PIDA-Promoted Selective C5 C?H Selenylations of Indolines via Weak Interactions

Article abstract of DOI:10.1002/adsc.201900766

An efficient PIDA (phenyliodine(III) diacetate)-promoted positional selective C?H selenylations of indolines with diaryl diselenides has been developed. This transformation conducted under mild reaction conditions with a broad functional group tolerance,

Full text of DOI:10.1002/adsc.201900766

Title: PIDA-Promoted Selective C5 C–H Selenylations of Indolines via
Weak Interactions
Authors: Linghui Gu, Xinyue Fang, Zhengyun Weng, Jiafu Lin, Meicui
He, and Wenbo Ma
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Advanced Synthesis & Catalysis
10.1002/adsc.201900766
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
PIDA-Promoted Selective C C–H Selenylations of Indolines
5
via Weak Interactions
a
#
a
#
a
a
a
*a
Linghui Gu, Xinyue Fang, Zhengyun Weng, Jiafu Lin, Meicui He, Wenbo Ma
a
Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province, Sichuan Industrial Institute of
Antibiotics, Chengdu University, People’s Republic of China, 610052.
Fax: (+86)-(0)28-84333218; phone: (+86)-(0)28-84333218; e-mail: wenboma@hotmail.com
#
These authors contributed equally to this work.
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract: An efficient PIDA (phenyliodine(III) diacetate)- protocol to selenylated indolines. Preliminary mechanistic
promoted positional selective C–H selenylations of indolines studies indicated a SET pathway was likely involved in this
with diaryl diselenides has been developed. This selenylation reaction.
transformation conducted under mild reaction conditions with
a broad functional group tolerance, thus providing an efficient
Keywords: PIDA; Selenylations; Indoline; C–H
functionalization; Radical reactions.
activation of aromatic rings with nucleophiles (NuH)
and functionalized nucleophiles (Nu–FG) might be
proceeded through single-electron-transfer (SET)
pathway. Hence, in the past decades, a variety of
Introduction
The indole and indoline motifs have become
privileged structures as they widely exist in numerous
biologically active natural products, pharmaceuticals,
agrochemicals
modifications of indoles and indolines for the
diversification of the scaffolds have received
increasing attentions over the last few years. Recent
advances in the transition-metal catalysed direct C–H
functionalization provided a powerful strategy for the
modification of indole and indoline structures.
Nevertheless, the derivation of indoles and indolines
were generally limited to the C -C and C positions
nucleophiles (Nu-H or FG-Nu) such as TMSN ,
3
pigments.[
1]
TMSOAc, PhSH and β-dicarbonyl compounds were
employed as suitable coupling partners in the directly
convert the C–H bonds for organic transformations to
and
Thus,
the
[8]
[2]
meet the strong demand of green chemistry.
The C–Se bond was an important linkage in the
biologically active compounds due to organic
selenides display promising properties as antitumor,
[3]
[9]
antibacterial, antioxidant, anti-inflammatory agents.
With the consideration the importance of indolines and
chalcogenides, it is of great interest to combine the two
into a single entity. Previous reports on the transition-
metal catalysed regio-selective C–H chalcogenations
of indoles and indolines with various chalcogen
reagents have been disclosed by Kame, Glorious, Jain,
1
4
7
governed by the effect of directing groups or the
inherent nucleophilic reactivity,[4] while the site-
selective C–H functionalization on the remote less
activated C position has remained a great challenge.
5
In recent years, direct C–H functionalization via a
radical pathway, which often complementary to
traditional methods, has been achieved in significant
advance and emerged as a sustainable approach for the
synthesis of complicated molecules. In particularly,
the hypervalent iodine (III) reagents promoted radical
C–H functionalization[ which was first reported by
Kita’s group in early 1990s, were widely explored in
replacing of highly toxic heavy-metal oxidants in
classical organic synthesis due to its low toxicity, mild
reactivity, high oxidation ability and easy handling.
[10]
Samanta, Wang and Ackermann groups. However,
some of examples suffer from limitations to some
extent such as the use directing groups to govern its
ortho-selectivity, stoichiometric amount of metal
oxidant/catalyst, expensive transition metal catalysts,
long reaction times with harsh reaction conditions and
oxygen-free techniques.
[5]
6]
[7]
More recently, transition-metal catalysed remote C5
C–H functionalization of quinoline through oxidative
[11]
radical pathway have been widely explored.
Transition metal catalyst coordinated with the
bidentate directing groups to form a cation-radical
(
Scheme 1a). For these oxidative coupling reactions of
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201900766
intermediate which enable coupling reactions with Results and Discussion
various free radicals, thus overcame the geometrically
inaccessible cyclometallations to achieve the distal C–
H functionalization. In this regard, C–C and C–
We commenced our investigations with probing
reaction conditions for the C–H selenylations of
indoline 1a with diphenyl diselenide 2a as selenium
heteroatom bonds formations on the C position of 8-
5
aminoquinolinamide derivatives have been widely
developed to access diverse functionalized quinoline
scaffolds. (Scheme 1b). Furthermore, Mal and co-
reagent. With Cu(TFA)
2
as the additive various
oxidants were tested at 80 °C in THF, PhI(OAc)
2
workers
reported
an
unprecedented
C–H
proved to be optimal and furnished the selective C5
selenylated product 3aa in 85% yield, while the other
mononitration of indolines at the C
5
position under
mild condition via multiple weak interactions and
oxidant such as silver salts, Cu(OAc)
2
, m-CPBA,
factors. (Scheme 1c). [ To the best of our knowledge,
12]
K
2
S
2
O
8
and TBHP resulted in lower isolated yields or
the C–H selenylations occured at C
indolines or indoles have been rare reported so far.
Therefore, developing general, mild and
5
position of
simply no reaction. (Table 1, entries 1-10) Further
optimization with a set of representative solvent,
[13]
a
CH
DMSO gave unsatisfied results. (entries 12–17)
Screening of the additives indicated that Cu(OTf) and
AgOTf exhibited similar efficiency, affording product
3
CN, 1,4-dioxane, MeOH, toluene, DMF and
regioselective protocol for the preparation of 5-
selenylated indoles and indolines is highly desirable.
2
3aa in 85% and 82% yield respectively, (entries 18 and
22) whereas other additives, including AgTFA,
Zn(OTf)
2
3 2
and CF CO H only gave inferior results
(
entries 19−21). Decreasing or increasing the reaction
temperature led to a lower yield (entries 23 and 24).
Control experiments revealed that less than 10%
selenylated product was observed in the absence of the
Cu(TFA)
2
or PhI(OAc)
2
,
demonstrating the
indispensable of the oxidant and additive (Table 1,
entries 11 and 25). Thus, the optimized reactions
conditions were ultimately identified as Cu(TFA)
2
as
additive, along with PhI(OAc)
2
as the oxidant in THF
at 80 ︒C under Ar.
Table 1. Optimization of C–H selenylations[a]
Entry Additive Oxidant
Solvent %Yields[b]
Ag
1
2
3
4
5
6
7
8
9
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
2
2
2
2
2
2
2
2
2
2
O
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
DMF
DMSO
8
5
28
--
--
--
trace
--
13
85
--
72
56
--
37
32
76
Ag CO
3
AgTFA
AgOAc
AgNO
Cu(OAc)
m-CPBA
2
3
2
2 2 8
K S O
TBHP
PhI(OAc)
--
PhI(OAc)
PhI(OAc)
PhI(OAc)
PhI(OAc)
PhI(OAc)
PhI(OAc)
Scheme 1. Regio-selective C–H functionalization
10
Cu(TFA)
2
2
1
1
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
2
Inspired by these reports and our interest on the
research of diaryl selenides synthesis [14], we herein
report the first example of PIDA-promoted direct
12
13
14
15
16
17
2
2
2
2
2
2
2
2
2
2
2
2
3
CH CN
5
selective C -selenylations of indolines with readily
MeOH
dioxane
toluene
available diselenides via radical process to access
diversely selenylated indoline derivatives. (Scheme 1d)
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201900766
1
1
2
2
2
2
2
2
8
9
0
1
2
3
4
5
Cu(OTf)
AgTFA
2
PhI(OAc)
2
THF
THF
THF
THF
THF
THF
THF
THF
85
42
49
67
82
withdraw directing groups on the C
positions participated well in this transformation and
afforded the selective C selenylated product up to 90%
yields. Indoline with fluro at C and methoxyl at C
positions exhibited decreased reactivity, and delivered
the selenylated product in 53% and 55% respectively.
(3na and 3oa) Next, the substrate scope was further
expanded to variety of substituted diaryl diselenides.
As shown in scheme 3, electron-withdraw groups
presented on the phenyl ring at the para, ortho and
meta positions of the diaryl diselenides worked
efficiently and gave the desired products in good
yields under the standard conditions. (3ad-3ag, 68%–
2
, C
3
, C
4
, C
6
PhI(OAc)
PhI(OAc)
PhI(OAc)
PhI(OAc)
PhI(OAc)
PhI(OAc)
PhI(OAc)
2
CF
3
CO
2
H
2
5
Zn(OTf)
AgOTf
2
2
2
2
2
2
4
6
[
c]
Cu(TFA)
Cu(TFA)
--
2
2
69
[
d]
70
<10
[
a]
Reaction conditions: 1a (0.25 mmol), 2a (2.0 equiv, 0.5
mmol), Additive (20 mol%), solvent (2 mL), 12h, under Ar.
[
b]
[c]
[d]
Isolated Yields. 60 ︒C . 100 ︒C
8
1
8% yields) The structure of compound 3ai (CCDC
With the optimized conditions in hand, we next
912789) was further confirmed through crystal X-ray
evaluated the effects of the N-substitutes of indolines
1
. (Scheme 2) Variety of alkyl substituted sulfonamide
diffraction analysis. In contrast, the diaryl disulfides
bearing electron-donating groups such as methyl and
methoxyl only resulted in unsatisfied yields. (3ab and
reacted with diphenyl diselenide smoothly, whereas
the cyclopropyl substituted substrates gave the best
yields of all. (3aa-3da). Gratifyingly, the more
congested aryl substituted sulfonamide also proceeded
efficiently to provide the desired products in good
yields with excellent regioselectivity. Electron
diversity groups presented on the aryl rings did not
significantly affect the result. (3ea-3ha) Furthermore,
heterocyclic sulfonamide such as 1i was compatible,
albeit resulted in lower yield. Additionally, the N-
acetyl indoline was also viable, and affording the
corresponding product in 58% yield. (3ja) Control
experiments that were conducted with NH-free
indolines or N-methyl indolines failed to give the
desired product, thus highlighting the key importance
of carbonyl or sulfone moieties.
3
ac) It was noteworthy that the methoxyl, fluro, chloro
and bromo groups, were well tolerated under these
reaction conditions which provided a possibility
handle for further useful transformation.
Scheme 2. Effect exerted on the N-substitutent.
Subsequently, the versatility of the established method
was further probed with differently substutitued
indolines 1 and diaryl diselenides 2. (Scheme 3) The
indolines bearing electron-donating or electron-
Scheme 3. Scope of the C–H selenylations of substituted
indolines and diaryl diselenides
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201900766
As expected, this optimized system was also found to
be applicable to the C–H selenylations of tetrahydro-
quinolines derivatives 4 with different substituted
diaryl diselenides 2. Thus, tetrahydroquinoline
sulfamide 4 smoothly reacted with different readily
synthesized diaryl diselenides and afforded the
corresponding products with more than 80% yields.
(
1
5ad-5ah) The structure of compound 5ae (CCDC
912788) was further confirmed through crystal X-ray
diffraction analysis. However, seven-membered
tetrahydro-1H-benzoazepine substrate was not
compatible in this reaction and resulted no desired
products probably due to its congested effect.
Scheme 5. Late-stage C–H selenylations
After the investigation of the substrate scope and
synthetic utility, we went on to carry out further
elaborations of the products, as depicted in scheme 6.
The indolines could be easily converted into indoles in
good yields in the presence of DDQ in 1,4-dioxane
under mild conditions. Moreover, the directing group
could be successfully removed by treatment with red-
Scheme 4. Scope of C–H selenylations of tetrahydro-
quinolines
o
Al in toluene at 120 C for 14 h, and affording the 5-
selenylated NH-free indoline in 64% yield.
Subsequently, the synthetic utility of this selenylation
established as a tool for late-stage modification of
bioactive compounds was explored. For example, the
compounds 1u and 1v that displayed a promising
antiparasitic propertites, were also compatible in this
selenylations and give the corresponding products in
15]
8
0% and 68% respectively.[
Meanwhile, the
compound 4c, a retinoic acid receptor-related orphan
receptor γ (RORγ) agonist which is a key regulator of
inflammatory gene programs involved in T helper 17
(
TH17) cell proliferation that could regulate immune
[16]
response for cancer immunotherapy, participated in
this selenylation reaction smoothly and provided the
desired product in 54% yield.
Scheme 6. Traceless removal of directing groups
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201900766
To explore the reaction mechanism, a series of control
experiments were carried out (Scheme 7). Two radical
capture experiments conducted with stoichchiometric
TEMPO and BHT as radical scavenger. These
reactions were entirely suppressed and resulted no
desired product, which suggested that a SET (single
electron transfer) pathway might be involved in this
transformation. (Scheme 7a) Furthermore, the
subsequent radical clock experiment of pent-4-en-1-ol
with diphenyl diselenide (2a) under the standard
delocalization.[19] Meanwhile, the phenylthiol radical
(PhS·) generated through a homolytic cleavage under
thermal conditions attacked the C position of D via
5
the coupling reaction to give intermediate E. Finally, a
deprotonation process occurred at the thus formed
intermediated E to deliver the desired product F. The
addition of Cu(TFA) or the other metal additives
2
could promote the reaction significantly probably due
to the metal salts not only accelerated the formation of
[
12], [20]
the cation radical
but also coordinated to the
condition
afforded
2-(phenylselanylmethyl)
radical pair via a cation–π interactions according to the
[21]
tetrahydrofuran in 21% yield which further supported
the involvement of radical species in the reaction
process. (Scheme 7b). [ Finally, the selenylation
soft acid–soft base nature,
thus enhanced the
efficiency of the degradation to the free radical species
17]
[8b]
of the reaction. Furthermore, the N-centers of the
3
reaction conducted with CD OD as cosolvent revealed
indolines protected with mesyl or acetyl groups were
essential for this transformation, whereas the 1-Methyl
indoline and 1-H indoline failed to give the desired
product, probably due to the n-p* S=O or C=O non-
covalent interaction the lone-pair of nitrogen could be
no deuterium scrambling in the recovered starting
material or the product (Scheme 7c and 7d), thus
indicated the C−H bond cleavage is irreversible.
[12], [22]
avoided to react with highly oxidizing PIDA.
Scheme 8. Proposed mechanism
Conclusion
In summary, we have realized a novel and facile direct
PIDA-promoted positional selective C−H selenylation
of indolines and tetrahydroquinolines with diaryl
diselanes though radical pathway under mild reaction
conditions. This reaction tolerated a broad range of
functional groups presented either on the indolines,
tetrahydroquinolines or diaryl diselenids to access
diversely selenylated indoline and tetrahydroquinoline
derivatives. Furthermore, this method was also
applicable for the modification of complex bioactive
indoline compounds. The intense research on the
detailed mechanistic study and development of this
new selenylated reactions for the modification of
indolines for drug discovery are currently being
pursued in our laboratory, and will be reported in due
course.
Scheme 7. Investigation of the mechanism
Although the detailed mechanism was still unclear at
this stage and required further comprehensive
investigation, a plausible mechanism involved cation
radical pathway was proposed based on the preceding
[
6],
control experimental results and previous reports.
[8],[18]
Firstly, the interaction between the PhI(OAc)
2
reagent and indolines facilitated the generation of
intermediate B, followed by a SET oxidation process
to give the cation radical species C. C could be
transformed to intermediate D via extensively
5
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Advanced Synthesis & Catalysis
10.1002/adsc.201900766
Experimental Section
2013, 42, 7900–7942; d) G. Fang X. Cong, G. Zanoni,
Q. Liu, X. Bi, Adv. Synth, Catal. 2017, 359, 1422–1502.
[6] a) Y. Kita, T. Dohi, Chem. Rec. 2015, 15, 886–906; b)
Q. Feng, D. Chen, M. Hong, F. Wang, S. Huang, J. Org.
Chem. 2018, 83, 7553–7558; c) H. Sahoo, S. Singh, M.
Baidya, Org. Lett. 2018, 20, 3678–3681; d) Y.-C. Shieh,
K. Du, R. S. Basha, Y.-J. Xue, B.-H. Shih, L. Li, C.-F.
Lee, J. Org. Chem. 2019, 84, 6223–6231.
A
suspension of substituted indoline (1a) or
tetrahydroquinoline (0.25 mmol), 1,2-diphenyldiselane (2a)
(
156 mg, 0.50 mmol), Cu(TFA)
PhI(OAc) (90.5 mg, 0.50 mmol) in THF (2.0 mL) was
stirred under argon at 80 ︒C for 12 h. At ambient
temperature, the reaction mixture was quench with H O (10
mL) and extracted with EtOAc (3 x 25 mL). The combined
organic layers were dried over anhydrous Na SO . After
2
(15.9 mg, 20 mol %),
2
2
[7] Y. Kita, H. Tohma, M. Inagaki, K. Hatanaka, Y. Yakura,
Tetrahedron Lett. 1991, 32, 4321–4324.
2
4
filtration and evaporation of the solvents in vacuo, the crude
product was purified by column chromatography on silica
gel (Petroleum ether /EtOAc: 30/1→3/1) to yield 3aa or 5aa
product.
[8] a) Y. Kita, T. Takada, S. Mihara, B. A. Whelan, H.
Tohma J. Org. Chem. 1995, 60, 7144–7148; b) Y. Kita,
H. Tohma, K. Hatanaka, T. Takada, S. Fujita, S. Mitoh,
H. Sakurai, S. Oka, J. Am. Chem. Soc. 1994, 116, 3684–
3
691; c) M. Arisawa, N. G. Ramesh, M. Nakajima, H.
Tohma, Y. Kita, J. Org. Chem. 2001, 66, 59–65; d) K.
Sun, Y. Li, T. Xiong, J. Zhang, Q. Zhang, J. Am. Chem.
Soc. 2011, 133, 1694–1697; e) A. P. Antonchick, R.
Samanta, K. Kulikov, J. Lategahn, Angew. Chem. Int.
Ed. 2011, 50, 8605–8608; Angew. Chem., 2011, 123,
8764–8767; f) C. Mudithanapelli, L. P. Dhorma, M.
Kim, Org. Lett. 2019, 21, 3098–3102; g) C. Tian, X.
Yao, W. Ji, Q. Wang, G. An, G. Li, Eur. J. Org. Chem.
2019, 5972–5979; h) Y. Zhang, C. Wen, J. Li, Org.
Biomol. Chem. 2018, 16, 1912–1920.
Acknowledgements
The authors wish to thank the Sichuan Science and Technology
Program (Grant No. 2018JY0247, 2019YJ0282), the National
Natural Science Foundation of China (Grant No. 21502010), Key
Laboratory of Medicinal and Edible Plants Resources
Development of Sichuan Education Department (Grant No.
1
0Y201708) and the youth foundation of Chengdu University
(Grant No. 2018XZB01)
[
9] a) G. Mugesh, W. W. du Mont, H. Sies, Chem. Rev.
2
001, 101, 2125–2180; b) D. de Souza, D. O. Mariano,
References
F. Nedel, E. Schultze, V. F. Campos, F. Seixas, R. S. da
Silva, T. S. Munchen, V. Ilha, L. Dornelles, A. L. Braga,
J. B. Rocha, T. Collares, O. E. Rodrigues, J. Med. Chem.
2015, 58, 3329–3339; c) L. Engman, D. Stern, H. Frisell,
K. Vessman, M. Berglund, B. Ek, C.-M. Andersson,
Bioorg. Med. Chem. 1995, 3, 1255–1262.
[
1] a) T. Owa, A. Yokoi, K. Yamazaki, K. Yoshimatsu, T.
Yamori, T. Nagasu, J. Med. Chem. 2002, 45, 4913–
4
922; b) A. J. Kochanowska-Karamyan, M. T. Hamann,
Chem. Rev. 2010, 110, 4489–4497; c) D. Zhang, L. Zhao,
L. Wang, X. Fang, J. Zhao, X. Wang, L. Li, H. Liu, Y.
Wei, X. You, S. Cen, L. Yu, J. Nat. Prod. 2017, 80, 371–
[10] a) T. Gensch, F. J. R. Klauck, F. Glorius, Angew. Chem.
Int. Ed. 2016, 55, 11287–11291; Angew. Chem. 2016,
128, 11457–11461; b) P. Sharma, S. Rohilla, N. Jain,
J. Org. Chem. 2015, 80, 4116–4122; c) S. Maity, U.
Karmakar, R. Samanta, Chem. Commun. 2017, 53,
12197–12220; d) W. Xie, B. Li, B. Wang. J. Org.
Chem. 2016, 81, 396–403; e) P. Gandeepan, J. Koeller,
L. Ackermann, ACS Catal. 2017, 7, 1030–1034.
3
76; d) A. T. A. Boraei, M. S. Gomaa, E. S. H. E. Ashry,
A. Duerkop, Eur. J. Med. Chem. 2017, 125, 360–371.
2] T. Vivekanand, B. Satpathi, S. K. Bankara, S. S. V.
Ramasastry, RSC Adv. 2018, 8, 18576–18588.
[
[
3] a) J. A. Leitch, Y. Bhonoah, C. G. Frost, ACS Catal.
2
017, 7, 5618–5627; b) J. Kalepu, P. Gandeepan, L.
Ackermann, L. T. Pilarski, Chem. Sci. 2018, 9, 4203–
216.
4] a) J. Chen, Y. Jia, Org. Biomol. Chem. 2017, 15, 3550–
567; b) C. Wang, B. Maity, L. Cavallo, M. Rueping
[
11] a) B. Khan, H. S. Dutta, D. Koley, Asian J. Org. Chem.
019, 7, 1270–1297; b) A. M. Suess, M. Z. Ertem, C.
J. Cramer, S. S. Stahl, J. Am. Chem. Soc. 2013, 135,
4
2
[
3
9
2
797–9804; c) Y. Du, Y. Liu, J.-P. Wan, J. Org. Chem.
018, 83, 3403–3408; d) H. Qiao, S. Sun, F. Yang, Y.
Org. Lett. 2018, 20, 3105–3108; c) J. Li, Y. An, J. Li, S.
Yang, W. Wu, H. Jiang, Org. Chem. Front. 2017, 4,
Zhu, J. Kang, Y. Wu, Y. Wu, Adv. Synth. Catal. 2017,
59, 1976–1980.
12] A. Bose, P. Mal. Chem. Commun. 2017, 53, 11368–
1371.
1
590–1594; d) P. Sang, Z. Chen, J. Zou, Y. Zhang,
3
Green Chem. 2013, 15, 2096–2100; e) H. Zhang, C.
Wang, C. Li, G. Mei, Y. Li, F. Shi, Angew. Chem. Int.
Ed. 2017, 56, 116–121, Angew. Chem. 2017, 129, 122–
[
1
[
[
13] Z. Tan, Y. Liang, J. Yang, L. Cao, H. Jiang, M. Zhang,
Org. Lett. 2018, 20, 6554–6558.
1
27; f) J. K. Kirsch, J. L. Manske, J. P. Wolfe. J. Org.
Chem. 2018, 83, 13568–13573; g) T. Zhou, B. Li, B.
Wang, Chem. Commun. 2017, 53, 6343–6346; h) S.
Lancianesi, A. Palmieri, M. Petrini, Chem. Rev. 2014,
14] a) W. Ma, H. Dong, D. Wang, L. Ackermann, Adv.
Synth. Catal. 2017, 359, 966–973; b) W. Ma, Z. Weng,
T. Rogge, L. Gu, J. Lin, A. Peng, X. Luo, X. Gou, L.
Ackermann, Adv. Synth. Catal. 2018, 360, 704–710; c)
W. Ma, Z. Weng, X, Fang, L. Gu, Y. Song, L.
Ackermann, Eur. J. Org. Chem. 2019, 41–45; d) L. Gu,
X. Fang, Z. Weng, Y. Song, W. Ma, Eur. J. Org.
Chem., 2019, 1825–1829; e) G. Cera, L. Ackermann,
Chem. Eur. J. 2016, 22, 8475–8478; f) T. Müller, L.
Ackermann, Chem. Eur. J. 2016, 22, 14151–14154; g)
1
14, 7108–7149; i) Q, Zhang, Y, Ban, P. Yuan, S. Peng,
J. Fang, L. Wu, Q. Liu, Green Chem. 2017, 19, 5559–
563.
5
[
5] a) H. Yi, G. Zhang, H. Wang, Z. Huang, J. Wang, A. K.
Singh, A. Lei, Chem. Rev. 2017, 117, 9016–9085; b) J.
Xuan, A. Studer, Chem. Soc. Rev. 2017, 46, 4329–4346;
c) F. Dénès, C. H. Schiesser, P. Renaud, Chem. Soc. Rev.
6
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.201900766
W. Ma, P. Gandeepan, J. Li, L. Ackermann, Org. Chem.
Front. 2017, 4, 1435–1467.
A. Hajra, Adv. Synth. Catal. 2019, 316, 842–849; d) J.
Xu, L. Qiao, B. Ying, X. Zhu, C. Shenb, P. Zhang, Org.
Chem. Front. 2017, 4, 1116–1120.
[
[
15] R. J. Pagliero, M. Kaiser, R. Brun, M. J. Nieto, M. R.
[
19] a) N. Itoh, T. Sakamoto, E. Miyazawa, Y. Kikugawa, J.
Org. Chem. 2002, 67, 7424–7428. b) T. Tian W.-H.
Zhong, S. Meng X.-B. Meng, Z.-J. Li, J. Org. Chem.
Mazzieri, Bioorg. Med. Chem. Lett. 2017, 27, 3945–
3
949.
16] C. Doebelin, R. Patouret, R. D. Garcia-Ordonez, M. R.
Chang, V. Dharmarajan, D. S. Kuruvilla, S. J. Novick,
L. Lin, M. D. Cameron, P. R. Griffin, T. M.
Kamenecka, ChemMedChem, 2016, 11, 2607–2620.
17] a) H. Sahoo, A. Mandal, S. Dana, M. Baidya. Adv.
Synth. Catal. 2018, 360, 1099–1103; b) H. Sahoo, A.
Mandal, J. Selvakumar, M. Baidya. Eur. J. Org. Chem,
2
013, 78, 728–732; c) Y. Wang, Y. Wang, Z. Guo, Q.
Zhang, D. Li, Asian J. Org. Chem. 2016, 5, 1438–1441.
20] a) K. Mizuno, N. Kamiyama, N. Ichinose, Y. Otsuji,
Tetrahedron 1985, 41, 2207–2214; (b) T. Tamai, K.
Mizuno, I. Hasida, Y. Otsuji, J. Org. Chem. 1992, 57,
[
[
[
5
338–5442.
[
21] H. Mayr, M. Breugst, A. R. Ofial, Angew. Chem. Int.
Ed. 2011, 50, 6470–6505.
22] S. Maiti, P. Mal, J. Org. Chem. 2018, 83, 1340−1347.
2
016, 4321–4327.
18] a) D. Ji, X. He, Y. Xu, Z. Xu, Y. Bian, W. Liu, Q. Zhu,
Y. Xu, Org. Lett. 2016, 18, 4478–4481; (b) T. Liang,
X. He, D. Ji, H. Wu, Y. Xu, Y. Li, Z. Wang, Y. Xu, Q.
Zhu, Eur. J. Org. Chem, 2019, 2513–2519; c) A. Deya
[
7
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10.1002/adsc.201900766
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PIDA-Promoted Selective C C–H Selenylations of
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Indolines via Weak Interactions.
Adv. Synth. Catal. 2019, 361, Page – Page
Linghui Gu, Xinyue Fang, Zhengyun Weng, a
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Jiafu Lin, Meicui He, Wenbo Ma.*
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