Nickel catalyzed site selective C-H functionalization of α-aryl-thioamides

Article abstract of DOI:10.1039/c8ob01712c

A catalytic site selective intramolecular C-S bond forming reaction is demonstrated for the first time. The C-H bond functionalization of α-aryl-thioacetanilides was efficiently catalyzed by 2 mol% NiBr₂, resulting in valuable 2-aminobenzo[b]thiophenes in moderate to good yields. Furthermore, the selective sp² C-H bond functionalization over sp³ is exemplified.

Full text of DOI:10.1039/c8ob01712c

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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DOI: 10.1039/C8OB01712C
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Nickel Catalyzed Site Selective C−H Functionalization of α-Aryl-
thioamides
Debashruti Bandyopadhyay,‡ Annaram Thirupathi,‡ Nagsen Munjaji Dhage, Nirmala Mohanta,
and S. Peruncheralathan*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A catalytic site selective intramolecular C
is demonstrated for the first time. The C
of α-aryl-thioacetanilides was efficiently catalyzed by 2 mol% NiBr2 construction of the benzo[b]thiophene core.8d In 2008, Inmoto
―
―
S bond forming reaction cross-coupling of C―S bond with aryl halides.13 However, the
H bond functionalization C―H bond functionalization strategy is rarely used for the
and resulting in the valuable 2-aminobenzo[b]thiophenes in and
co-workers
H bond diarylbenzo[b]thiophenes from the aryl substituted thioenols
through a palladium catalyzed C―H thiolation at 120
C.14
have
first
reported
the
2,3-
moderate to good yields. Further, selective sp2
functionalization over sp3 is exemplified.
C―
°
Later, Antonchick’s15 and Duan’s16 groups demonstrated
synthesis of dibenzothiophenes17 via an interesting palladium
catalyzed tandem C―H bond functionalization strategy.
Metal catalyzed C―H functionalization of sp2 carbon is a
powerful tool for the construction of C―C and C―X (X = O, N,
S, P, B… etc.) bonds in organic synthesis.1 Particularly, the
regioselective C―H bond functionalization has received much
attention among synthetic chemists.2 In this context, the
significant progress has been achieved by use of precious metals
such as Pd, Rh, Ru, and Ir as catalyts.3 However, non-precious
metals such as Fe, Cu, Co, and Ni are less explored.4 Recently,
Chatani’s group reported5 an excellent combination of a nickel
catalyst and an N,N’-bidentate chelating group that has been
used for several C―H bonds functionalization reactions.6 The
mechanism for the nickel catalyzed reaction was also
investigated by computational studies.7 These results
encouraged us to explore nickel catalysts for the site selective
C―H functionalization of arenes and their applications in the
synthesis of S-heterocycles.
Recently,
highly
substituted
and
functionalized
benzo[b]thiophenes were reported that involved palladium/
copper mediated intramolecular C―S bond formation at 90
°
C.18 Despite good yields, these methods have their own
limitations such as high reaction temperature,14 longer reaction
time,14 and use of co-catalyst.18b Therefore, developing a newer
catalytic method for the synthesis of benzo[b]thiophenes in
ambient conditions is highly desirable.
The use of nickel-catalyzed C―H bond functionalization
reactions for the synthesis of heterocycles have been reported
recently.5 Particularly, a number of saturated and unsaturated
N-heterocyles, such as lactums, indoles, isoquinolones, were
synthesized through nickel mediated C―N bond formation.19
Although, nickel has been found to form C―S bond efficiently
via C―H functionalization.20 To the best of our knowledge,
Benzo[b]thiophene is an interesting class of heterocyclic
compounds. This core is found in various drugs and materials.8
In particular, 2-aminobenzo[b]thiophenes act as inhibitors in
tubulin polymeriztion9 and acetyl-CoA carboxylase10 and are
also used as precursors in the synthesis of the drug raloxifene
and its various analogues.11 In literature, several methods have
been
reported
for
the
synthesis
of
2-
aminobenzo[b]thiophenes.12,13 The most of the methods
involve either a multi-step synthesis12 or an intramolecular
School of Chemical Sciences, National Institute of Science Education and Research
Bhubaneswar, HBNI, Jatni, Khurda – 752050, Odisha, India. Fax: +91-674-2494004;
Tel: +91-674-2494173; E-mail: peru@niser.ac.in
Scheme 1. Site Selective C
thioamides
―H Functionalization of α-Aryl-
‡These authors contributed equally
†Electronic Supplementary Information (ESI) available: [Experimental procedures
and spectral characterization of compounds 3, 4, 5, and 6. Copies of 1H, 13C NMR,
and HRMS Spectra of all compounds. The X-ray data were also deposited with the
CCDC (entries 1855418 & 1855419)]. See DOI: 10.1039/x0xx00000x
3
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catalytic nickel mediated synthesis of S-heterocycles via an additive, the C―H bond functionalization process was
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23
intramolecular C―S bond formation is not reported.21 In significantly improved (Table 1, Entry D5O,I: 1602.1%0)3.9/C8NOoB0t1r7a12cCe
continuation of our ongoing interest in developing practical amount of benzo[d]thiazole was formed. To improve the yield
methods for the construction of heterocycles with novel of the 2-anilinobenzo[b]thiophene 4a, the reaction was
physical properties,22 we report herein the NiBr2 catalyzed performed with the Ad2PBu ligand (4 mol%) affording a slightly
highly site selective C―H bond functionalization of α-aryl- lower yield (52%, Entry 6, Table S1, ESI†). However, in the
thioacetanilides (Scheme 1).
absence of KI, the yield of the product drastically dropped to
18% even in the presence ligand (Entry 7). No significant effect
was found in increasing the catalyst loading from 2 mol% to 10
mol% (Entries 8 & 9). The reaction when performed in the
presence of KI and HFIP, and without NiBr2, the yield dropped
to 30% (Entry 10). Similarly, the reaction when carried out in the
presence of the oxidant only, 4a was formed in 10% yield (Entry
11).24 The reaction was found to be equally effective in the
presence of TEMPO (Entry 12) suggesting that the C―H
functionalization reaction does not involve a radical pathway.
From the above studies, nickel and KI have a synergistic effect
Table 1. Optimization of the Nickel Catalyzed Site Selective C
Functionalization of α-Aryl-thioacetanilide 3aa,b
―H Bond
Entry
NiBr2
Additive
Oxid
Solvent
Temp
Yield of 4a
in increasing the yield of the C―H functionalized product 4a
.
1.
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
2 mol%
2 mol%
2 mol%
2 mol%
2 mol%
2 mol%
2 mol%
5 mol%
10 mol%
-
-
-
Dioxane
Dioxane
Dioxane
HFIP
rt
12%
22%
2.
60 °C
120 °C
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
Table 2. Nickel Catalyzed Site Selective C
thioacetanilide 3a
―H Functionalization of α-Aryl-
3.
-
32%
4.
-
35%
KI
KI
-
HFIP
62%c
52% c,d
18% d,e
60%c
54%c
30%c,h
10%f
5.
6.
HFIP
7.
HFIP
8.
KI
KI
KI
-
HFIP
9.
HFIP
10.
11.
12.
HFIP
-
HFIP
2 mol%
KI
HFIP
60%c,g
aReaction conditions: 3a (0.5 mmol), NiBr2 (x mol%), PIDA (1 equiv) solvent (2.0 mL),
temperature, 1-2 h. bIsolated yields. cKI (2 equiv) was used. dAd2PBu (4 mol%) was added.
eWithout KI. fWithout NiBr2.gWithout KI and NiBr2.hTEMPO (1 equiv) was used. HFIP-
Hexafluroisopropanol. TEMPO-(2,2,6,6-Tetramethylpiperidin-1-yl)oxy
The key step of the present methodology is the nickel-catalyzed
site selective C―H Functionalization of thioanilides
required thioanilides were prepared by treating the anion α-
aryl acetonitriles with substituted isothiocyanates in
moderate to good yields (Scheme S1, ESI†). After having the
thioanilides in our hand, the thioanilide 3a was chosen as
3. The
3
1
2
3
model substrate for the site-selective C―H bond
functionalization process (Thiophene vs Thiazole, Scheme 1).
Initial experiment was performed with NiBr2 affording only 12%
of the product 4a (Table 1, Entry 1). This product was
characterized
as
2-anilino-3-cyano-4,5-dimethoxy-
benzo[b]thiophene (4a) by spectral and analytical data analysis.
Further, it is confirmed by single crystal X-ray analysis (Table 2).
Various conditions were examined to increase the yield of
benzo[b]thiophene 4a (Table 1). The reactions were performed
at higher temperatures in dioxane and the yield of the product
aIsolated yields.
With the optimized conditions in our hand, we studied a series
of thioanilides 3b-o for the site selective bond
functionalization reactions. The electron donating substituent on
aryl moieties 3b-d smoothly underwent H functionalization
C―H
4a was increased to 32% at 120
reaction when carried out in HFIP, 4a was formed at 50
°
C (Table 1, Entry 3). The same
C with
°
C
―
comparable yield (35%, Entry 4). Interestingly, with KI used as
reaction affording exclusively the benzo[b]thiophenes 4b-d in
2 | J. Name., 2012, 00, 1-3
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59 to 67% yields (Table 2) within 2 hours. Similarly, methyl substituted N-cyclohexyl 5a was subjected to a site selective
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DOI: 10.1039/C8OB01712C
substituted 3e was transformed to benzo[b]thiophene 4e in C―H bond functionalization reaction under the optimized
60% yield under the optimized conditions. However, halo conditions. Interestingly, the benzo[b]thiophene 6a was
derivatives 3f-g gave only 20-25% of the corresponding obtained in 30% yield (Table 3). No trace amount of sp3 C―H
benzo[b]thiophenes 4f-g. The unsubstituted thioanilide 3h was bond functionalization was found. The yield of the product 6a
also transformed to 2-anilino-3-cyanobenzo[b]thiophene (4h
)
was increased to 50% by the addition of the Ad2PBu ligand (4
in 41% yield. Interestingly, 1-(3,5-ditbutylphenyl)-1’- mol%) (Table 3). A similar result was also observed for the
cyanothioacetamide 3i smoothly underwent a highly hindered unsubstituted cyclohexyl thioamide 5b giving 68% of
C―H bond functionalization affording 2-anilino-3-cyano-5,7- benzo[b]thiophene 6b. Next, the N-ethyl thioamides 5c-d were
ditbutyl-benzo[b]thiophene (4i) in 55% yield within 1 hour studied. These thioamides 5c-d were transformed to the
under the identical reaction conditions. Various N-aryl benzo[b]thiophenes 6c-d exclusively under similar reaction
substituted thioamides 3j-p were also studied for the site conditions (Table 3). These results clearly suggested that the
selective C―H functionalization reaction (Table 2). The N-2- present nickel catalyst is highly selective for sp2 C―H bond
chlorophenyl substituted thioamide 3j was transformed to functionalization over sp3 C―H bond.
benzo[b]thiophene 4j (55%) without forming the thiazole
derivative. Similarly, the N-3,5-dimethylphenyl thioamide
Table 4. Nickel Catalyzed Controlled C―H Bond Functionalization for
Synthesis of Five-membered vs Six-membered S-Heterocyclesa,b
derivative 3k was converted to the corresponding
benzo[b]thiophene 4k in 45% yield. Interestingly, electron
withdrawing CF3 group containing N-phenyl thioamide 3l
underwent C―H bond functionalization reaction affording
exclusively benzo[b]thiophene 4l in 61% yield. The same trend
was observed in fluoro derivative 3m afforded the
benzo[b]thiophene 4m in 58% yield. The 3-methyl and 3,5-
dimethyl-N-phenyl derivatives 3n-o were transformed to
benzo[b]thiophenes 4n-o in 45% yields respectively. However,
the 4-isopropyl substituted N-phenyl derivative 3o gave only
32% benzo[b]thiophene 4p (Table 2). All newly synthesized
aIsolated yields. bThe parenthesis is yield of product
6 without ligand
benzo[b]thiophenes 4b-p were confirmed by spectral and
analytical data analysis. X-ray analysis was also used to confirm
the structure of one of the benzo[b]thiophenes (4b, Table 2).
Next, we studied a controlled C―H bond functionalization for
the selective synthesis of five-membered over six-membered S-
heterocycles. The required N-benzyl substituted thioamides 5e-
Table 3. Nickel Catalyzed Site Selective C
Bond vs sp3 C―H Bonda,b
―
S Bond Formation of sp2 C―H
g
were prepared (Scheme S2, ESI†). These thioamides 5e-g were
subjected under the similar reaction conditions. The
benzo[b]thiophenes 6e-g were formed exclusively in moderate
to good yields. No other products were detected (Table 4). The
yield of products 6e and 6g were better in the presence of ligand
(Table 4).
Conclusion
We have demonstrated the first nickel catalyzed site selective
C―H bond functionalization of thioanilides for the synthesis of
2-aminobenzo[b]thiophenes. The present protocol is mild, low
catalyst loading, and short reaction time and gives access to a
variety of 2-amino-3-cyano-benzo[b]thiophenes in moderate to
good yields. The potential application of the reaction was
further extended to a highly site selective C─S bond formation
of sp2 C―H bond over sp3 C―H bond, and 5-membered ring
over 6-membered ring. Currently, metal-free site selective C―H
bond functionalization reactions are in progress in our
laboratory.
aIsolated yields. bThe parenthesis is yield of product
6 without ligand.
Generally, nickel catalysts have been shown to functionalize
both the sp2 and sp3 C―H bonds.24 To this end, an investigation
of the current catalytic system on the selectivity of sp2 vs sp3
C―H bond is fundamental interest. We have chosen two model
substrates 5a
& 5c for the study of site-selective process. Thus,
the required thioamides 5a-d were synthesized by treating the Notes and references
anion of α-aryl acetonitrile
isothiocyantes (Scheme S2, ESI†). After having aliphatic
thioamides 5a-d in our hand, the first electron donating
1 with cyclohexyl and ethyl
1
Selected Reviews: (a) K. Godula and D. Sames, Science, 2006,
312, 67; (b) C. S. Yeung and V. M. Dong, Chem. Rev., 2011,
111, 1215; (c) K. M. Engle, T.-S. Mei, M. Wasa and J.-Q. Yu,
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
Vijay Kumar, B. Saraiah and H. Ila, J. Org. Chem.V2ie0w1A5r,tic8le0O, nline
14 K. Inamoto, Y. Arai, K. Hiroya and T. DoDi,OCI:h1e0m.10. 3C9o/mC8mOuB0n1.,712C
2008, 5529.
Acc. Chem. Res., 2012, 45, 788; (d) F. Zhang and D. R. Spring,
Chem. Soc. Rev., 2014, 43, 6906; (e) H. M. L. Davies and D.
Morton, ACS Cent. Sci., 2017,
Yamada, T. Kaneda and K. Itami., Chem. Rev., 2017, 117
2884.
3
, 936; (f) K. Murakami, S.
,
9302.
15 R. Samanta and A. P. Antonchick, Angew. Chem. Int. Ed.,
2011, 50, 5217.
2
3
Selected Reviews: (a) T. Brueckl, R. D. Baxter, Y. Ishihara and
P. S. Baran, Acc. Chem. Res., 2012, 45, 826; (b) J. Schranck, A. 16 H. Huang, J. Li, C. Lescop and Z. Duan, Org. Lett., 2011, 13
,
Tlili and M. Beller, Angew. Chem. Int. Ed., 2014, 53, 9426; (c)
H. M. L. Davies and D. Morton, J. Org. Chem., 2016, 81, 343;
(d) J. A. Leitch and C. G. Frost, Chem. Soc. Rev., 2017, 46
5252.
17 M. Tobisu, Y. Masuya, K. Baba and N. Chatani, Chem. Sci.,
,
2016, 7, 2587.
7145; (e) A. Dey, S. Agast, D. Maiti, Org. Biomol. Chem, 2016, 18 (a) A. Acharya, S. V. Kumar and H. Ila, Chem. Eur. J., 2015, 21
14, 5440; (f) C. Yuan, L. Zhu, C. Chen, X. Chen, Y. Yang, Y.
Lang and Y. Zhao, Nat. Commun., 2018, , 1 and cited therein
,
17116; (b) B. Saraiah, V. Gautam, A. Acharya, M. A. Pasha
and H. Ila, Eur. J. Org. Chem. 2017, 5679.
9
Selected Reviews: (a) R. H. Crabtree, Chem. Rev., 2010, 110
575; (b) J. F. Hartwig, Chem. Soc. Rev. 2011, 40, 1992; (c)
,
19 Selected Reports: (a) X.-Q. Tang and J. Montgomery, J. Am.
Chem. Soc. 2000, 122, 6950; (b) C.-C. Liu, K. Parthasarathy,
and C.-H. Chenig, Org. Lett., 2010, 12, 3518; (c) H. Shiota, Y.
Ano, Y. Aihara, Y. Fukumoto, and N. Chatani, J. Am. Chem.
H.M. L. Davies and D. Morton, Chem. Soc. Rev., 2011, 40
,
1857; (d) J. Wencel-Delord, T. Droege, F. Liu and F. Glorius,
Chem. Soc. Rev., 2011, 40, 4740; (e) P. B. Arockiam, C.
Soc., 2011, 133, 14952; (d) D. M. S.-McAtee, S. Dasgupta, and
M. P. Watson, Org. Lett., 2011, 13, 3490; (e) C. Liu, D. Liu, W.
Zhang, L. Zhou, and A. Lei, Org. Lett., 2013, 15, 6166; (f) W.
Song and L. Ackermann, Chem. Commun., 2013, 49, 6638; (g)
X. WU, . Zhao and H. Ge, Chem. Eur. J. 2014, 20, 9530; (h) C.
Lin, J. Zhang, Z. Chen, Y. Liu, Z. Liu, and Y. Zhang, Adv. Synth.
Catal. 2016, 358, 1778; (i) Y. Li, K. Kuai, Y. Ping, Y. Wang and
W. Kong, Org. Lett., 2018, 20, 921.
Bruneau and P. H. Dixneuf, Chem. Rev., 2012, 112, 5879; (f)
L. Ackermann, Acc. Chem. Res., 2014, 47, 281; (g) C. Shen, P.
Zhang, Q. Sun, S. Bai, T. S. A. Hor and X. Liu, Chem. Soc. Rev.,
2015, 44, 291; (h) O. Daugulis, J. Roane and L. D. Tran, Acc.
Chem. Res. 2015, 48, 1053; (i) R.-Y. Zhu, M. E. Farmer, Y.-Q.
Chen and J.-Q. Yu, Angew. Chem. Int. Ed., 2016, 55, 10578.
Selected Reviews: (a) S. Z. Tasker, E. A. Standley and T. F.
Jamison, Nature, 2014, 509, 299; (b) X.-X. Guo, D.-W. Gu, Z.
Wu and W. Zhang, Chem. Rev., 2015, 115, 1622; (c) M.
4
20 Selected Reports: (a) X. Wu, Y. Zhao, and H. Ge, Chem. Eur. J.,
2014, 20, 9530; (b) S.-Y. Yan, Y.-J. Liu, B. Liu, Y.-H. Liu and B.-
F. Shi, Chem. Commun., 2015, 51, 4069; (c) A. Yokota and N.
Chatani, Chem. Lett., 2015, 44, 902; (d) C. Lin, D. Li, B. Wang,
J. Yao, and Y. Zhang, Org. Lett., 2015, 17, 1328; (d) K. Yang, Y.
Wang, X. Chen, A. A. Kadi, H.-K. Fun, H. Sun, Y. Zhang and H.
Lu, Chem. Commun., 2015, 51, 3582; (e) X. Ye, J. L. Petersen
and X. Shi, Chem. Commun., 2015, 51, 7863; (f) V. P. Reddy,
R. Qiu, T. Iwasaki and N. Kambe, Org. Biomol. Chem., 2015,
13, 6803.
Moselage, J. Li and L. Ackermann, ACS Catal., 2016, 6, 498;
(d) R. Shang, L. Ilies and E. Nakamura, Chem. Rev., 2017, 117
9086; (e) R. Ueno, S. Natsui and N. Chatani, Org. Lett. 2018,
20, 1062 and cited therein.
N. Chatani, Top. Organomet. Chem., 2015, 56, 19 and cited
therein
Selected Reports: (a) Y. Aihara and N. Chatani, J. Am. Chem.
Soc., 2013, 135, 5308; (b) Y. Aihara, M. Tobisu, Y. Fukumoto
and N. Chatani, J. Am. Chem. Soc., 2014, 136, 15509; (c) Y.-J.
Liu, Y.-H. Liu, S.-Y. Yan and B.-F. Shi, Chem. Commun., 2015,
,
5
6
21 Selenium containing heterocycle: M. Iwasaki, N. Miki, Y.
Tsuchiya, K. Nakajima and Y. Nishihar, Org. Lett. 2017, 19
1092 and site therein.
,
51, 6388; (d) J. Yi, L. Yang, C. Xia and F. Li, J. Org. Chem. 2015,
80, 6213; (e) T. Uemura, M. Yamaguchi and N. Chatani,
Angew. Chem., Int. Ed., 2016, 55, 3162; (f) L. C. M. Castro, A.
22 (a) S. Mukherjee, P. S. Salini, A. Srinivasan and S.
Peruncheralathan, Chem. Commun., 2015, 51, 17148; (b) M.
Janni, S. Arora and S. Peruncheralathan, Org. Biomol. Chem.,
2016, 14, 8781; (c) M. Janni, A. Thirupathi, S. Arora and S.
Peruncheralathan, Chem. Commun., 2017, 53, 8439.
Obata, Y. Aihara and N. Chatani, Chem. Eur. J., 2016, 22
,
1362.
7
8
H. M. Omer and P. Liu, J. Am. Chem. Soc. 2017, 139, 9909.
Selected Review: (a) B. Godoi, R. F. Schumacher and G. Zeni,
23 B. Li, Z. Chen, H. Cao, and H. Zhao Org. Lett. 2018, 20, 3291.
Chem. Rev. 2011, 111, 2937; (b) K. Takimiya, I. Osaka, T. Mori 24 Various oxidants were examined (See ESI†, Table S2).
and M. Nakano, Acc. Chem. Res., 2014, 47, 1493; (c) H. Yao,
L. Ye, H. Zhang, S. Li, S. Zhang and J. Hou, Chem. Rev. 2016,
116, 7397; (d) B. Wu and N. Yoshikai, Org. Biomol.
Chem., 2016, 14, 5402 and cited therein.
R. Romagnoli, P. G. Baraldi, M. D. Carrion, C. L. Cara, D. Preti,
F. Fruttarolo, M. G. Pavani, M. A. Tabrizi, M. Tolomeo, S.
Grimaudo, A. D. Cristina, J. Balzarini, J. A. Hadfield, A.
Brancale and E. Hamel J. Med. Chem., 2007, 50, 2273.
25 Selected Reports: (a) Y. Aihara and N. Chatani, J. Am. Chem.
Soc., 2014, 136, 898; (b) X. Wu, Y. Zhao, and H. Ge, J. Am.
Chem. Soc., 2014, 136, 1789; (c) (d) C. Lin, W. Yu, J. Yao, B.
Wang, Z. Liu, and Y. Zhang, Org. Lett., 2015, 17, 1340; (e) X.
Wang, R. Qiu, C. Yan, V. P. Reddy, L. Zhu, X. Xu, and S.-F. Yin,
Org. Lett., 2015, 17, 1970; (f) S.-Y. Yan, Y.-J. Liu, B. Liu, Y.-H.
9
Liu, Z.-Z. Zhang and B.-F. Shi, Chem. Commun., 2015, 51
,
7341; (g) X. Wu, Y. Zhao, and H. Ge, J. Am. Chem. Soc., 2015,
137, 4924; (h) S. Maity, S. Agasti, A. M. Earsad, A. Hazra, and
D. Maiti, Chem. Eur. J., 2015, 21, 11320; (i) H. Tang, X.-R.
Huang, J. Yao, and H. Chen, J. Org. Chem., 2015, 80, 4672; (j)
C. Lin, Z. Chen, Z. Liu, and Y. Zhang, Org. Lett., 2017, 19, 850.
10 T. Chonan, D. Wakasugi, D. Yamamoto, M. Yashiro, T. Oi, H.
Tanaka, A. Ohoka-Sugita, F. Io, H. Koretsune and A. Hiratate,
Bioorg. Med. Chem., 2011, 19, 1580 and cited therein.
11 S. Dadiboyena, Eur. J. Med. Chem. 2012, 51, 17 and cited
therein.
12 (a) G. W. Stacey, F. W. Villaescusa and T. E. Wollner, J. Org.
Chem., 1965, 30, 4074; (b) A. Y. Solovyev, D. A. Androsov, D.
C. Neckers, J. Org. Chem. 2007, 72, 3122; (c) D. A. Androsov,
A. Y. Solovyev, M. L. Petrov, R. J. Butcher, J. P. Jasinski,
Tetrahedron, 2010, 66, 2474; (d) M. Adib, M. Soheilizada, S.
Rajai-daryasaraeia, P. Mirzae, Synlett 2015, 26, 1101.
13 (a) S. Krishnananthan, D. Smith, S. C. Traeger, A. Mathur, J.
Li, Tetrahedron Lett. 2015, 56, 3766; (b) C. Hou, Q. He and C.
Yang, Org. Lett. 2014, 16, 5040; (c) Y-S. Kim, S. H. Kwak and
Y-D, Gong, ACS Comb. Sci. 2015, 17, 365; (d) A. Acharya, S.
4 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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DOI: 10.1039/C8OB01712C
TOC Graphic
Nickel catalyzed C―H bond functionalization reaction has been used for the first time to study an
intramolecular site-selective C―S bond formation of arenes.