One-pot synthesis of 2-hydroxymethylindoles: via photoredox-catalyzed ketyl-ynamide coupling/1,3-allylic alcohol transposition

Article abstract of DOI:10.1039/d0gc01522a

An efficient visible-light-mediated ketyl-ynamide coupling by employing ynamides bearing alkyl sulfonyl substituents to deliver eneindolin-3-ols has been developed. Subsequent 1,3-transposition of allylic alcohols in one pot is capable of synthesizing 2-hydroxymethylindoles in generally moderate to good yields. The synthetic utility of this protocol has also been demonstrated by the facile and practical synthesis of two bioactive molecules. The use of readily available substrates, a simple procedure and benign reaction conditions render this method a viable alternative for the synthesis of 2-hydroxymethylindoles. This journal is

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One-pot synthesis of 2-hydroxymethylindoles via
photoredox-catalyzed ketyl-ynamide coupling/1,3-
allylic alcohol transposition
Cite this: DOI: 10.1039/x0xx00000x
Ze-Shu Wang,a‡ Yang-Bo Chen,a‡ Kun Wang,a Zhou Xu*b and Long-Wu Ye*a,c
Received 00th January 2012,
Accepted 00th January 2012
An efficient visible-light-mediated ketyl-ynamide coupling by employing ynamides bearing
alkyl sulfonyl substitutents to deliver eneindolin-3-ols has been developed. Subsequent 1,3-
transposition of allylic alcohols in one-pot is capable of synthesizing 2-hydroxymethylindoles
in generally moderate to good yields. The synthetic utility of this protocol has also been
demonstrated by the facile and practical synthesis of two bioactive molecules. The use of
readily available substrates, a simple procedure and benign reaction conditions render this
method a viable alternative for the synthesis of 2-hydroxymethylindoles.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Introduction
Ketyl radical reactions especially those generated from
carbonyls by means of single electron transfer (SET) under
2-Hydroxymethylindoles and their oxidative products, 2-
acylindoles, are significant structural motifs which have been
found in various bioactive molecules (Fig. 1).1 It is surprising,
however, that only a few synthetic methods have been reported.
Ph
photocatalysis have attracted much attention in recent years.2
This protocol not only enables various carbonyl umpolung
reactions induced by light to effectively construct C–C bonds,
but also avoids using stoichiometric Kagan’s reagent (SmI2)
which are extremely sensitive to air and difficult to obtain.3 In
addition, most reactions involving photoredox-catalyzed ketyl
coupling with unsaturated bonds focused on substrates
containing C=C, C=N and aromatic ring.2 The first
photocatalytic ketyl-olefin coupling taking advantage of
concerted proton-coupled electron transfer (PCET) was
elegantly demonstrated by Knowles and co-workers in 2013.2f
Afterwards, the use of Lewis acids or Brønsted acids as
additives was necessary in favor of ketyl radical formation in
most cases. Photocatalytic ketyl-alkyne cyclization was first
described by Rueping et al. in 2016, but the reaction had to rely
on the alkyne bearing electron-donating groups (EDG).2b
NC
CF3
HO2C
N
Ph
N
OH
N
F3C
OH
H
N
OH
H
antiandrogen activity
antifungal activity
Ph
antitumor activity
Br
Ph
Ph
Ph
HO2C
Ph
O
N
O
H
N
H
N
O
anti-botrytis allii &
analgesic activity
antipyretic activity &
anti-inflammatory activity
antitumor activity
Fig.
1 Selected examples of 2-hydroxymethylindoles and 2-acylindoles in
bioactive compounds.
For example, Sonogashira coupling of o-aminoiodobenzenes
and propargyl alcohols and subsequent cyclization in situ
provided a convenient route to prepare 2-hydroxymethylindoles,
but this method was only applicable to 3-unsubstituted
indoles.1c Thus, the development of novel methods for the
construction of these two kinds of N-heterocycles is highly
desirable, especially those with high efficiency, flexibility, and
benign reaction conditions.
a.State Key Laboratory of Physical Chemistry of Solid Surfaces and Key
Laboratory for Chemical Biology of Fujian Province, College of
Chemistry and Chemical Engineering, Xiamen University, Xiamen
361005,China.
E-mail: longwuye@xmu.edu.cn
b.Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy,
School of Pharmacy, Xuzhou Medical University, Xuzhou 221004,
China.
E-mail: xuzhou@xzhmu.edu.cn
c. State Key Laboratory of Organometallic Chemistry, Chinese Academy
of Sciences, Shanghai 200032, China.
† Electronic supplementary information (ESI) available. CCDC 1998433
(3a). For ESI and crystallographic data in CIF or other electronic format
see DOI: 10.1039/
‡ These authors contributed equally to this work.
This journal is © The Royal Society of Chemistry 2013
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Ynamides are versatile reagents for organic synthesis and
We then wondered whether the above eneindolin-3-ol could be
have received extensive attention over the past decades.4,5 converted into the corresponding 2-hydroxymethylindole through
However, few radical reactions based on ynamides have been 1,3-allylic alcohol transposition. As shown in Scheme 2a,
developed so far compared with ionic reactions.6,7 Usually, eneindolin-3-ol 2a could not be converted into the desired 2-
radical addition occurs on the β position of ynamides, given hydroxymethylindole 3a by just elevating the reaction temperature to
o
that generated vinly radical can be stabilized by contiguous 80 C.12 Instead, significant formation of the dehydroxylated indole
nitrogen atom.6 Intramolecular radical α position addition 2aa was formed presumably via the reduction of 2a by Hantzsch
would be achieved based on radical tethered ynamides leading ester.13 To remove
to thermodynamically stable N-heterocycles.7 In our study on
developing ynamide chemistry for heterocycle synthesis,8 we
Table 1 Optimization of reaction conditionsa
O
very recently disclosed the first ynamide Smiles rearrangement
HO
photocatalyst (1 mol %)
Ph
Ph
Hantzsch ester (4 equiv)
that was triggered by photoredox-catalyzed regioselective
ketyl-ynamide coupling, allowing the facile synthesis of
Ph Ph
N
solvent, N2, rt, 1-4 h
30 W blue LED
N
Ms
Ms
synthetically
useful
2-benzhydrylindoles
and
3-
1a
2a
benzhydrylisoquinolines (Scheme 1a).9 Of note, the use of
arylsulfonyl group protected ynamides (R = aryl) was necessary.
When R was replaced by the alkyl group, the Smiles
rearrangement was inhibited, leading to the formation of
eneindolin-3-ols.9 On the basis of these findings, we envisioned
that the formed eneindolin-3-ols might undergo further 1,3-
transposition of allylic alcohols10 to produce the corresponding
valuable 2-hydroxymethylindoles. Herein, we describe the
realization of such a visible-light-mediated ketyl-ynamide
coupling by employing ynamides bearing alkyl sulfonyl
substitutents, delivering functionalized eneindolin-3-ols.11
Subsequent 1,3-allylic alcohol transposition in one-pot was
capable of synthesizing various 2-hydroxymethylindoles in
generally moderate to good yields under benign reaction
conditions (Scheme 1b).
Yieldb (%)
Entry Photocatalyst
1
Reaction Conditions
E/Z
DMF, rt, 1 h
87
99c
87
48
99
63
58
72
76
91
46
82
84
92
33
89
58
3/1
6/1
3/1
1/1
1/1
1/1
2/1
1/1
2/1
4/1
2/1
13/1
7/1
17/1
32/1
5/1
1/2
[Ir(ppy)2(dtbbpy)]PF6
2
DMSO, rt, 1 h
DMA, rt, 1 h
[Ir(ppy)2(dtbbpy)]PF6
[Ir(ppy)2(dtbbpy)]PF6
[Ir(ppy)2(dtbbpy)]PF6
[Ir(ppy)2(dtbbpy)]PF6
[Ir(ppy)2(dtbbpy)]PF6
[Ir(ppy)2(dtbbpy)]PF6
[Ir(ppy)2(dtbbpy)]PF6
[Ir(ppy)2(dtbbpy)]PF6
[Ir(dF(CF)3ppy)2(dtbbpy)]PF6
fac-Ir(ppy)3
3
4
MeCN, rt, 3 h
MeOH, rt, 3 h
1,4-dioxane, rt, 4 h
iPrOH, rt, 4 h
DCE, rt, 1 h
5
6
7
8
9
THF, rt, 1 h
10
11
12
13
14
15
16d
17e
DMSO, rt, 3 h
DMSO, rt, 3 h
DMSO, rt, 3 h
DMSO, rt, 3 h
DMSO, rt, 1 h
DMSO, rt, 4 h
DMSO, rt, 3 h
DMSO, rt, 1 h
a) Ketyl-ynamide coupling followed by Smiles rearrangement (previous work)
O
HO
R2
Ru(bpy)3(PF6)2
R2
R
R
HO
R
R2
IrIII
R
R2 R1
R1
R
R1
R
R1
Ru(bpy)3Cl2

N

N
HE
(R = aryl)
N
N
SO2
H
SO2R
4CzIPN
SO2R
Mes-AcrClO4
b) Ketyl-ynamide coupling followed by 1,3-allylic alcohol transposition (this work)
O
[Ir(ppy)2(dtbbpy)]PF6
[Ir(ppy)2(dtbbpy)]PF6
HO
HO
R2
R2
R2
R
R
R
R
R1
R1
IrIII
R2 R1
R1

N
N
N
1,3-
transposition
OH
N
HE
(R = alkyl)

a
SO2R
Reaction conditions: 1a (0.03 mmol), Hantzsch ester (0.12 mmol),
SO2R
SO2R
SO2R
photocatalyst (0.3 umol), solvent (0.3 mL), rt, 1-4 h, N2; 30 W blue LED is
used and the distance between light source and Schlenk tubes is about 3 cm. b
Measured by 1H NMR using Hantzsch ester and Hantzsch pyridine as internal
Scheme 1 Photoredox-mediated regioselective ketyl-ynamide coupling.
standard. c Isolated yield was 84%. d 2 equiv of Hantzsch ester was used. e
equiv of Hantzsch ester was used.
3
Results and discussion
At the outset, Ms-substituted benzoyl ynamide 1a was employed
as the model substrate to optimize this visible light-mediated ketyl-
ynamide coupling, as outlined in Table 1. To our delight, solvent
screening (Table 1, entries 1–9) revealed that the use of DMSO
could lead to the formation of the corresponding eneindolin-3-ol 2a
in almost quantitative yield with 6/1 E/Z ratio (Table 1, entry 2). In
addition, other types of photocatalysts were also investigated, but
failed to further improve the reaction (Table 1, entries 10–15).
Finally, it was found that reducing the loading of Hantzsch ester led
to significantly decreased efficiency of the reaction (Table 1, entries
16–17).
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CF3
F
With the above optimized reaction conditions in hands, we next
explored the substrate scope (Table 2). The one-pot reaction
occurred efficiently with various Ms-substituted ynamides 1, leading
to the desired 2-hydroxymethylindoles 3 in generally moderate to
good yields. A range of aryl-substituted ynamides bearing both the
electron-withdrawing and electron-donating substituents were first
investigated to furnish the desired products 3b−3f in 63−86% yields
(Table 2, entries 1–6). In addition, chlorophenyl, tolyl, even thienyl
group on 2-hydroxymethylindoles 3g−3i could be obtained in
71−78% yields (Table 2, entries 7–9). This reaction was also
applicable to the formyl and acetyl substituted ynamides to produce
the expected 3j and 3k in 47% and 23% yields, respectively (Table 2,
entries 10 and 11). Moreover, ynamides bearing different R groups
could react smoothly to deliver the desired 2-hydroxymethylindoles
3l−3n in good yields (Table 2, entries 12–14). Besides Ms-
substituted ynamides, n-propyl sulfonyl group substituted ynamide
was also evaluated, delivering the corresponding product 3o in 33%
yield (Table 2, entry 15). Of note, attempts to extend the reaction to
styryl-substituted ynamide 1p, terminal ynamide 1q and i-propyl
sulfonyl group substituted ynamide 1r only resulted in complex
mixture of products.15 Thus, this one-pot strategy provides a
convenient and practical route for the preparation of the synthetically
useful 2-hydroxymethylindoles.
t-Bu
t-Bu
t-Bu
t-Bu
N
N
O
O
N
N
N
N
F
F
EtO
OEt
Ir
Ir
N
H
N
N
F
CF3
[Ir(ppy)2(dtbbpy)]+
[Ir(dF(CF3)ppy)2(dtbbpy)]+
Hantzsch ester
2+
N
N
Ir
N
NC
CN
N
N
N
N
Ru
N
N
N
N
N
N
[Ru(bpy)3]2+
fac-Ir(ppy)3
4CzIPN
the residual Hantzsch ester, we treated it under O2 (1 atm)
atmosphere mediated by photocatalysis process and were pleased to
find that the conversion of Hantzsch ester to Hantzsch pyridine was
very effective (Scheme 2b).14 Thus, we performed this one-pot
reaction and found that 2-hydroxymethylindole 3a could be formed
in 76% yield, as depicted in Scheme 2c: the treatment of ynamide 1a
with Hantzsch ester in the presence of
1
mol
%
of
[Ir(ppy)2(dtbbpy)]PF6 irradiated by blue LED at room temperature to
produce 2a; then the reaction system was charged with O2 and the
same blue LED to remove the residual Hantzsch ester; finally, the
reaction was warmed up to 80 C, delivering the desired 3a. The
molecular structure of 3a was further confirmed by X-ray diffraction
o
Table 2 Reaction scope studya
(Fig. 2).
R2
R2
1) [Ir(ppy)2(dtbbpy)]PF6 (1 mol %)
Hantzsch ester (4 equiv)
DMSO, N2, rt, 30 W blue LED, 1 h
R
R1
R
a)
O
R1
HO
Ph
Ph
Ph
N
Ph
OH
standard
condition
N
2) DMSO, O2, rt, 30 W blue LED, 2 h,
then 80 °C, 1-4 h
1a
+
PG
PG
1
N2, 80 °C, 5 h
N
Ms
N
Ms
3
2a
, 55%
2aa
, 22%
b)
[Ir(ppy)2(dtbbpy)]PF6
(0.25 mol %)
EtO2C
CO2Et
EtO2C
CO2Et
DMSO, O2, rt
30 W blue LED, 2 h
N
H
N
99%
c)
O
1) [Ir(ppy)2(dtbbpy)]PF6 (1 mol %)
Hantzsch ester (4 equiv)
DMSO, N2, rt, 30 W blue LED, 1 h
Ph
Ph
Ph Ph
N
Ms
OH
N
2) DMSO, O2, rt, 30 W blue LED, 2 h,
then 80 °C, 1 h
Ms
1a
3a
, 76%
Scheme 2 Attempts to synthesize 2-hydroxymethylindole 3a in one-pot.
Fig. 2 Crystal structure of compound 3a.
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example, indole compound 6 with anti-botrytis allii and analgesic
activity1e could be obtained in 84% total yield from 2-
hydroxymethylindole 3a through DMP oxidation followed by the
removal of Ms group. Moreover, the treatment of indole 3d with the
above same procedures followed by the protection with methyl
group afforded 2-benzoylindole 7 in 60% yield (3 steps), which
shows antipyretic and anti-inflammatory activity.1d We also tested
the above 2-hydroxymethylindoles for their bioactivity and found
that compounds 3a−3c exerted significant cytotoxic effects on the
melanoma cells A375 and esophageal cancer cells SK-GT-4,16
indicating the potential utility of these compounds in medicinal
chemistry.
F
Cl
Ph
Ph
Ph
Ph
N
Ms
OH
N
N
Ms
OH
OH
Ms
3b
3a
(1) , 76%
3c
(2) , 84%
(3) , 83%
Br
Ph
Ph
Ph
N
OH
N
Ms
OH
N
OH
Ms
Ms
3d
3e
3f
(6) , 67%
(4) , 86%
(5) , 63%
Ph
Cl
Ph
1) DMP (5.0 equiv)
Ph
Ph
O
DCM, 0 °C - rt, 15 min
S
N
Ms
OH
N
2) Cs2CO3 (0.5 equiv)
EtOH, 80 °C, 30 min
H
Ph
OH
Ph
6
, 84% (2 steps)
anti-botrytis allii & analgesic activity
Ph
OH
3a
N
Ms
N
OH
N
Br
Br
Ms
3h
Ms
3g
1) DMP (5.0 equiv)
3i
(7) , 78%
(8) , 75%
(9) , 71%
DCM, 0 °C - rt, 15 min
Ph
Ph
2) Cs2CO3 (0.5 equiv)
EtOH, 80 °C, 30 min
Ph
Ph
N
Ph
OH
Br
O
Ph
OH
N
Ms
3d
OH
3) NaH (1.5 equiv)
CH3I (1.5 equiv)
DMF, rt, 1.5 h
N
Ms
OH
7
, 60% (3 steps)
antipyretic & anti-inflammatory activity
N
Ms
N
Ms
b
c
3l
(12) , 84%
3j
3k
(10) , 47%
(11) , 23%
Scheme 4 Synthetic applications.
Ph
Ph
Ph
MeO
Ph
Ph
Ph
To further probe the reaction mechanism, several control
experiments were performed. To our surprise, eneindolin-3-ol
2a could not be converted into 3a at 80 C in DMSO and most
N
N
Ms
N
Ms
OH
SO2nPr
3o
(15) , 33%
OH
OH
o
of 2a (>95%) was recovered (Scheme 5a). Instead, when 2a
was exposed to photocatalyst under O2 atmosphere, 2a was
readily transformed into 3a in 75% yield (Scheme 5b). We
believed DMSO could partly transfer into MsOH in
photocatalysis process,17 which was detected by electrospray
ionization mass spectrometry (ESI-MS) in the negative-ion
mode. Thus, MsOH should play the key role in promoting this
1,3-allylic alcohol transposition, as confirmed by the fact that
the treatment of 2a with 10 mol % of MsOH led to the desired
3a in 83% yield (Scheme 5c). In other words, the second
photocatalysis process under O2 atmosphere not only removes
the residual Hantzsch ester, which may lead to the formation of
the dehydroxylated indole via reduction, but also promotes the
1,3-allylic alcohol transposition under benign conditions.
Finally, it was found that 74% labeled oxygen was incorporated
into 3a when 1a was exposed to standard conditions in the
presence of 10 equiv of H218O, indicating that the oxygen of the
newly formed hydroxyl group originates from water but not
molecular oxygen (Scheme 5d).
3m
3n
(14) , 70%
(13)
, 71%
a
Reaction conditions: step 1: 1a (0.2 mmol), Hantzsch ester (0.8 mmol),
[Ir(ppy)2(dtbbpy)]PF6 (0.002 mmol), DMSO (2 mL), rt, 1 h, N2; 30 W blue
LED is used and the distance between light source and Schlenk tubes is about
o
3 cm; step 2: rt, 2 h, O2, 30 W blue LED; 80 C, 1-4 h; isolated yields are
reported. b The reaction was operated on step 1 without applying step 2, 15 h.
c Step 1 required 2 h.
Besides, the photoredox-catalyzed ketyl-ynamide coupling
reaction could be extended to one more methylene of ynamide
4 in the presence of DCE as solvent,16 delivering the
corresponding tetrahydroisoquinolin-4-ol 5 in 33% yield with
only the E configuration of the double bond, as shown in
Scheme 3. Notably in this case, the subsequent 1,3-allylic
alcohol transposition of 5 failed under the above reaction
conditions or even in the presence of proton acids.
Ph
[Ir(ppy)2(dtbbpy)]PF6 (1 mol %)
Hantzsch ester (4 equiv)
Ph
Ms
O
HO Ph
N
DCE, N2, rt
30 W blue LED, 1 h
N
Ms
Ph
4
5
, 33%
Scheme 3 Photoredox-catalyzed coupling of ketyl-ynamide 4.
In addition, the synthetic applications of the synthesized 2-
hydroxymethylindoles 3 were also demonstrated (Scheme 4). For
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a)
Ph
Ph
Ph
IrIII
HE
HO
Ph
Ph
O
Ph
Ph
Ph
DMSO
N
then heat
OH
N
Ms
3a
N
Ms
2a
N
Ms
3a
Ms
1a
80 °C, 2 h
OH
H
N
1,3-
transposition
b)
R
R
R
Ph
HE +
SET
IrIII*
[Ir(ppy)2(dtbbpy)]PF6
(1 mol %)
Ph
OH
H
N
IrII
2a
N
Ms
HO
80 °C, 2 h
DMSO, O2, rt
30 W blue LED, 2 h
Ph
Ph
R
SET
3a
, 75%
HE
N
Ms
2a
c)
(R = CO2Et)
Ph
IrIII
Ph
OH
MsOH (10 mol %)
DMSO, 80 °C, 2 h
H
N
N
2a
HAT
N
Ms
HAT
R
R
R
R
3a
, 83%
H
Ox-HE
HE
d)
Ph
1) [Ir(ppy)2(dtbpy)]PF6 (1 mol %)
Hantzsch ester (4 equiv)
HO
O
Ph
Ph
regioselective
ketyl-ynamide coupling
74% 18
O
OH Ph
H218O (10 equiv), DMSO
N2, rt, 30 W blue LED, 1 h
Ph
Ph
Ph Ph

N
Ms
N

18OH
N
Ms
N
2) DMSO, O2, rt, 30 W blue LED, 2 h,
then 80 °C, 2 h
Ms
A
Ms
B
1a
3a
, 61%
Scheme 6 Plausible reaction mechanism.
Scheme 5 Mechanistic studies.
Conclusions
On the basis of the above experimental observations and
previous work,8 a plausible mechanism to rationalize the
formation of 3a is proposed (Scheme 6). Initially, IrIII is
activated to IrIII* (excited-state) under blue LED irradiation.
Next, Hantzsch ester (HE) reacts with IrIII* through reductive
quenching to deliver HE•+ and IrII. Subsequently, ynamide 1a
activated by HE•+ undergoes SET with IrII to generate ketyl
radical species A followed by regioselective ketyl-ynamide
coupling, producing the vinly radical intermediate B.
Subsequent hydrogen atom transfer (HAT) may occur to afford
enamide 2a containing E/Z isomers. Finally, enamide 2a is
converted into the corresponding 2-hydroxymethylindole 3a
through acid-promoted 1,3-allylic alcohol transposition.
In summary, we have developed a photoredox-catalyzed ketyl-
ynamide coupling to deliver eneindolin-3-ols by employing
ynamides bearing alkyl sulfonyl substitutents. Subsequent 1,3-
allylic alcohol transposition in one-pot was capable of
synthesizing 2-hydroxymethylindoles in generally moderate to
good yields. In addition, this chemistry enables the facile and
practical synthesis of two bioactive molecules. The use of
readily available substrates, a simple procedure and benign
reaction conditions render this method potentially useful in
organic synthesis. The development of other radical reactions
based on ynamides is being investigated in our laboratory.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We are grateful for financial support from the National Natural
Science Foundation of China (21772161 and 21622204), the
Natural Science Foundation of Fujian Province of China
(2019J02001), the President Research Funds from Xiamen
University (20720180036), NFFTBS (No. J1310024), PCSIRT,
Science & Technology Cooperation Program of Xiamen
(3502Z20183015), the Qing Lan Project of Jiangsu Province,
the 333 Project of Jiangsu Province and the Jiangsu Six Talent
Peaks Program (YY-042). We thank Professor Xianming Deng
from Xiamen University (School of Life Sciences) for
assistance with biological tests analysis.
Notes and references
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1
For selected examples, see: (a) Q. Zhang, D. Li, P. Wei, J. Zhang, J.
55, 4547; (j) H. Jin, L. Huang, J. Xie, M. Rudolph, F. Rominger and
A. S. K. Hashmi, Angew. Chem. Int. Ed., 2016, 55, 794.
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6 | J. Name., 2012, 00, 1-3
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ARTICLE
Li, Nat. Commun., 2020, 11, 638; (b) L.-Y. Xie, Y.-S. Bai, X.-Q.
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12 By prolonging the reaction time (18 h), 2aa could be formed in 53%
yield.
13 For the relevant reduction of enamines to indoles, see: C. Chowdhury,
B. Das, S. Mukherjee and B. Achari, J. Org. Chem., 2012, 77, 5108.
14 For the relevant photoinduced aromatization of dihydropyridines, see:
L. Zheng, Y.-Q. Yang and H.-X. Li, Synthesis, 2016, 48, 4221.
15 For the structures of ynamides 1p−1r see below:
Ph
Ph
Ph
O
Ph
O
Ph
O
N
N
N
SO2iPr
Ms
Ms
1q
1p
1r
16 For details, see the Supporting Information.
17 E. Robert-Banchereau, S. Lacombe and J. Oliivier, Tetrahedron,
1997, 53, 2087.
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 7