfides. Reac-
tion conditions: 1 (0.5 mmol), cyclohexane (2 mL), DTBP
yield (79%, Table 1, entry 11). Further optimization (4.0 equiv.), 1208C, 24 h. Isolated yields based on 1.
2
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Metal-Free Preparation of Cycloalkyl Aryl Sulfides
Scheme 4. Thiolation of hexane with disulfides. Reaction
conditions: 1b (0.5 mmol), hexane (2 mL), DTBP
(4.0 equiv.), 1208C, 24 h.
Scheme 3. Thiolation of cyclopentane with disulfides. Reac-
tion conditions: 1 (0.5 mmol), cycloalkanes (2 mL), DTBP
(4.0 equiv.), 1208C, 24 h. Isolated yields based on 1.
Scheme 5. Thiolation of 2,3-dimethylbutane with disulfides.
Reaction conditions: 1b (0.5 mmol), 2,3-dimethylbutane
(2 mL), DTBP (4.0 equiv.), 1208C, 24 h.
for 3h). These results imply that the electronegativity
of the substituents in the diaryl disulfides has an obvi-
ous effect on the chemical yields. In addition, the dis-
ubstituted diaryl disulfide is also well tolerated in this
reaction to give the target product with a slightly
lower yield of 80% (3i). Notably, the heterocyclic di- cloheptane and cyclooctane, comparative chemical
sulfides thienyl or pyridinyl disulfide can work well in yields were obtained (4h–j).
the reaction to provide the corresponding alkyl
Then, a linear substrate, hexane was tried in this re-
heteroaryl sulfide (3j–k). It is worthy of note that the action (Scheme 4). The reaction could proceed well
ACHTUNGTRENNUNG
reaction with the complex heterocyclic disulfides 2,2’- and give in total a 73% chemical yield, however,
dithiobis(benzothiazole) and 5,5’-dithiobis(1-phenyl- three isomers 5a–5c were obtained in the ratio of
1H-tetrazole) also proceed successfully under the op- 0.08:0.50:0.39, and could not be isolated.
timized condition (3l and 3m). Disappointingly, 1,2-di-
benzyldisulfane was not a suitable substrate for the ried out. 2,3-Dimethylbutane was tried as substrate
current thiolation system (3n). for this reaction (Scheme 5). It was unfortunate to
Also, the examination of branched alkane was car-
Subsequently, other cycloalkanes, including cyclo- find that 2,3-dimethylbutane was not a suitable sub-
pentane, cycloheptane and cyclooctane were em- strate for the current reaction, and only a trace
ployed as substrates for this reaction to further exam- amount of the desired product was found.
ine the reaction scope (Scheme 3). Fortunately, they
Then intramolecular and intermolecular competi-
work well in the system under the optimized condi- tion experiments were carried out. Firstly, heteroaryl
tions, and can react with different diaryl disulfides 1, aryl disulfide 1o was used for the investigation of the
giving the corresponding products 4a–j in 67–89% intramolecular competition reaction (Scheme 6). We
chemical yield. Comparing with the results shown in found both of these two ArSC could react with cyclo-
Scheme 2 for cyclohexane as a substrate, the reactions hexane well, giving the cross-coupling products 3l and
with cyclopentane showed a lower efficiency, and ob- 3b in 85% and 86% chemical yields, respectively.
vious lower yields were found (67–82%, 4a–g). How-
Then, the examination of the intramolecular com-
ever, for the cases of larger cycloalkanes, such as cy- petition reaction was performed with the using of di-
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Jincan Zhao et al.
Scheme 6. Investigation of the intramolecular competition
reactions. Reaction conditions: 1o (0.5 mmol), cyclohexane
(2 mL), DTBP (4.0 equiv.), 1208C, 24 h.
Scheme 9. A possible reaction mechanism.
and almost no desired product was observed. These
results indicate that the transformation may proceed
via a radical course.
Based on the above results and literature re-
ports,[4,10,13] a possible mechanism for the cycloalkane
thiolation reaction is illustrated in Scheme 9, which
includes a key radical oxidative coupling step. At the
beginning, homolysis of DTBP gives tert-butoxy radi-
cal intermediate A under the conditions of heating.
Then, cyclohexane radical intermediate B is generat-
ed via reaction of intermediate A and cyclohexane 2a
Scheme 7. Investigation of the intermolecular competition
reactions. Reaction conditions: 1l (0.25 mmol), 1b (0.25
mol), cyclohexane (2 mL), DTBP (8.0 equiv.), 1208C, 24 h.
À
through a C H bond cleavage. The following step is
the reaction between intermediate B and 1,2-diphe-
nyldisulfane 1, affording the final target product 3a,
along with the formation of PhSC free radical inter-
mediate C. Finally, the free radical C couples with cy-
clohexane radical B, giving another molecular of
product 3a.
In conclusion, we have presented a novel and
À
highly efficient method for C S cross-coupling
3
À
through direct C
N
cloalkanes with diaryl sulfides using DTBP as the oxi-
dant without use of any metal catalyst. Varieties of
substituted diphenyl disulfides and heterocyclic disul-
fides could be tolerated and coupled with cycloal-
kanes, giving the cycloalkyl aryl sulfides in good to
excellent yields. Moreover, this synthetic strategy for
À
Scheme 8. Insights into the mechanism.
sulfides 1l and 1b as substrates at the same time direct C S bond formation might be very valuable
(Scheme 7). The reaction with both of these two disul- and attractive in radical chemistry.
fides proceeded very well, and good chemical yields
were obtained (3l and 3b in 82% and 84%, respec-
tively).
Experimental Section
To gain insights into the reaction mechanism, sever-
al control experiments were carried out (Scheme 8).
Addition of the radical-trapping reagents 2,2,6,6 tetra-
General Procedure for Thiolation of Cycloalkanes
methylpiperidine N-oxide (TEMPO) or azobisisobu-
tyronitrile (AIBN) can completely inhibit the reaction bar was charged with diaryl disulfides (0.5 mmol), DTBP
A sealable reaction tube equipped with a magnetic stirrer
4
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UPDATES
Metal-Free Preparation of Cycloalkyl Aryl Sulfides
(di-tert-butyl peroxide, 2.0 mmol, 377 mL), and cycloalkanes
(2.0 mL). The rubber septum was then replaced by a Teflon-
coated screw cap, and the reaction vessel placed in an oil
bath at 1208C. After stirring at this temperature for 24 h,
the reaction mixture was cooled to room temperature and
diluted with ethyl acetate, washed with water, dried over
MgSO4. After the solvent had been removed under reduced
pressure, the residue was purified by column chromatogra-
phy on silica gel (petroleum) to afford the direct cross-cou-
pling product, cycloalkyl aryl sulfides. In this reaction,
0.5 mol of diaryl disulfides can afford 1 mol of PhS· free rad-
ical as shown in Scheme 9, which finally can give 1 mol of
cross-coupling product. So the yields and amounts of prod-
ucts are given based on this.
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Acknowledgements
We gratefully acknowledge the financial support from the Na-
tional Natural Science Foundation of China (No. 21102071)
and the Fundamental Research Funds for the Central Univer-
sities (No. 1107020522 and No. 1082020502). The Jiangsu 333
program (for Pan) and Changzhou Jin-Feng-Huang program
(for Han) are also acknowledged.
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Metal-Free Preparation of Cycloalkyl Aryl Sulfides via Di-
7
3
À
tert-butyl Peroxide-Promoted Oxidative C
Thiolation of Cycloalkanes
N
Adv. Synth. Catal. 2014, 356, 1 – 7
Jincan Zhao, Hong Fang, Jianlin Han,* Yi Pan, Guigen Li
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