Regioselective transition metal- and halogen-free direct dithiolation at C(sp3)-H of nitrotoluenes with diaryl disulfides

Article abstract of DOI:10.1039/c6ob01856d

Here we describe a potassium tert-butoxide-mediated regioselective direct C-S bond formation at the C(sp³)-H position of nitrotoluenes with disulfides in DMSO at room temperature. The developed reaction generated, in good yields, various dithioacetals having OMe, halogen, and NH₂ functionalities at various positions of the arene rings of the disulfides. Interestingly, in the absence of nitrotoluene, diaryl disulfides and diselenides underwent one-carbon homologation to form dithioacetals and diselenoacetals. Synthesized dithioacetals were transformed into 4-nitrobenzaldehyde and 7-(bis(phenylthio)methyl)-1H-indole.

Full text of DOI:10.1039/c6ob01856d

View Article Online
View Journal
Organic &
Biomolecular
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: S. Kumar, R. V.
Kadu and S. KUMAR, Org. Biomol. Chem., 2016, DOI: 10.1039/C6OB01856D.
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. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it 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/obc

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 1 of 5
View Article Online
DOI: 10.1039/C6OB01856D
Journal Name
COMMUNICATION
Regioselective Transition Metal- and Halogen-Free Direct
Dithiolation at C(sp3)-H of Nitrotoluenes with Diaryl Disulfides
Shailesh Kumar,a Rahul Kadu,a Sangit Kumar*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A potassium tert-butoxide mediated regioselective direct C-S bond
formation at C(sp3)-H position of nitrotoluenes with disulfides is
described in DMSO at room temperature. The developed reaction
generated various dithioacetals having OMe, halogens, and NH2
functionality at various position of arene ring of disulfides in good
yields. Interestingly, diaryl disulfides and diselenides underwent
one carbon homologation leading to dithioacetals and
diselenoacetals in the absence of nitrotoluene. Synthesized
dithioacetals were transformed into 4-nitrobenzaldehyde and 7-
(bis(phenylthio)methyl)-1H-indole.
Scheme 1 Direct dithiolation at C(sp3)-H bond of nitrotoluenes
functional groups and most of the nitroarenes are
economical.9 Dithioacetals constitute an important class of
organic compounds and are often used as a precursors of
carbon anion equivalent which have exhibited tremendous
utilities in the construction of C-C bonds.10 The traditional
method for synthesis of dithioacetals is the acid catalysed
reaction of carbonyl compounds with thiols or dithiols.11
To the best of our knowledge, dithiolation has not been
achieved by C(sp3)-H bonds functionalization by any method.
The direct dithiolation of C(sp3)-H bonds would reduce the
additional step, conversion of CH3 bond to CHO followed by
acid catalyzed dithiolation. Also precursors, benzaldehydes, for
dithioacetals are prone to oxidation and difficult to store for a
longer period of time. In continuation of our work on carbon–
carbon and carbon–heteroatom coupling reactions,12 herein,
we report for the first time, dithiolation of nitrotoluenes via
C(sp3)-H functionalization with diaryl disulfides at room
temperature (Scheme 1). Further, synthetic applicability of this
direct dithiolation is demonstrated by performing
deprotection of two representative dithioacetals to construct
4-nitrobenzaldehyde and 7-(bis(phenylthio)methyl)-1H-indole.
Also homologation of diaryl disulfides and diselenides has
been carried out under the similar reaction conditions in
absence of nitrotoluene.
The functionalization of C-H bonds play an important role in
the synthesis of organic molecules and have drawn much
attention from research community.1 Transition metal
catalyzed C−H bond functionalization has emerged as a
powerful strategy for carbon−carbon2 and carbon-heteroatom3
bond formations during the past decades. Several
methodologies have been developed for carbon-heteroatom
bond construction. But carbon-chalcogen4,5 bond forming
reactions are less studied as compared with other
heteroatoms. Conventionally, the carbon-chalcogen bond has
been constructed by cross-coupling of REH or R2E2 (E = S, Se)
with aryl halides. Recently, the direct C–chalcogen bond
formation through functionalization of C(sp2)–H bond has been
succesfully realized with or without transition metals.6,7
However, the direct carbon–chalcogen bond formations
through C(sp3)–H bond functionalization is less studied. Also,
recent reports on carbon-chalcogen bond formation under
transition metal free conditions require an oxidant at elevated
temperature to accomplish the transformation.8
Nitroarenes are synthetically very useful organic molecules
beacuse the nitro group can be transformed into various
Initially, diphenyl disulfide and 4-nitrotoluene were chosen
as substrates for the optimization of reaction conditions for
a.Department of Chemistry, Indian Institute of Science Education and Research
Bhopal, Bhopal By-pass Road, Bhauri, Bhopal 462 066, India.
E-mail: sangitkumar@iiserb.ac.in; web: home.iiserb.ac.in/~sangitkumar/
screening of various solvents, bases to obtain dithioacetal
1
Electronic Supplementary Information (ESI) available: Experimental details, (Table 1).
spectroscopic data, X-ray crystallographic data. CCDC No. 1487922 ( ), 1487921
14), 1500695 (29). See DOI: 10.1039/x0xx00000x
6
(
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 2 of 5
COMMUNICATION
Journal Name
Table 1. Optimization of reaction conditionsa
View Article Online
DOI: 10.1039/C6OB01856D
entry
1
2
3
4
5
6
7
8
base
solvent
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
time (h)
yield (%)
NR
5
trace
trace
9
60
10
26
50
K2CO3
Cs2CO3
K3PO4
LiOtBu
NaOtBu
KOtBu
KOH
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
KH
9
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
10
11
12
13
14
15
16
17
18
DMAc
CH3CN
THF
48
9
0
45
NMP
DCE
0
0
tBuOH
DMSO
DMSO
DMSO
36b
18c
35d
a All reactions were performed at 0.5 mmol scale using disulfide (1 equiv),
4-nitrotoluene (2 equiv), base (2 equiv) and solvent (1 mL). b Disulfide (2
Scheme 2 Reactivity screening on disulfides and nitrotoluene
equiv) and nitrotoluene (1 equiv) was used. c KOtBu (1 equiv) was used.
d
KOtBu (3 equiv) was used
at the ortho/para-positions of arene ring reacted smoothly
with 4-nitrotoluene to generate the corresponding products
in 46−72% yields, respectively. The reactions of 4-
nitrotoluene with diaryl disulfides having an electron
withdrawing halogens F, Cl, Br at the ortho/para-positions of
arene ring also showed the compatibility under the optimized
Bases such as K2CO3, K3PO4 and even LiOtBu did not provide
2
,
any dithioacetal
1 and reactants diphenyl disulfide and 4-
3
& 8
nitrotoluene were recovered quantitatively from the reaction
(entries 1, 3-4, Table 1). Further, bases Cs2CO3, NaOtBu and
KOH provide the desired product in less than 10% yields
(entries 2, 5, 7, Table 1). Interestingly, the reaction afforded
reaction conditions and corresponding dithioacetals
obtained in moderate 45-68% yields.
4-7 were
the corresponding product
1 in 60% yield in the presence of
KOtBu as base and DMSO as solvent at room temperature
under nitrogen atmosphere. After that various solvents such as
The structures of dithioacetals
6 and 14 (vide infra) also
established by X-ray single crystal structure study (Figure 1).
t
DMF, DMAc, CH3CN, THF, NMP, DCE, BuOH were screened.
Polar solvents DMF, DMAc and NMP gave the comparable
yields (see Table 1, entries 9-10, 13) as DMSO. But the yields
decreased drastically when CH3CN (entry 11, Table 1) was used
as solvent and no product was observed in case of THF, DCE,
tBuOH (entries 12, 14-15). One equiv of diphenyl disulfide, two
equiv of nitrotoluene, and two equiv of KOtBu realized
optimum for the formation of dithioacetal
1 (entry 6, Table 1).
Further variation in stoichiometries of the substrates and
KOtBu considerably lower the yield of
18).
1 (Table 1, entries 16-
Figure 1. Crystal structures of dithioacetals 14
& 6
After screening of bases and solvents, we studied the
substrate scope of coupling partners utilizing two equiv of
KOtBu in DMSO and results are presented in scheme 2. A
variety of diaryl disulfides were subjected to the reaction, and
the corresponding products were obtained in moderate to
high yields with various functional group compatibility. Diaryl
disulfides with an electron-rich group such as MeO, Me and
NH2
Further, heterocyclic 2-thienyl disulfide and 2,2′-
dithiobis(benzothiazole) coupled with 4-nitrotoluene
successfully to give respective dithioacetals 11 and 12
Next, di(2,5-dichlorodiphenyl) disulfide and 1-naphthyl
disulfide also smoothly generated the anticipated products
.
9
and 10 in 51% and 64% yields, respectively. Gratifyingly,
diselenoacetal 13 was obtained in 68% yield when diphenyl
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
Organic & Biomolecular Chemistry
Please do not adjust margins
Journal Name
COMMUNICATION
diselenide and 4-nitrotoluene were subjected to the reaction
condition.
View Article Online
DOI: 10.1039/C6OB01856D
After variation of substitution in disulfides, 2-nitrotoluenes
were subjected for dithiolation under the optimized reaction
condition. 2-nitrotoluene reacted smoothly with diphenyl
disulfide, 2-aminophenyl disulfide, bis(4-chlorophenyl)
Scheme 5 Synthetic utility of dithioacetals
disulfide to furnish the desired product 14, 16-17 in 45%, 37%
and 43% yields, respectively. Next, 2,4-dinitrotoluene coupled
with diphenyl disulfide to furnish product 15 in 27% yield.
To our delight, addition of SOCl2 and aqueous H2O2 to
dithioacetal in 2:4:1 stoichiometry yielded para-
1
nitrobenzaldehyde in 60% yield. Similarly, addition of an
excess of vinyl magnesium bromide provide dithioacetal-indole
in 70% yield.
Scheme 3 Synthesis of benzyl phenyl thioethers
1-Ethyl-2-nitrobenzene and 1-ethyl-4-nitrotoluene were
subjected for coupling with diphenyl disulfide which resulted
in unsymmetrical benzyl phenyl sulfides 18 and 19 under the
reaction condition in 30%
& 43% yields, respectively.
Thioethers; unsymmetrical benzyl phenyl sulfides are
promising scaffolds in biology13 and material sciences14. After
this interesting observation, we sought to synthesize
unsymmetrical benzyl phenyl sulfides under the optimized
reaction conditions. Interestingly, reaction of di(2,4-
dichlorodiphenyl) disulfide with 4-nitrotoluene provided
thioether 20 in 48% yield. Also, aliphatic nitromethane coupled
with diphenyl disulfide under the reaction condition to give 21
in 32% yield.
Scheme 6 Reaction of para-nitro toluene with KOtBu
Further, to gain the mechanistic insight into the reaction, para-
nitrotoluene alone was stirred in DMSO at room temperature.
This yielded para-nitro substituted ketone 29 (Scheme 6),
which also characterized by single crystal X-ray study. Reaction
of benzenethiol with para-nitrotoluene provided traces of
desired dithioacetal
1 under the reaction condition and
nitrotoluene was recovered quantitatively.
A plausible reaction mechanism has been proposed on the
basis of control experiments (Schemes 4 and 6). The benzylic
proton can be abstracted by KOtBu and thus have benzyl anion
I, which adds to the electrophilic sulphur of disulfide to
generate monothiolated species III (Scheme 7). Next, proton
abstraction by KOtBu from III leads to intermediate IV which
reacts with disulfide to generate the dithioacetal 1.
Scheme 4 Synthesis of dithio/diselenoacetal
During optimization of the reaction conditions, we observed
one carbon homologation of diphenyl dichalcogenides when
corresponding diphenyl dichalcogenides were treated in DMSO
o
without addition of nitrotoluenes at 100 C (Scheme 4). The
dithioacetals 22 and 23 were obtained in 25 and 23%, whereas
corresponding diselenoacetals 24 and 25 were obtained in 65
and 60% yields, respectively. When reaction was performed in
deuterated DMSO-d6, deuterated dithioacetls 26 was observed
which suggests that the CH2 group transfer from DMSO.
Further, the synthetic utility of synthesized dithioacetals were
explored for the synthesis of aldehyde and indole derivative
(Scheme 5).
Scheme 7 Proposed mechanism for C-H dithiolation of nitrotoluene
The phenyl thiolate could be oxidized to diphenyl disulfide by
DMSO in the presence of KOtBu. The oxidation of phenyl
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 4 of 5
COMMUNICATION
thiolate to diphenyl disulfide could also occurred by aerial
Journal Name
42, 5400; (c) N. Taniguchi, J. Org. Chem. 2006,View Article Online
71, 7874; (d)
M. Iwasaki, D. Fujino, T. Wada, A. Kondoh, H. Yorimitsu and
DOI: 10.1039/C6OB01856D
oxygen as the reaction proceeds to form dithioacetal
open flask, albeit in low yield.
1 in an
K. Oshima, Chem. Asian J., 2011,
and J. P. Stambuli, Molecules, 2011, 16, 590; (f) H. Liu and X.
Jiang, Chem. Asian J., 2013, , 2546; (g) M. Iwasaki, T. Fujii, A.
Yamamoto, K. Nakajima and Y. Nishihara, Chem. Asian J.,
2014, , 58; (h) C.-F. Lee, Y.-C. Liu and S. S. Badsara, Chem. –
Asian J., 2014, , 706; (i) M. Iwasaki, T. Fujii, K. Nakajima and
6, 3190; (e) C. C. Eichman
In summary, we have developed a novel KOtBu mediated
direct dithiolation at C(sp3)−H of nitrotoluenes with diaryl
disulfides at room temperature. A number of disulfides
reacted with nitrotoluenes to generate the corresponding
dithioacetals in good yields. The reaction exhibited advantages
including mild condition and good functional group
compatibility. Further, these dithioacetals has been
transformed to commercially valuable 4-nitrobenzaldehyde
and 7-(bis(phenylthio)methyl)-1H-indole.
8
9
9
Y. Nishihara, Angew. Chem. Int. Ed., 2014, 53, 13880; (j) N.
Taniguchi, Tetrahedron, 2014, 70, 1984; (k) N. Taniguchi, J.
Org. Chem. 2015, 80, 7797; (l) N. Taniguchi, Eur. J. Org.
Chem. 2016, 2016, 2157.
5
(a) N. Taniguchi, J. Org. Chem., 2007, 72, 1241 (b) I. P.
Beletskaya and V. P. Ananikov, Eur. J. Org. Chem. 2007, 3431;
(c) N. Taniguchi, Tetrahedron, 2009, 65, 2782; (d) D. Singh, A.
M. Deobald, L. R. S. Camargo, G. Tabarelli, O. E. D. Rodrigues
and A. L. Braga, Org. Lett., 2010, 12, 3288. (e) Y. Li, H. Wang,
X. Li, T. Chen and D. Zhao, Tetrahedron, 2010, 66, 8583; (f) I.
SK thanks DST-SERB New Delhi (EMR/2015/000061) for
generous funding. We thank Professor Harkesh B. Singh, IIT
Bombay for HRMS analysis. We also thank Mr. Amit Kumar
Mishra for his assistance. SK and RK thanks IISER Bhopal for
fellowship.
P. Beletskaya and V. P. Ananikov, Chem. Rev., 2011, 111
,
1596; (g) D. Kundu, S. Ahammed and B. C. Ranu, Green
Chem., 2012, 14, 2024. (h) N. Taniguchi, Tetrahedron, 2012,
68, 10510; (i) P. Mizar, R. Niebuhr, M. Hutchings, U. Farooq
and T. Wirth, Chem. Eur. J. 2016, 22, 1614.
6
(a) X. Zhao, E. Dimitrijevic and V. M. Dong, J. Am. Chem. Soc.,
2009, 131, 3466; (b) S. Zhang, P. Qian, M. Zhang, M. Hu and
J. Cheng, J. Org. Chem., 2010, 75, 6732; (c) P. Anbarasan, H.
Neumann and M. Beller, Chem. Commun., 2011, 47, 3233;
(d) O. Saidi, J. Marafie, A. E. W. Ledger, P. M. Liu, M. F.
Mahon, G. Kociok-Köhn, M. K. Whittlesey and C. G. Frost, J.
Am. Chem. Soc., 2011, 133, 19298; (e) P. Saravanan and P.
Anbarasan, Org. Lett., 2014, 16, 848. (f) M. Iwasaki, M.
Iyanaga, Y. Tsuchiya, Y. Nishimura, W. Li, Z. Li and Y.
Nishihara, Chem. Eur. J., 2014, 20, 2459; (g) M. Iwasaki, W.
Kaneshika, Y. Tsuchiya, K. Nakajima and Y. Nishihara, J. Org.
Chem., 2014, 79, 11330; (h) M. Iwasaki, Y. Tsuchiya, K.
Nakajima and Y. Nishihara, Org. Lett., 2014, 16, 4920; (i) N.
Taniguchi, J. Org. Chem. 2015, 80, 1764.
Notes and references
1
a) B. M. Trost, Angew. Chem. Int. Ed. 1995, 34, 259 (b) J.
Wencel-Delord and F. Glorius, Nat. Chem., 2013,
R. Tang, G. Li and J.-Q. Yu, Nature, 2014, 507, 215;
5, 369; (c)
2
Transition metal catalyzed C-C coupling: (a) I. Ban, T. Sudo, T.
Taniguchi and K. Itami, Org. Lett., 2008, 10, 3607; (b) C. –J. Li,
Acc. Chem. Res. 2009, 42, 335; (c) P. Fang, M. Li and H. Ge, J.
Am. Chem. Soc. 2010, 132, 11898; (d) W. Shi, C. Liu and A.
Lei, Chem. Soc. Rev., 2011, 40, 2761. (e) N. Kuhl, M. N.
Hopkinson, J. Wencel-Delord and F. Glorius, Angew. Chem.
Int. Ed., 2012, 51, 10236; (f) D. A. Colby, A. S. Tsai, R. G.
Bergman and J. A. Ellman, Acc. Chem. Res. 2012, 45, 814; (g)
W. Song, S. Lackner and L. Ackermann, Angew. Chem. Int.
Ed., 2014, 53, 2477; (h) X.-S. Zhang, K. Chen and Z.-J. Shi,
7
(a) C. Y. Kawasoko, P. Foletto, O. E. Rodrigues, L. Dornelles,
R. S. Schwab and A. L. Braga, Org. Biomol. Chem., 2013, 11
,
5173; (b) S.-r. Guo, Y.-q. Yuan and J.-n. Xiang, Org. Lett.,
2013, 15, 4654; (c) J. B. Azeredo, M. Godoi, G. M. Martins, C.
C. Silveira and A. L. Braga, J. Org. Chem., 2014, 79, 4125; (d)
J. Rafique, S. Saba, A. R. Rosário, G. Zeni and A. L. Braga, RSC
Chem. Sci., 2014, 5, 2146; (i) N. Dastbaravardeh, T. Toba, M.
E. Farmer and J.-Q. Yu, J. Am. Chem. Soc. 2015, 137, 9877; (j)
L. Xu, C. Zhang, Y. He, L. Tan and D. Ma, Angew. Chem. Int.
Ed., 2016, 55, 321; (k) W. C. Fu, C. M. So, O. Y. Yuen, I. T. Lee
and F. Y. Kwong, Org Lett., 2016, 18, 1872; (l) Z. Ruan, S.
Adv., 2014, 4, 51648; (e) J. Zhao, H. Fang, J. Han, Y. Pan and
G. Li, Adv. Synth. Catal., 2014, 356, 2719 (f) B. Du, B. Jin and
P. Sun, Org. Lett., 2014, 16, 3032. (g) N. L. Ferreira, J. B.
Azeredo, B. L. Fiorentin and A. L. Braga, Eur. J. Org. Chem.,
2015, 2015, 5070; (h) S. Saba, J. Rafique and A. L. Braga, Adv.
Synth. Catal., 2015, 357, 1446. (i) A. A. Vieira, J. B. Azeredo,
M. Godoi, C. Santi, E. N. da Silva Junior and A. L. Braga, J.
Org. Chem., 2015, 80, 2120; (j) J. Rafique, S. Saba, A. R.
Rosário and A. L. Braga, Chem. Eur. J., 2016, 22, 11854.
Lackner and L. Ackermann, ACS Catal. 2016, 6, 4690. (m) W.
Hou, Y. Yang, Y. Wu, H. Feng, Y. Li and B. Zhou, Chem.
Commun., 2016, 52, 9672.
3
Transition metal catalyzed C-heteroatom coupling: (a) Z. Li,
D. A. Capretto, R. O. Rahaman and C. He, J. Am. Chem. Soc.,
2007, 129, 12058; (b) J. M. Lee, E. J. Park, S. H. Cho and S.
Chang, J. Am. Chem. Soc. 2008, 130, 7824; (c) M. R. Luzung,
C. A. Lewis and P. S. Baran, Angew. Chem. Int. Ed., 2009, 48
,
8
9
(a) S.-r. Guo, Y.-q. Yuan and J.-n. Xiang, Org. Lett., 2013, 15,
7025; (d) P. Thansandote and M. Lautens, Chem. Eur. J.,
2009, 15, 5874; (e) T.-S. Mei, D.-H. Wang and J.-Q. Yu, Org.
Lett., 2010, 12, 3140; (f) N. Guimond, S. I. Gorelsky and K.
Fagnou, J. Am. Chem. Soc., 2011, 133, 6449; (g) B.-J. Li, H.-Y.
Wang, Q.-L. Zhu and Z.-J. Shi, Angew. Chem. Int. Ed., 2012,
51, 3948; (h) D.-G. Yu, M. Suri and F. Glorius, J. Am. Chem.
Soc., 2013, 135, 8802; (i) J. Bariwal and E. V. Eycken, Chem.
Soc. Rev., 2013, 42, 9283; (j) M. Shang, S.-Z. Sun, H.-X. Dai
and J.-Q. Yu, J. Am. Chem. Soc., 2014, 136, 3354. (k) W. C. Fu,
C. M. So and F. Y. Kwong, Org Lett., 2015, 17, 5906; (l) Y. P.
4654; (b) J. Zhao, H. Fang, J. Han, Y. Pan and G. Li, Adv. Synth.
Catal. 2014, 356, 2719 (c) S. S. Badsara, Y.-C. Liu, P.-A. Hsieh,
J.-W. Zeng, S.-Yi Lu, Y.-W. Liu and C.-F. Lee, Chem. Comm.,
2014, 50, 11374; (d) B. Du, B. Jin and P. Sun, Org. Lett., 2014,
16, 3032.
(a) K. Pothula, L. Tang, Z. Zha and Z. Wang, RSC Adv., 2015, 5,
83144; (b) R. B. Nasir Baig, S. Verma, M. N. Nadagouda and
R. S. Varma, Green Chem., 2016, 18, 1019; (c) N. M. Patil, T.
Sasaki and B. M. Bhanage, ACS Sustainable Chem. Eng., 2016,
4
, 429; (d) F. Zhao, B. Li, H. Huang and G.-J. Deng, RSC Adv.,
2016, , 13010.
10 (a) E. J. Corey and D. Seebach, Angew. Chem. Int. Ed., 1965,
He, C. Zhang, M. Fan, Z. Wu and D. Ma, Org Lett., 2015, 17
,
6
496; (m) P. T. Rabet, G. Fumagalli, S. Boyd and M. F. Greaney,
Org Lett., 2016, 18, 1646; (n) M. Reitti, P. Villo and B.
Olofsson, Angew. Chem. Int. Ed. 2016, 55, 8928.
(a) T. Kondo and T.-a. Mitsudo, Chem. Rev., 2000, 100, 3205;
(b) S. V. Ley and A. W. Thomas, Angew. Chem. Int. Ed., 2003,
4
, 1075; (b) D. Seebach, Angew. Chem. Int. Ed., 1969, 8, 639;
(c) M. Yus, C. Najera and F. Foubelo, Tetrahedron, 2003, 59
,
4
6147.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
Organic & Biomolecular Chemistry
Please do not adjust margins
Journal Name
COMMUNICATION
11 (a) S. Muthusamy, S. A. Babu and C. Gunanathan,
View Article Online
DOI: 10.1039/C6OB01856D
Tetrahedron Lett., 2001, 42, 359; (b) S. Samajdar, M. K. Basu,
F. F. Becker and B. K. Banik, Tetrahedron Lett., 2001, 42
,
4425; (c) M. Zahouily, A. Mezdar, J. Rakik, A. Elmakssoudi, A.
Rayadh and S. Sebti, J. Mol. Catal. A: Chemical, 2005, 233
,
43; (d) E. J. Lenardão, YE. L. Borges, S. R. Mendes, G. Perin
and R. G. Jacob, Tetrahedron Lett., 2008, 49, 1919; (e) B. C.
Ranu, A. Saha and T. Mandal Tetrahedron, 2009, 65, 2072; (f)
S. Madabhushi, K. K. R. Mallu, N. Chinthala, C. R. Beeram and
V. S. Vangipuram, Tetrahedron Lett., 2012, 53, 697.
12 Our work on C-C and C–Chalcogen coupling reactions: (a) A.
Kumar, B. S. Bhakuni, C. D. Prasad, S. Kumar and S. Kumar,
Tetrahedron, 2013, 69, 5383; (b) C. D. Prasad, S. Kumar, M.
Sattar, A. Adhikary and S. Kumar, Org. Biomol. Chem., 2013,
11, 8036; (c) C. D. Prasad, S. J. Balkrishna, A. Kumar, B. S.
Bhakuni, K. Shrimali, S. Biswas and S. Kumar, J. Org. Chem.,
2013, 78, 1434; (d) S. Kumar, V. Rathore, A. Verma, C. D.
Prasad, A. Kumar, A. Yadav, S. Jana, M. Sattar, Meenakshi
and S. Kumar, Org. Lett., 2015, 17, 82.
13 (a) G. Liu, J. R. Huth, E. T. Olejniczak, R. Mendoza, P. DeVries,
S. Leitza, E. B. Reilly, G. F. Okasinski, S. W. Fesik and T. W.
von Geldern, J. Med. Chem., 2001, 44, 1202; (b) G. D.
Martino, M. C. Edler, G. L. Regina, A. Coluccia, M. C. Barbera,
D. Barrow, R. I. Nicholson, G. Chiosis, A. Brancale, E. Hamel,
M. Artico and R. Silvestri, J. Med. Chem., 2006, 49, 947.
14 (a) J. Liu, J. Yang, Q. Yang, G. Wang and Y. Li, Adv. Funct.
Mater., 2005, 15, 1297; (b) A. Dondoni, Angew. Chem. Int.
Ed., 2008, 47, 8995.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins