Selective approach to thioesters and thioethers via sp3 C-H activation of methylarenes

Article abstract of DOI:10.1039/c4ra09450f

Novel C-S cross-dehydrogenative coupling (CDC) approaches for the selective synthesis of thioesters and thioethers have been developed via sp³ C-H activation of methylarenes and subsequent functionalization. The reaction of methylarenes with thiols resulted in thioesters in the presence of a FeBr₂/TBHP system, while treatment of methylarenes with thiols in the Pd(OAc)₂/O₂/TBHP system led to the formation of thioethers. Both the green protocols demonstrate good functional group tolerance and satisfactory yields. This journal is

Full text of DOI:10.1039/c4ra09450f

View Article Online
View Journal
RSC Advances
This article can be cited before page numbers have been issued, to do this please use: J. Feng, G. Lu and
C. Cai, RSC Adv., 2014, DOI: 10.1039/C4RA09450F.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. This Accepted Manuscript will be replaced by the edited,
formatted and paginated article as soon as this is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/advances

View Article Online
DOI: 10.1039/C4RA09450F
Page 1 of 8
RSC Advances
Journal Name
RSC
ARTICLE
Selective approach to thioesters and thioethers via sp3
C-H activation of methylarenes
J. Feng,a G.-P. Lu a and C. Cai a ,
Novel C-S cross-dehydrogenative coupling (CDC) approaches for selective synthesis of
thioesters and thioethers has been developed via sp3 C-H activation of methylarenes and
subsequent functionalization. The reaction of methylarenes with thiols resulted in thioesters in
the presence of FeBr2/TBHP system, while treatment of methylarenes with thiols in the
Pd(OAc)2/O2/TBHP system led to the formation of thioethers. Both the two green protocols
demonstrate good functional group tolerance and satisfactory yields.
functionalization of methylarenes has drawn scientist’s
Introduction
attention.2e,16 Through this strategy, methyl arenes especially
methylbenzenes are found to be useful precursors and have
been used as ArCOO−,17 ArCO−,3h,5b,18 ArCH2O−19 and
ArCH2− surrogates.20 Considering the availability and economy
of methylarenes and the few reported C-S formation examples
via CDC protocol,6a,21 herein we wish to report two novel
methods for synthesis of thioesters and thioethers via sp3 C-H
activation of methylarenes, thus the use of more traditional
coupling partners that require prefunctionalisation, including
aryl halide, acyl halide, aryl acid, aryl aldehyde etc. are avoided.
The direct C−H activation path is now being extensively
investigated as the short step and greener alternative to the
traditional transition-metal-catalyzed couplings.1 One such
strategy, cross-dehydrogenative coupling (CDC) is of immense
importance because it does not require substrate
prefunctionalisation and enjoys the advantage of atom
economy.2 Screening of reference revealed that the CDC based
protocols in the construction of a C–C3, C-O4, C-N5 bond have
been well achieved using transition metal catalysts in
combination with various oxidants. However there is still a
6
dearth of information on C-S bond formation. In this regard, Results and discussion
C-S bond formation and eventual synthesis of thioesters and
thioethers involving C-H bond activation of methylarenes
remains the cherished target.
Encouraged by recent Fe-catalyzed synthesis of thioesters
from thiols and aldehydes15k, we initiate our work using toluene
and 4-chlorobenzenethiol under the similar conditions (Fe,
TBHP system). The aimed thioesters was observed in low yield
by GC-MS along with the formation of benzaldehyde and
disulfide22 (Table 1, entry 7). In the process to optimize the
reaction conditions, it was found that small amount of thioether
was formed when Pd(OAc)2 was used (Table 1, entry 6).
Promising to selectively obtain thioesters and thioethers we
optimized both the two reactions respectively.
As the reaction was conducted in water, surfactants may
accelerate the reaction process. Screening nonionic and ionic
surfactants revealed that nonionic surfactants such as Trion-X
100, Prij were ineffective, whereas in the presence of TBAI, the
yield increased to 25%. The addition of 2%wt.SDS/water
boosted the yield to 65% (Table 1, entries 7-10). Next, we
examined the metal catalysts in a quest to improve the yield
(Table 1 entries 3-6).
Sulfur-containing compounds, especially thioesters and
thioethers represent a class of important synthetic intermediates
due to their ease of transformation.7 Besides that, they are
excellent building blocks for chemical biology, and hence are
frequently found in a number of biologically active and
medicinal agents.8 Traditionally, thioethers were formed by
coupling reactions between halides and thiols (or sulfur
surrogates),9 the SNAr reactions,10 substitution reactions11 etc.
whereas thioesters were commonly prepared via acylation with
thiols (or sulfur surrogates) and carboxylic acids 12, carboxylic
acid halides 13, carboxylic acid anhydrides14 or aldehydes15.
Although, many elegant protocols for synthesis of thioethers
and thioesters emerged, in accordance with the importance of
them, the synthesis of thioethers or thioesters by
unconventional approaches
was always appreciable,
particularly through functionalization of inert C−H bonds.
Methylarenes, derived from oil industry, constitute the most
inexpensive and readily available feed stocks for chemistry. Of
late, the sp3 C−H activation and subsequent oxidative
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 1

View Article Online
DOI: 10.1039/C4RA09450F
RSC Advances
Page 2 of 8
ARTICLE
Journal Name
product (Table 2, 3n) in moderate yield. Unfortunately, the reaction
failed to proceed in the case of 1H-benzo[d]imidazole-2-thiol witha
collection of byproducts including open ring product, C-N coupling
product instead of the aimed thiester obtained (Table 2, 3q).
Table 1. Screening for optimal conditionsa
Table 2. Scope of thiols in the oxidative esterification a
Entry
Change from the “standard conditions”
Yieldb
65(80c)
<1
1
none
2
No FeBr2
Entry
Product
Yield(%)[b]
3
FeCl2 instead of FeBr2
62
1
2
3
4
5
6
7
8
9
R=4-Cl
R=2-CH3
R=4-CH3
R=4-F
3a
3b
3c
3d
82
45
56
66
84
64
71
72
65
4
Fe(acac)3 instead of FeBr2
Cu(OAc)2 instead of FeBr2, no surfactant
Pd(OAc)2 instead of FeBr2, no surfactant
No surfactant
43
5
8
6
<1 (7d)
12(80e)
10
7
R=4OCH3 3e
8
2 wt.% Prij L23 instead of 2 wt.% SDS
2 wt.% Trion X100 instead of 2 wt.% SDS
0.1eq TBAI instead of 2 wt.% SDS
BPO instead of TBHP
R=4-F
R=H
3f
3g
3h
3i
9
11
10
11
12
a
25 (69e)
0 (95e)
0 (10e)
R=4-CH3
DTBP instead of TBHP
Standard conditions: toluene 1.5 mmol, 4-chlorobenzenethiol 0.5
mmol, FeBr2 0.01 mmol, TBHP(70% in water) 1.5 mmol, 2%
o
b
c
wt.SDS/H2O 1 mL, 100 C, 24 h. the yield was determined by GC;
10
11
3j
10
thiol was added in a dropwise fashion. d the yield of thioether. e the yield
of disulfide.
Among all the catalysts tested, FeBr2 was still found to be the best
choice. Oxidants were also checked. In the presence of BPO, 4-
chlorobenzenethiol converted to the corresponding disulfide quickly
without the desired thioester formed (Table 1, entry 11), while in
case of DTBP, most starting materials were not converted (Table 1,
entry 12). Among all the conditions, the formation of disulfide
seemed inevitable. When the thiol was added in a dropwise fashion,
the yield of thioester could increase to 80% (Table 1, entry 1).
Having established the optimized reaction conditions, the present
oxidative esterification reactions were then implemented on the
reaction between toluene and a series of substituted thiophenols and
thiols. As is shown in Table 2, thiophenols containing electron-
donating or electron-withdrawing groups reacted smoothly with
toluene, giving thioesters in moderate to good yields (Table 2, 3a-3e).
There is a decrease of yield when thiophenols bear methyl group at
different positions (Table 2, 3b, 3c). It was found that the methyl
group can also be activated with small amount of
mercaptobenzaldehyde and mercapto thioesters observed. Alkyl
thiols can also successfully couple with toluene (Table 2, 3f-3k, 3m，
3o). In general, the product yields for the alkyl thiols are lower than
those of thiophenols. Especially, sterically demanding substrates
yield the product in a lower level (Table 2, 3j). It is worth to note
that thiols bearing fluorous tail can also undergo this coupling which
may be useful in fluorine chemistry23 (Table 2, 3p). We further
checked heterocyclic thiophenols. To our delight, the reaction
between toluene and benzo[d]thiazole-2-thiol afforded the aimed
3k
3l
35
0
12
13
3m 52
14
3n
46
15
16
3o
3p
42[c]
45
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

View Article Online
DOI: 10.1039/C4RA09450F
Page 3 of 8
Journal Name
RSC Advances
ARTICLE
17
3q
0
4k
15
’
a
Reaction conditions: toluene 1.5 mmol, thiol 0.5 mmol, FeBr2 0.01
a Reaction conditions: toluene 1.5 mmol, thiol 0.5 mmol, FeBr2 0.01 mmol,
TBHP(70% in water) 1.5 mmol, 2 wt.%SDS/H2O 1 mL, 100 oC, 24 h;b
o
mmol, TBHP(70% in water) 1.5 mmol, 2 wt.% SDS/H2O 1 mL, 100 C,
b
c
24 h. Isolated yield. Reaction conditions: toluene 1.5 mmol, thiol 1
mmol, FeBr2 0.02 mmol, TBHP(70% in water) 3 mmol, 2 wt. %
SDS/H2O 1 mL, 100 oC, 36 h.
c
Isolated yield; Reaction conditions: toluene 1.5 mmol, thiol 0.25 mmol,
FeBr2 0.02 mmol, TBHP(70% in water) 3 mmol, 2 wt.% SDS/H2O 1 mL,
100 oC, 36 h.
As mentioned above, thioether instead of thioester was obtained
when FeBr2 was replaced by Pd(OAc)2. Aimed to selective
preparation of thioethers, we further explored the palladium-
catalyzed CDC thiolation. Details of optimizations are shown in
Table 4. The yield of the desired thioether slightly increased when
the reaction was moved from the Argon atmosphere to the open air
albeit in a low yield (Table 4, entry 9). It indicated that oxidants may
play a key role in the CDC process, thus we put the reaction in a
pure oxygen atmosphere (Table 4, entry 1) and increased the
After that we turned our attention to the functional group
compatibility of methylarenes. Methylarenes containing a methyl-,
chloro-, bromo- or methoxy-substituent were all tolerated under the
reaction conditions (Table 3, 4a-4d, 4f-4g). However, methylarene
bearing a –N(CH3)2 substituent failed to couple with the thiophenol.
The demethylation of the N-CH3 was observed under the standard
condition.The steric hindrance had little influence with similar yields
obtained with 4b, 4g. When there are more than one methyl group in
the benzene ring (for example 4k), the “dithioester” could be
afforded when added more TBHP and extended the reaction time. equivalent of TBHP respectively (Table 4, entry 11). The addition
Acompany with 4k, S-(p-tolyl) 3-formylbenzothioate 4k’ was also
observed. Remarkably, naphthalene-containing methylarenes could
also serve as coupling partners with thiols (Table 3, 4j). But
unfortunately, only trace amount of the aimed product was observed
when pyridine-containing substrate was used.
of excess TBHP had no positive effect to the present reaction but
produced more benzaldehyde and sulfur oxidation products in
adverse. Gratefully, when the reaction was conducted under oxygen
atmosphere, the yield increased to 86%. In view of this result, TBHP
may not be necessary. However, the yield dropped sharply in
absence of TBHP (Table 4, entry 7). It is known that thioether may
be oxidised by TBHP under heated conditions, however, only trace
amount of sulfur oxidation products were observed with the present
conditions . As same with the above reaction, surfactant was also
tried to accelerate the reaction, but it didn’t give any
improvement(Table 4, entry 6). Finally, some commercial available
palladium catalysts and copper catalysts were examined. Still,
Pd(OAc)2 was the best choice (Table 4, entries 3-5). And a decrease
in catalyst loading (5 mol %) had an adverse effect on product yield
(Table 4, entry 12).
Table 3. Scope of methylarenes in the oxidative esterification a
Entr
y
Product
Yield(%)
b
1
2
3
4
R=4-CH3
R=2,4-Cl
R=3-Br
4a
4b
4c
4d
69
79
77
83
Table 4. Optimal conditions for palladium-catalyzed CDC thiolation a
R=4-
OCH3
5
R=4-
N(CH3)2
4e
Trace
Entry
Change from the “standard conditions” Yield[b]
1
2
3
4
5
6
none
86
0
6
7
8
9
R=4-NO2 4f
52
No Pd(OAc)2
R=4-Cl
4g
4h
4i
80
Cu(OAc)2 instead of Pd(OAc)2
Pd(PPh3)2Cl2 instead of Pd(OAc)2
Pd(dppf)Cl2 instead of Pd(OAc)2
0
R=4-CF3
Trace
Trace
55
37
84
The addition of SDS (0.02 eq) as
surfactant
a
10
4j
75
45
7
8
9
No TBHP, 48h
Under Ar atomosphere
In the air
16
8(12c)
30
11[c]
4k
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3

View Article Online
DOI: 10.1039/C4RA09450F
RSC Advances
Page 4 of 8
ARTICLE
Journal Name
10
11
12
a
the addition of FeBr2
3eq TBHP
26(35d)
13
5m
55[d]
21(55c, 9d)
62
Pd(OAc)2 loading decreased to 5%
14
15
5n
5o
80
80
Standard conditions: toluene 1.5mmol, 4-chlorobenzenethiol 0.5mmol,
Pd(OAc)2 0.05mmol, TBHP(70% in water) 0.5mmol, 1 atom O2, 115oC,
24h. b The yield was determined by GC. c The yield of benzaldehyde. d The
yield of thioester.
Then these optimized conditions were applied for the reaction of
structurally different methylarenes and thiophenols or thiols. A
series of unsymmetrical aryl alkyl thioethers could be successfully
prepared from substituted methylarenes whereby electronic effect
showed no significant association with the yield (Table 4, 5a-5g).
Differently with the thioesterification described above, the steric
hindrance affected the product yield significantly(Table 4, 5b ,5g).
Like the above esterification reaction, the “di-thioether” could be
obtained under harsher reaction conditions (Table 5, 5q). We have
also investigated the applicability of our method using different
thiols or thiophenols. As expected, thiophenols could easily convert
to the aimed products for all the electronic-donating and the
electronic-withdrawing substituents (Table 5, 5i-5l). Alkyl thiols
including benzyl thiol and cyclohexanethiol were also applied for the
coupling. Symmetric thioether was obtained in good yield with
benzyl thiol (Table 5, 5n), while cyclohexanethiol reacted sluggishly
and a 55% yield was obtained by prolonging the reaction time (Table
5, 5m). At last, heterocyclic thiols were tested. Similarly,
benzo[d]thiazole-2-thiol underwent the present reaction smoothly
while benzo[d]imidazole-2-thiol failed this reaction (Table 5, 5o, 5p).
16
17
5p
5q
0
28[e]
[a] Reaction conditions: methylarenes 1.5mmol, thiol or thiophenol
0.5mmol, Pd(OAc)2 0.05mmol, TBHP(70% in water) 0.5mmol, 1atm O2,
115oC, 24h. [b] isolated yield. [c] the yield of 1,4-bis(((4-
chlorophenyl)thio)methyl)benzene. [d] reaction time 48h. [e] reaction
conditions: m-xylene 1.5mmol, thiophenol 1mmol, Pd(OAc)2 0.1mmol,
TBHP(70% in water) 1mmol, 1atm O2, 120oC, 36h.
To gain insight into the catalytic pathway of the two reactions, we
conducted some mechanistic experiments (Scheme 1). In the
presence of TBHP, thiophenol could easily convert to the disulfide.
Table 5. Scope of methylarenes in the oxidative thioetherification [a]
Entr
y
Product
Yield(%)[
b]
1
2
3
4
5
6
7
8
R=-H
5a
5b
5c
5d
5e
5f
84
R=4-F
77
R=4-CH3
R=4-NO2
R=4-CN
R=4-Br
R=2-F
62(4[c])
58
62
83
5g
5h
71
Scheme 1. Controlled experiments for preliminary mechanistic studies.
8
Thus disulfide was used for the developed two reactions to replace
the thiophenol. Under the standard conditions, both thioesterification
and thioetherification could proceed, but with lower yields. It means
thiophenol was more appropriate for the two reactions although the
formation disulfide was inevitable. During the reaction of toluene
with FeBr2/TBHP, both aldehyde and benzoic acid were observed
while in the Pd(OAc)2/O2 conditions, only trace amount of aldehyde
was observed. So we further put benzaldehyde and 4-chlorobenzoic
acid simultaneously into the thioesterification reaction. The
9
R=2-CH3
R=4-CH3
R=4-OCH3
R=4-F
5i
72
77
70
46
10
11
12
5j
5k
5l
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

View Article Online
DOI: 10.1039/C4RA09450F
Page 5 of 8
Journal Name
RSC Advances
ARTICLE
crossover experiment showed that benzaldehyde reacted with 4-
chlorobenzenethiolunder the present experimental conditions which
ruled out the usual esterification of acid and thiol. Also, the
thioesterification reaction was treated with a radical inhibtor. When
excess TEMPO (5 equivalents) was added, no thioester could be
observed which indicated that the Iron-catalyzed thoesterification
may follow a radical mechanism.
Based on the above results and in combination with the already
known mechanism in the literature15j, a plausible mechanism was
proposed as shown in scheme 2. In the Iron-catalyzed reaction,
toluene was firstly oxidized to form benzaldehyde which further
reacted with t-BuOO• to give an acyl radical. On the other hand, iron
salts promoted TBHP to form t-BuOO• and the FeBr2 converted to
immediate A which further reacts with the thiol or disulfide to give
an iron(III) thiolate complex B and release HBr. Then the complex B
traps the acyl radical to provide the aimed thioester and complex C,
C reacted with HBr to regenerate FeBr2 to close the circle.
As for the Pd-catalyzed cycle, the catalytic cycle starts with PdII-
mediated C-H cleavage to form benzyl Pd complex A’. The
benzylation products may result from nucleophilic attack on the
benzylic carbon by thiophenol (Path A). Alternatively, undergo
ligand exchange to afford benzyl Pd(II)carboxylate B’, and
subsequent reductive elimination yields thioether products (Path B).
The Pd0 species generated in Path A or B is oxidised to PdII by O2 to
continue the catalytic cycle. It should be noted that the existing
TBHP may accelerate the C-H cleavage and palladium oxidation
process (Pd0-PdII).
tetramethylsilane (TMS) was used as a reference. Elemental analysis
was performed on a Yanagimoto MT3CHN recorder. Preparative
high performance liquid chromatography was performed on an
Agilent Technologies 1200 Column: XDB- C18 9.6×250mm.
General procedure for synthesis of thioesters
A 5 ml vial with condenser was charged with toluene (1.5 mmol),
FeBr2 (0.01mmol), TBHP(1.5 mmol), 2% wt. SDS /H2O (2 ml), thiol
(or thiophenol)(0.5mmol) was then added in a dropwise (in portion
for solids) at 100oC. The reaction mixture was stirred at 100 oC for
24h. Upon completion, the reaction mixture was then cooled,
extracted with ethyl acetate, and dried over anhydrous Na2SO4. After
filtration, the organic solutions were concentrated and the residue
was purified by column chromatography on silica gel to give the
pure product (hexane/ethyl acetate=20/1).
General procedure for synthesis of thioethers
A mixture of toluene (1.5 mmol), Pd(OAc)2 (0.05 mmol), TBHP(1.5
mmol) thiol (thiophenol)(0.5mmol) was introduced in a pressure
reactor. The suspension was stirred at 115 oC for 24 h under 1 atm of
oxygen. After this, the pressure was released and the mixture was
extracted with ethyl acetate, and dried over anhydrous Na2SO4. After
filtration, the organic solutions were concentrated and the residue
was purified by column chromatography on silica gel to give the
pure product (hexane/ethyl acetate=50/1).
Conclusions
In summary, we developed two facile and efficient protocols
thus thioesters and thioethers can be selectively prepared via
the Fe-catalyzed C-H functionalization thioesterification and
Pd-catalyzed
C-H
functionalization
thioetherification
respectively. The major advantages of this method include the
use of toluene as the benzylation or benzoylation reagent and
oxygen or TBHP as the green oxidant, which owns high atom
economy, avoids the prefunctionalization of substrates and
reduces the production of chemical wastes. In addition, the two
rarely reported protocols demonstrate good functional group
tolerance and moderated to good yields.
Acknowledgements
We gratefully acknowledge Natural Science Foundation of
Jiangsu Province (BK 20131346) for financial support.
Notes and references
a
Chemical Engineering College, Nanjing University of Science &
Technology, 200 Xiaolingwei, Nanjing 210094, P. R. China. E-mail:
c.cai@ njust.edu.cn; Fax: +86-25-84315030
Scheme 2. Proposed mechanism for the Fe-catalyzed thioesterification and
Pd-catalyzed thioetherification via sp3 C-H activation of methylarenes.
Electronic Supplementary Information (ESI) available: [Experimental
procedures; spectral data for all reported compounds.. See
DOI: 10.1039/b000000x/
Experimental Section
1
For selected reviews or books on transition-metal-catalyzed C−H
functionalization, see: (a) G. Dyker, Handbook of C-H
Transformations: Applications in Organic Synthesis; Wiley-VCH:
Weinheim, 2005. (b) J.-Q. Yu and Z.-J. Shi, C-H Activation;
Springer: Berlin, Germany, 2010. (c) C. L. Sun, B. J. Li and Z. J. Shi,
Melting points are uncorrected. All commercial materials were used
without further purification. Thiols were synthesized according to
the literature [24]; TBHP used was 70% TBHP in water. GC-MS
analyses were performed on an Agilent 7890A-5975C instrument
(Column: DB-5 MS). NMR was recorded on Bruker DRX 500 and
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 5

View Article Online
DOI: 10.1039/C4RA09450F
RSC Advances
Page 6 of 8
ARTICLE
Journal Name
Chem. Rev. 2011, 111, 1293. (d) A. N. Campbell and S. S. Stahl, Acc. [7] (a) H. Tokuyama, S. Yokoshima, T. Yamashita and T. Fukuyama,
Chem. Res. 2012, 45, 851. (e) L. Ackermann, Chem. Rev. 2011, 111
,
Tetrahedron. Lett.1998, 39, 3189. (b) V. P. Mehta, A. Sharma and E.
Van der Eycken, Org. Lett. 2008, 10, 1147. (c) I. A. Os’kina and V.
1315.
2
(a) C. J. Li, Acc. Chem. Res. 2009,42, 335. (b) C. J. Scheuermann,
Chem. Asian J. 2010, , 436. (c) J. Le Bras and J. Muzart, Chem. Rev.
M. Vlasov, Russ. J. Org. Chem. 2009, 4, 523. (d) H. Azuma, K.
5
Okano and H. Tokuyama, Chem. Lett. 2011, 40, 959. (e)M. N.
Burhardt, A. Ahlburg, T. Skrydstrup, J. Org. Chem. DOI:
10.1021/jo5009965. (f) R. J. Cremlyn, An Introduction to
Organosulfur Chemistry, John Wiley & Sons: Chichester, 1996;
2011, 111, 1170. (d) C. S. Yeung and V. M. Dong, Chem. Rev. 2011,
111, 1215. (e) S. A. Girard, T. Knauber and C. J. Li, Angew.Chem.,
Int. Ed. 2014, 53, 74. (f) J. A. Ashenhurst, Chem. Soc. Rev.2010, 39
,
540.
[8] (a) D. N. Jones, Comprehensive Organic Chemistry, (Eds.: D. H.
Barton, D. W. Ollis), Pergamon, NewYork,1979. (b) A. Marcincal-
Lefebvre, J. C. Gesquiere and C. Lemer, J. Med. Chem.1981, 24,889.
[3] For selected recent references on CDC C-C formation see: a) Y. Wu,
B. Li, F. Mao, X. Li and F. Y. Kwong, Org. Lett. 2011, 13, 3258. (b)
F. Péron, C. Fossey, T. Cailly and F. Fabis, Org. Lett. 2012, 14, 1827.
(c) R. K. Chinnagolla and M. Jeganmohan, Org. Lett. 2012, 14, 5246.
(d) K. Padala and M. Jeganmohan, Org. Lett. 2011, 13, 6144. (e) M.
Brasse, J. Campora, J. A. Ellman and R. G. Bergman, J. Am. Chem.
Soc. 2013,135, 6427. (f) L. Liu, H. Lu, H. Wang, C. Yang, X. Zhang,
D. Zhang-Negrerie, Y. Du and K . Zhao, Org. Lett. 2013, 15, 2906.
(g) X. Cong, J. You, G. Gao and J. Lan, Chem. Commun. 2013, 49,
662. (h) S. Guin. S. K. Rout, A. Banerjee, S. Nandi and B. K. Patel,
Org. Lett.2012, 14, 5294.
(c)S. V. Ley and A. W. Thomas, Angew. Chem. Int. Ed. 2003, 42
,
5400. (d) T. Kondo and T. Mitsudo, Chem. Rev. 2000, 100, 3205. (e)
S. Magens and B. Plietker, Chem. Eur. J. 2011, 17, 8807. (f) A. R.
Katritzky, A. A. Shestopalov and K. Suzuki, Synthesis. 2004, 1806.
(g) S. Limura, K. Manabe and S. Kobayashi, Chem. Commun. 2002,
94. (h)C. C. Silveira, A. L. Braga and E. L. Larghi,
Organometallics.1999, 18, 5183. (i) H. M. Meshram, G. S. Reddy, K.
H. Mindu and J. S. Yadav, Synlett. 1998, 877.
[9] (a) A. V. Bierbeek and M. Gingras, Tetrahedron Lett.1998, 39,6283.
(b) C. C. Eichman and J. P. Stambuli, J. Org. Chem. 2009, 74, 4005.
(c) T. Dahl, C. W. Tornøe, B. Bang-Andersen, P. Nielsen and M.
Jørgensen, Angew. Chem. 2008, 120, 1726. (d) V. Percec, J. Y. Bae
and D. H. Hill, J. Org. Chem.1995, 60,6895. (e) Y. C. Wong, T. T.
[4] For selected recent references on CDC C-O formation see: a) W.
Zhou, L. Zhang and N. Jiao, Angew. Chem., Int. Ed. 2009, 48, 7094.
(b) S. K. Rout, S. Guin, K. K. Ghara, A. Banerjee and B. K. Patel,
Org. Lett. 2012, 14,3982. (c) X. F. Cheng, Y. Li, Y. M. Su, F. Yin, J.
Y. Wang, J. Sheng, H. U. Vora, X. S. Wang and J. Q. Yu, J. Am.
Chem. Soc. 2013, 135, 1236. (d) D. J. Covell and M. C. White,
Angew. Chem., Int. Ed. 2008, 47, 6448. (e) P. Novak, A. Correa, J.
Jayanth and C. H. Cheng, Org. Lett. 2006,
and T. Onami, J. Org. Chem. 2004, 69, 915. (h) F. Y. Kwong and S.
L. Buchwald, Org. Lett. 2002, , 3517. (i) Y. J. Chen and H. H. Chen,
Org. Lett. 2006, , 5609. (j) V. P. Reddy, K. Swapna, A. V. Kumar
8, 5613. (f) N. Taniguchi
4
Gallardo-Donaire and R. Martin, Angew. Chem., Int. Ed. 2011, 50
,
8
12236. (f) K. Takenaka, M. Akita, Y. Tanigaki, S. Takizawa and H.
Sasai, Org. Lett. 2011,13, 3506. (g) Y. Wei and N. Yoshikai, Org.
Lett. 2011,13, 5504. (h) E. Shi, Y. Shao, S. Chen, H. Hu, Z. Liu, J.
Zhang and X. Wan, Org. Lett. 2012, 14, 3384. (i) W. Liu, L.
and K. R. Rao, J.Org. Chem. 2009, 74, 3189. (k) V. P. Reddy, A. V.
Kumar, K. Swapna and K. R. Rao, Org. Lett. 2009, 11,1697. (l) A.
Correa, M. Carril and C. Bolm, Angew. Chem. Int. Ed.2008, 47, 2880.
(m) J. R. Wu, C. H. Lin and C. F. Lee, Chem. Commun.2009, 4450.
Ackermann, Org. Lett. 2013, 15, 3484. (j) F. Yang and L. Ackermann, [10] J. R. Campbell, J. Org. Chem.1964, 29, 1830.
Org. Lett. 2013, 15, 718. (k) T. S. Jiang and G. W. Wang, J. Org. [11] J. Ham, I. Yang and H. Kang, J. Org. Chem.2004, 69, 3236.
Chem.2012, 77, 9504. (l) W. Li and P. Sun, J. Org. Chem. 2012, 77
,
[12] (a) B. C. Ranu and R. Jana, Adv. Syn. Catal. 2005, 347, 1811. (b) T.
Uno, T. Inokuma and Y. Takemoto, Chem. Commun. 2012, 48, 1901.
(c) C. Simiona, I. Hashimotob, Y.Mitomac, A. M. Simiona and N.
8362-8366.
[5] For selected recent references on CDC C-N formation see: (a) K.
Kamata, T. Yamaura and N. Mizuno, Angew. Chem., Int. Ed.2012, 51
7250. (b) R. Vanjari, T. Guntreddi, K. N. Singh, Org. Lett. 2013, 15,
4908. (c) M. L. Louillat, F. W. Patureau, Org. Lett. 2013, 15, 164. (d)
J. Hu, S. Chen, Y. Sun, J. Yang, Y. Rao, Org. Lett. 2012,14, 5030. (e)
J. L. Liang, S. X. Yuan, J. S. Huang, W. Y. Yu, C. M. Che,
,
Egashirac, Phosphorus, Sulfur, 2010, 185
,
2480. (d) S.
Narayanaperumal, E. E. Alberto, K. Gul, C.Y. Kawasoko, L.
Dornelles, O.E.D. Rodrigues and A.L. Braga, Tetrahedron, 2011, 67
4723. (e) B. Basu, S. Paul and A. K. Nanda, Green Chem. 2010, 12
767.
,
,
Angew.Chem., Int. Ed. 2002, 41, 3465. (f) M. R. Yadav, R. K. Rit, A. [13] (a) S. Iimura, K. Manabe and S. Kobayashi, Chem. Commun. 2002,
1
K. Sahoo, Org. Lett. 2013,15, 1638. (g) R. J. Tang, C. P. Luo, L.
Yang and C. J. Li, Adv. Synth.Catal.2013, 355, 869. (h) C. Tang and
94. (b) N. Iranpoor, H. Firouzabadi, D. Khalili and S. Motevalli, J.
Org. Chem. 2008, 73, 4882.
N. Jiao, J. Am. Chem. Soc. 2012, 134, 18924. (i) J. Shi, B. Zhou, Y. [14](a) A. R. Massah, R. J. Kalbasi, M. Toghiani, B. Hojati, M.
Yang and Y. Li, Org. Biomol. Chem. 2012, 10, 8953. (j) C.
Grohmann, H. Wang and F. Glorius, Org. Lett. 2012, 14, 656. (k) K.
H. Ng, Z. Zhou and W. Y. Yu, Org. Lett. 2012, 14, 272.
Adibnejad and A. R. Massah, Journal of Chemistry, 2012, 9, 2501.
(b) S. K. Prajapti, A. Nagarsenkar and B.N. Babu, Tetrahedron Lett.
2014, 55, 1784.
[6] (a) B. N. Du, B. Jin and P. P. Sun, Org. Lett. 2014, 16, 3032. (b) S. R. [15] Selected recent references see a) S. Rossi, M. Benaglia, F. Cozzi, A.
Guo, Y. Q. Yuan and J. N. Xiang, Org. Lett. 2013,15, 4654. (c) B.
Basu, B. Mandal, S. Das and S. Kundu, Tetrahedron Lett. 2009, 50
Genoni and T. Benincori, Adv. Synth. Catal. 2011, 353, 848. (b) D.
Crich and I. Sharma, Angew. Chem., Int. Ed.2009, 48, 2355. (c) D.
Crich and K. Sasaki, Org. Lett. 2009, 11, 3514. (d) K. Matsuo and M.
Sindo, Org. Lett. 2010, 12, 5346. (e) K. Kunchithapatham, C. C.
Eichman and J. P. Stambuli, Chem. Commun. 2011, 47, 12679. (f) T.
Uno, T. Inokuma and Y. Takemoto, Chem. Commun.2012, 48, 1901.
,
5523. (c) In the process for preparation of the paper, Prof.
BhismaK.Patel reported similar thioesterification using copper
catalysts see: W. Ali, S. Guin, S.K. Rout, A. Gogoi, B. K. Patel, Adv.
Synth. Catal., DOI:10.1002/adsc.201400360.
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

View Article Online
DOI: 10.1039/C4RA09450F
Page 7 of 8
Journal Name
RSC Advances
ARTICLE
(g) X. Zhu, Y. Shi, H. Mao, Y. Cheng and C. Zhu, Adv. Synth. Catal.
2013, 355, 3558. (h) S. Iwahana, H. Iida and E. Yashima, Chem. Eur.
J .2011, 17, 8009. (i) C.-L. Yi, Y.-T.Huang and C.-F. Lee, Green
Chem. 2013, 15, 2476. (j) J.-W. Zeng, Y.-C. Liu, P.-A. Hsieh, Y.-T.
Huang, C.-L. Yi, S. S. Badsara and C.-F. Lee, Green Chem. 2014, 16
,
2644. (k) Y.-T. Huang, S.-Y. Lu, C.-L. Yi and C.-F. Lee, J. Org.
Chem. 2014, 79, 4561.
[16 selected reviews see: (a) Li, C.-J. Acc. Chem. Res.2009, 42, 335. (b)
X. Shang, Z.-Q. Liu, Chem. Soc. Rev. 2013, 42, 3253. (c) S. I.
Kozhushkov and L. Ackermann, Chem. Sci. 2013, 4, 886.
[17](a) G. Majji, S. Guin, A. Gogoi, S. K. Rout and B. K. Patel,
Chem.Commun.2013, 49, 3031. (b) L. Liu, L. Yun, Z. Wang, X. Fu
and C.-H. Yan, Tetrahedron Lett. 2013, 54, 5383. (c) S. K. Rout, S.
Guin, W.Ali, A. Gogoi and B. K. Patel, Org. Lett.
dx.doi.org/10.1021/ol5011906
[18] (a) Y.-J. Bian, C.-B. Xiang, Z.-M. Chen and Z.-Z. Huang, Synlett.
2011, 16, 2407. (b) S. K. Rout, S. Guin, A. Banerjee, N. Khatun, A.
Gogoi and B. K. Patel, Org. Lett. 2013, 15, 4106. (c) Z. Yin and P.
Sun, J. Org. Chem.2012, 77,11339. (d) Y. Wu, P. Y. Choy, F. Mao
and F. Y. Kwong, Chem. Commun.2013, 49, 689. (e) D. L.
Priebbenow, C. Bolm, Org. Lett.2014, 16, 1650.
[19] S. K. Rout, S. Guin, K. K. Ghara, A. Banerjee and B. K. Patel, Org.
Lett. 2012, 14, 3982.
[20] (a) H. Liu, G. Shi, S. Pan, Y. Jiang and Y. Zhang, Org. Lett. 2013,15
4098. (b) L. Ju, J. Yao, Z. Wu, Z. Liu and Y. Zhang, J. Org. Chem.
2013, 78,10821.
,
[21] (a) R. Tang, Y. Xie, Y. Xie, J . Xiang, J. Li, Chem. Commun. 2011,
47, 12867. (b) Y. P. Zhu, M. Lian, F. C. Jia, M. C. Liu, J. J. Yuan, Q.
H. Gao, A. X. Wu, Chem. Commun .2012,48, 9086. (c) Q. Wu, D.
Zhao, X. Qin, J. Lan, J. You, Chem. Commun .2011, 47, 9188. (d) F.
Yang, S. Tian, Angew. Chem., Int. Ed. 2013, 52, 4929.
[22] B. Mandal and B. Basu, RSC Adv. 2014, 4, 13854.
[23] T. Darmanin, E. T. de Givenchy, S. Amigoni and F. Guittard, J.
Fluorine. Chem, 2012, 134, 85.
[24] C.-C. Han, and R. Balakumar, Tetrahedron Lett. 2006, 47, 8255.
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 7

RSC Advances
Page 8 of 8
View Article Online
DOI: 10.1039/C4RA09450F
Graphic abstract
Text
Novel CDC approaches for synthesis of thioesters and thioethers was developed via sp3 C-H activation of
methylarenes and subsequent functionalization