Diastereoselective olefin amidoacylationviaphotoredox PCET/nickel-dual catalysis: reaction scope and mechanistic insights

Article abstract of DOI:10.1039/d0sc01459a

The selective 1,2-aminoacylation of olefins provides opportunities for the rapid construction of nitrogen-containing molecules. However, the lack of CO-free acylation reactions has limited their application. By using photoredox proton-coupled electron transfer (PCET)/Ni dual-catalysis, a highly regio- and diastereoselective amidoacylation of unactivated olefins has been developed. Various acyl electrophiles are compatible, including alkyl- and aryl acyl chlorides and anhydrides, as well asin situactivated carboxylic acids. Hammett studies and other mechanistic experiments to elucidate features of the diastereoselectivity, a transient absorption study of the PCET step, as well as computational evidence, provide an in-depth understanding of the disclosed transformation.

Full text of DOI:10.1039/d0sc01459a

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DOI: 10.1039/D0SC01459A
ARTICLE
Diastereoselective Olefin Amidoacylation via Photoredox
PCET/Nickel-Dual Catalysis: Reaction Scope and Mechanistic
Insights
Received 00th January 20xx,
Accepted 00th January 20xx
Shuai Zheng,a Shuo-Qing Zhang,b Borna Saeednia,a Jiawang Zhou,a Jessica M. Anna,a Xin Hong*b and
Gary A. Molander*a
DOI: 10.1039/x0xx00000x
The selective 1,2-aminoacylation of olefins provides opportunities for the rapid construction of nitrogen-containing
molecules. However, the lack of CO-free acylation reactions has limited their application. By using photoredox proton-
coupled electron transfer (PCET)/Ni dual-catalysis, a highly regio- and diastereoselective amidoacylation of unactivated
olefins has been developed. Various acyl electrophiles are compatible, including alkyl- and aryl acyl chlorides and anhydrides,
as well as in situ activated carboxylic acids. Hammett studies and other mechanistic experiments to elucidate features of the
diastereoselectivity, a transient absorption study of the PCET step, as well as computational evidence, provide an in-depth
understanding of the disclosed transformation.
partners and/or polarity reversal,9-13 as well as kinetically
favorable radical cyclization approaches.14,15 Among these
transformations, carboamination has received significant
Introduction
Transition-metal
catalyzed
1,2-difunctionalizations
of
attention because of the prevalence of nitrogen-containing
unactivated olefins have emerged as powerful methods for the

A. -Amino ketones in bioactive molecules
B. Representative methods for amino-/amidoacylation of olefins
Cl
O
N
OBz
-
CO
Ar4B ,
N
R2
N
O
N
R1
N
[Pd], L
N
Ar
R1
75 - 85 ºC
Bower et al.
O
R2
O
H
H
N
Pagoclone
Anxiolytic Agent
O
O
O
O
AQ
I CO
Ar- ,
O
O
O
[Pd], L, base
N
NHAQ
O
O
N
R
Me
100 ºC
Wu et al.
H
N
Ar
OH
R
O
O
Me
Cethromycin
Antibiotics
(-)-Hygrine
Alkaloid from Coca Leaves
O
C. Utilizing N-centered radicals in Transition Metal Catalysis
D. Amidoacylation via photoredox PCET/Ni dual catalysis (this work)
concerted PCET
O
[N] [C]
O
R1
R2
[PC]*
e-
R1
R2
[C]
[C] Nu
Y
M = Cu, Ni
O
Ar
[Ni]/[PC]
Base
N
O
N
N
H
R
n
Ar
N
M = Cu, Ni, Pd
Ar
R
pendant olefin or alkyl
N
[C]
R
X
R1
n = 0,2
R1
H
direct C-N formation
Figure 1. Amidoacylation of Olefin Species
cascade 1,5-HAT or olefin functionalization
Base
O
elaboration of commodity chemicals over the past decades, small molecules and heterocycles in bio-active and drug-like
with attractive capabilities for rapidly building molecular molecules.16 Progress has been achieved using amines as
complexity.1-5 Multiple strategies have been employed to nucleophilic species for directed aminopalladation6,17 or
achieve selectivity in the heterodifunctionalization, such as trapping of cationic species after C-C bond formation.8,18 Efforts
directed migratory insertion,6 nucleometalation,7 radical-polar have also been made to utilize prefunctionalized, reductively
crossover of activated olefins,8 utilization of bulky coupling generated amidyl- and iminyl radicals19-21 to improve efficiency
and selectivity, while the oxidative proton-coupled electron
transfer (PCET) approach has been utilized to generate N-
a. Roy and Diana Vagelos Laboratories, Department of Chemistry, University of
centered radicals directly from N-H functional units.14,15,22-25
Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-
6323, United States
b. Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, China
Electronic Supplementary Information (ESI) available. See DOI: 10.1039/x0xx00000x
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Although β-amino ketone structures are reasonably prevalent abstraction from the solvent,23 which led us to a further solvent
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among bioactive molecules (Figure 1A), aminoacylation optimization. Acetonitrile was eventuallyDidOeI:n1t0i.f1i0e3d9/aDs0tShCe01m45o9sAt
reactions and aminocarbonylative transformations of olefins suitable solvent, rendering a 75% yield of 1 (entry 7). Owing to
appear relatively rare (Figure 1B). Early efforts were focused on the vast availability of carboxylic acid functional groups in a
net-oxidative transformations, rendering β-amino esters as the variety of commodity chemicals, we also examined the
final product,26,27 while the Lambert group accessed possibilities of employing in situ activation of carboxylic acids as
amidoacylation products by tethering
a
Pd-catalyzed the source of the acyl electrophile.39 After several attempts
carbonylation process with a Lewis acid-catalyzed Friedel-Crafts (entries 8-11), oxalyl chloride was identified as an appropriate
acylation of electron-rich (hetero)aromatic systems.28 Later, activator, affording a 73% yield.
others utilized an umpolung approach using a tethered oxime
O
O
(dMeObpy)NiCl2 (6 mol %)
Ph
O
ester as an electrophilic nitrogen source and disclosed
iminoacylation transformations using tetraaryl borates or
organozinc reagents.29,30 In a more recent report,31 such
transformations were achieved with aryl iodides using an 8-
aminoquinoline directing group.
Together, these approaches provide a powerful suite of
methods for the synthesis of N-heterocycles as well as β-amino
ketone structures, yet many challenges remain to be addressed.
One common feature of these transformations is the need for
CO gas, which, although inexpensive and abundant, is toxic and
flammable. Additionally, the majority of present
transformations require aryl electrophiles or nucleophiles,
while alkyl electrophiles remain challenging to incorporate.
Because of their good commercial availability and convenient
preparation, acyl (pseudo)halides are useful surrogates to
consider in such transformations.32
As attractive as the utilization of N-centered radicals might
be,20,33-35 the application of such intermediates in transition
metal catalysis still remains rare (Figure 1C). Apart from several
reports facilitating direct C-N bond construction,36 transition
metal-catalyzed cascade transformations, where C-centered
radicals were generated via either 1,5-HAT37,38 or 5-exo-trig
cyclization,15,20 to this points are scarce, possibly because of
potential selectivity issues and the incompatibility between
transition metal catalysts and N-radical generation. Therefore,
inspired by our recent efforts to meld photoredox PCET with
nickel catalysis for amidoarylation of olefins,15 we sought to
address the challenges of amidoacylation by utilizing acyl
electrophiles in photoredox PCET/Ni dual-catalyzed olefin
difunctionalization (Figure 1D).
N
H
[Ir-1] (3 mol %)
Ph
N
+
Cl
Ph
[P] base 2.5 equiv
DCE (0.05 M), hv
Bz
Me
Me
1a
entry
1b
1
-
Variation from standard conditionsa
none
yield (%)b
PF6
CF3
F
R
1
2
3
4
46
N
[Ir-2] instead of [Ir-1]
45
41
N
N
F
F
Ir
4CzIPN instead of [Ir-1]
Ni(phen)Cl2 instead of Ni(dMeObpy)Cl2
Ni(dtbbpy)Cl2 instead of Ni(dMeObpy)Cl2
Deviation from entry 5a
40
N
R
5
43
F
CF3
yield (%)b
entry
[Ir-1] R = H; [Ir-2] R = F
Ir-photocatalyst
6
PhCF3 instead of DCE
60
O
Bu4N+
7
MeCN instead of DCE
75
P
OBu
OBu
[P] base
Carboxylic Acid Activation
-O
O
O
entry 7
Activator
1
S1a
Ph
Y
Ph
entry
OH
O
O
MeO
O
OMe
Activatora
DMDC
yield (%)b
DMDC
8
9
25
NMe2
0
73
0
TFFH
-
PF6
Me2N
F
10
11
(COCl)2 with cat. DMF
TFFH
Succinimide
Scheme 1. Reaction Optimization. a Performed on 0.1 mmol scale. b Isolated yield.
With proper conditions in hand, an exploration of the scope of
the reaction was initiated. The developed reaction conditions
allowed excellent functional group tolerance. For substituted
benzoyl chlorides, electron-rich, electron-neutral, and electron-
poor substrates all rendered reasonably good yields (Scheme 2,
entries 1-7). Interestingly, even though the terminal methyl
group on the alkene seemed rather sterically undemanding,
exceptional diastereoselectivities were observed in all of these
examples. Other types of electrophiles, such as acyl anhydrides
(8) and alkyl acyl halides (9-11), are also compatible, despite
leading to a lower diastereoselectivity in some cases. Perhaps
most importantly, in situ activation of carboxylic acids did not
lead to a compromise in either the yield or dr of the reactions
(12,13), and interesting substructures, such as substituted
cyclopropyl (14) and difluorobenzodioxolyl (15), were installed
with reasonable yields directly from the corresponding
carboxylic acids.
Various anilide- and alkenyl backbones were next examined,
and their influence in this reaction was tested both to expand
the scope and to shed light on the diastereoselectivity. For
aniline derivatives bearing different substituents (16-22),
although the yields varied, the diastereoselectivities, where
relevant, remained consistent. Substrates leading to primary
alkyl radicals were generally compatible in the reaction (21, 24-
30), and although both methyl and a bulky Boc-protected amino
group at the α-carbonyl position induced diastereoselectivity to
Results and discussion
To test this strategy, an investigation was initiated using N-
phenyl hex-4-enamide and benzoyl chloride as cross-coupling
partners (Scheme 1). Previous reports pointed to 1,2-
dichloroethane (DCE) as a potential solvent for photoredox
PCET/Ni dual catalysis,15 which indeed rendered a 46% yield in
the initial attempt (Scheme 1, entry 1). Although it is
noteworthy that the less expensive organic photocatalyst
4CzIPN gave a comparable yield (entry 3), neither this nor a
more oxidizing Ir photocatalyst ([Ir-2], entry 2) significantly
improved the yield. Several ligands successfully promoted the
reaction, with the electron-rich dMeObpy being most
appropriate (entries 1, 4, 5). A careful examination of the
reaction profile indicated
a
significant amount of
hydroamidation byproduct, likely caused by hydrogen atom
2 | J. Name., 2012, 00, 1-3
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ARTICLE
CF3
View Article Online
DOI: 10.1039/D0SC01459A
-
F
F
PF6
(dMeObpy)NiCl2 6 mol %
[Ir-1]
O
N
Ir
O
O
P
Bu4N+
Ar
Ar
O
N
N
R1
F
F
3 mol %
N
N
OBu
OBu
-O
+
Y
Y
R
X
R1
H
R
Bu4N[OP(O)(OBu)2] 2.5 equiv
MeCN (0.05 M), blue LED
O
N
Bu4N[OP(O)(OBu)2]
[Ir-1]
CF3
R1 = aryl, alkyl, X = Cl
From anhydride
O
O
O
O
Ph
2
Ph
Ph
Ph
N
O
R =CF3 69%
OMe 52%
Me 57%
Cl 60%
N
O
N
O
N
O
R
3
4
5

6
7
R = OMe 78%
Cl 58%
Ph
Me
Me
Me
Me
8
, 43%
dr = 13:1
1
, 75%
dr > 20:1
R
dr > 20:1
dr > 20:1
R1 = alkyl, X = Cl
X = OH [activated by (COCl)2]
O
O
O
O
O
Ph
O
O
Ph
Ph
Ph
Ph
N
NPh O
Me
N
O
N
O
N
O
N
O
F
O
12 R = 3-Cl 57%
F
R
13
4-Me 66%
Me
Ph
Me
Me
10
Me
O
Me
14 b
9
11
dr > 20:1
15
, 59%
dr > 20:1
, 49%
dr = 4:1
, 44%
, 52%
,
54%
dr = 13:1
dr > 14:1
dr > 20:1
Anilines
MeO
N
R2
Radical Probe Substrate
F
R2 = Cl
MeO
51%
16
O
O
Ph
NH
Ph
O
O
41%
59%
48%
28%
17
18
19
O
PhCOCl
N
OMe
N
t-Bu
N
Ph
Standard
Bz
Bz
OPh
Bz
Conditions
O
23
, 67%
dr > 20:1 20
CO2Et
21
, 58%
22
, 53%
Me
Me
dr > 20:1
Olefins
O
O
O
O
O
Ph
O
O
Ph
Ph
Ph
Ph
Ph
Ph
N
O
Me
Me
N
O
N
O
N
O
N
O
N
O
N
O
Me
Me
BocHN
Ph
Ph
Ph
Ph
Ph
O
Ph
Ph
Me
28
29
dr = 3:1
30
, 61%
dr = 5:1
, 70%
, 64%
24
25
26
27
, 41%
, 56%
NPh
, 64%
O
, 85%
O
dr = 1:1.25
O
O
O
O
O
NPh
NPh
O
O
O
NPh
O
NPh
NPh
Ph
Ph
Ph
Ph
Ph
Ph
CbzHN
S
i-Pr
Ph
O
BocN
31
dr > 20:1
32
dr > 20:1
33
dr > 20:1
34
, 88%
dr > 20:1
35
dr > 20:1
36,
55%
dr > 20:1
, 60%
, 49%
, 51%
, 49%
Carbamates
O
O
O
Ph
Ph
O
O
O
O
N
N
O
O
Ph
O
N
Ph
O
Ph
O
N
O
O
Ph
Ph
Ph
N
Ph
O
Ph
O
Si
O
Si
O
PhN
Ph
t-Bu
t-Bu
t-Bu
t-Bu
O
O
O
40c
, 42%
37,
dr > 20:1
38
dr > 20:1
39
, 61%
dr > 20:1
41
, 68%
dr > 20:1
42
, 60%
dr > 20:1
61%
, 57%
dr > 20:1
Scheme 2. Reaction Scope. a Reaction conditions: amide S1-S42 (0.36 mmol, 1.2 equiv), acyl (pseudo)halides (0.3 mmol, 1.0 equiv), Bu4N[OP(O)(OBu)2] (0.75 mmol, 2.5 equiv),
Ni(dMeObpy)Cl2 (0.018 mmol, 6 mol %), [Ir-1] (0.009 mmol, 3 mol %), blue LED, 6 mL MeCN. b A 1:1 mixture of two diastereoisomers originating from the acyl coupling
partner. c 0.006 mmol, 2 mol % of Ni precatalyst was used.
some extent (29, 30), substitution β to the carbonyl seemed to
have minimal influence (28). Therefore, it seems that
substitution δ to the carbonyl, where the alkyl radical is
generated after cyclization, is crucial for the high
diastereoselectivity observed. Not surprisingly, polycyclic
This journal is © The Royal Society of Chemistry 20xx
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structures retain their high diastereoselectivity in the reaction excellent yields. The applicability of the protocol for
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(37-39).
amidoacylation of alkenyl carbamates DwOaI:s10.a10ls3o9/De0xSaCm01in45e9dA,
(a) Actual electrophile:
O
O
O
O
O
Bz-[P]
[Ni], [Ir], blue LED
n-Pr-CO[P]
[Ni], [Ir], blue LED
1 equiv Bu4N[P]
N
Ph
Bz
NHPh
[P]
isolated & characterized
Cl
N
Ph
O
full conversion after 15 min
1.5 equiv Bu4N[P]
73%
1.5 equiv Bu4N[P]
30%
[P] = OP(O)(OBu)2
Pr
(b) Probing the origin of high diastereoselectivity
Determined by Isomerization of Final Product?
Probing with opposite isomer
O
O
via
O
O
O
Standard
Conditions
NHPh
N
Ph
Bz
ref 11b
dr > 20:1
N+ Ph
Ph
O-
N
Ph
Bz
or
N
Ph
Bz
NO
Isomerization
S1'
Bz
1'
Determined at Reductive Elimination?
Ph
O
Ph
H
X
Me
N
H
radical
assoc.-dissoc.
N
H
Bz
red. elim.
Bz
N
N
N
Ph
Bz
N
N
Me
O
Ni
H
O
Ni
X
Favored
dr is dictated by ligands
dr
R
NMe2 34 : 1
yield
56%
R
R
OMe
t-Bu
H
20 : 1
10 : 1
9 : 1
75%
67%
73%
50%
N
N
N
N
72%
dr 5 : 1
Br
5 : 1
Scheme 3. Experimental Mechanistic Insights
Several functional groups were incorporated to test which initially led to a diminished yield (20%) of 40, with 35% of
compatibility, including thioether (32), ether (33), and pendant N-phenyl benzamide byproduct. This byproduct likely results
from an SN2’-type oxidative addition by the Ni(0) catalyst to the
ene carbamate,40 with loss of CO2 and capture of the resulting
aniline with the acid chloride. Lowering the loading of Ni
precatalyst to 2% improved the yield of 40 to 42%. Interestingly,
under standard reaction conditions, such a side reaction was
not observed in monosaccharide-derived substrates (41, 42),
rendering C-acyl amidoglycosides diastereoselectively in good
yields.
Several experiments were performed to aid in deciphering the
mechanism of the reaction. First, control experiments
suggested that nickel, Ir photocatalyst, light, and base are all
essential for the transformation (See Supporting Information
for further details). Radical probe substrate 23 supported the
proposed reaction pathway and indicated that the reaction
indeed underwent a single electron transfer process. To rule out
the possibility of energy transfer mechanism as seen in related
systems,41 we performed a transient absorption spectroscopy
study of the PCET step (Figure 2). By comparing the well-studied
triethanolamine (TEOA) system (black trace, Figure 2), which is
known to reduce the excited state of the Ir photocatalyst,42,43
with substrate 1a in the presence of base [Bu4N[OP(O)(OBu)2]
(red trace, Figure 2), the resulting spectrum suggested an
evident generation of reduced [Ir-1] photocatalyst, supporting
the proposed electron transfer mechanism, generating an N-
centered radical. Then, considering the versatility of different
electrophilic species, the nature of the actual electrophile in the
reaction was sought. After stirring a 1:1 mixture of benzoyl
chloride and Bu4N[OP(O)(OBu)2] in CH2Cl2 for 20 min, the mixed
benzoic-phosphonic anhydride was isolated and subjected to
Figure 2. Transient absorption studies on PCET-mediated N-radical generation at 10
μs time delay.
olefin (34) groups, as well as protected primary- (35) and
secondary (36) amines, all showing excellent dr and good to
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the reaction conditions, rendering
ARTICLE
mechanism appear viable, because Bz–X is in much higher
a
73% yield and a
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comparable diastereoselectivity to that observed under the concentration than the photogeneratedDrOadI:i1c0a.1ls03A9/Da0nSdC0B1,4t5h9Ae
normal reaction conditions (Scheme 3a). Further computational major reaction pathway proposed is one in which oxidative
studies also provide support that compared to benzoyl chloride, addition of Bz–X to a catalytically active nickel complex that
the benzoic-phosphonic anhydride appears to be a more stable initiates the process. Regardless of the mechanistic pathway,
species (See Supporting Information for further details). the diastereo-determining step will be the addition of radical B
Interestingly, a diminished yield was observed when an alkyl to nickel complex D (vide infra). Thus, Ni(0) catalyst C first
acyl chloride was used under the same protocol.
undergoes oxidative addition to Bz–X, forming Ni(II) species D,
Figure 3. (a) Free energy difference between 1 and 1’. (b) Proposed reaction mechanism of the acylation between 1a and 1b. (c) DFT computed free energy diagram between 1a
and 1c of the thermochemical part (from C to F) of the catalytic cycle calculated at B3LYP-D3(BJ)/def2-TZVPP-SMD(MeCN)//B3LYP-D3(BJ)/def2-SVP.
The origin of the high diastereoselectivity of this reaction was which subsequently binds the radical B generated through a
next explored. To investigate the stability of both kinetically favorable 5-exo-trig cyclization.46 The formed Ni(III)
stereoisomers, a synthesis of the opposite diastereoisomer was species E then undergoes reductive elimination, releasing
carried out. Thus, by applying the hydroamination reaction product 1 and generating Ni(I) species F. Further SET between F
developed by Knowles et al.,23 the designed substrate S1’ led to and reduced photocatalyst [PC]∙− regenerates active Ni(0)
diastereoisomer 1’. This isomer was subsequently subjected to catalyst C.
the standard reaction conditions, and no isomerization to 1 was Based on the proposed reaction mechanism in Figure 3b, the
observed (Scheme 3b). Further investigation revealed a most favorable computed free energy pathway for the
dependence between the electron density on the ligands and thermochemical part (B to F) of the catalytic cycle calculated by
the dr values (Scheme 3b). When an analysis was performed density functional theory (DFT) is shown in Figure 3c. Although
relating log dr to σ+ parameters,44 a good linear correlation was both BzCl and Bz-[P] (1c) exhibited reasonable reactivity toward
found. The negative ρ value from this plot indicated that higher oxidative addition, the mixed anhydride Bz-[P] was applied as
electron density on the ligand, which stabilizes the putative the initial point because of its greater stability and ease of
Ni(III) intermediates in the catalytic cycle, will lead to a higher formation (see Supporting Information for further details). The
diastereoselectivity in this transformation. Taken together, active triplet Ni(0) catalyst int1 is oxidized by Bz–[P] (1c) via an
these results suggested that the high dr must originate from the
catalytic process and not epimerization after product
formation.45
To gain deeper insights on the diastereo-determining step, the
investigation was continued using computational tools. First,
the free energy calculation of 1 and 1’ indicated that 1’ is the
thermodynamically more favorable isomer (Figure 3a).
Therefore, the diastereoselective formation of 1 is a kinetically
controlled process. Although either
a Ni(0)-Ni(I)-Ni(III)
mechanism,46 where radical addition takes place before
oxidative addition of acyl halide, or a Ni(0)-Ni(II)-Ni(III)
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Figure 4. 3D renderings of diastereoselectivity-determining radical bound transition
states TS5 and TS9 calculated at B3LYP-D3(BJ)/def2-TZVPP-SMD(MeCN)//B3LYP-
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D3(BJ)/def2-SVP. Trivial H atoms are omitted for clarity.

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open-shell singlet (OSS) transition state TS2, which is quite and Prof. Marisa C. Kozlowski (University of Pennsylvania) for
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facile, with a free energy barrier of only 17.0 kcal/mol. This helpful discussions. We acknowledge JohDnOsoI:n1-0M.10a3t9t/hDe0ySCfo0r14f5in9Ae
generates closed-shell Ni(II) species int3. This step is strongly chemicals donations. Financial support from the NSFC
exothermic and thus irreversible as proposed. Ligand exchange (21702182 and 21873081 to X.H.), “Fundamental Research
between the Cl− anion and the [P]− anion then generates a more Funds for the Central Universities” (2019QNA3009 to X.H.) and
stable Ni(II) species int4. The subsequent radical binding step China Postdoctoral Science Foundation (2018M640546 to S.-
between int4 and int5 via TS6 is also very fast, with a free Q.Z.) is gratefully acknowledged. Calculations were performed
energy barrier of only 4.7 kcal/mol, generating doublet Ni(III) on the high-performance computing system at the Department
species int7. Further irreversible and highly exothermic of Chemistry, Zhejiang University.
reductive elimination via TS8 possesses a free energy barrier of
8.0 kcal/mol, generating product 1 and doublet Ni(I) species
int9.
Notes and references
Somewhat surprisingly, TS6 is calculated to be 3.6 kcal/mol
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catalyzed
diastereoselective
amidoacylation
of
unfunctionalized olefins. Various acyl electrophiles, including
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Conflicts of interest
There are no conflicts to declare.
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The authors are grateful for the financial support provided by
NIGMS (R35 GM 131680 to G.A.M.). We thank Dr. Charles W.
Ross, III (University of Pennsylvania) for obtaining HRMS data.
We gratefully acknowledge Dr. Mike Gau and Dr. Pat Carroll
(University of Pennsylvania) for acquiring X-ray crystal
structures. We thank Dr. Alvaro Gutierrez-Bonet (Merck & Co.)
6 | J. Name., 2012, 00, 1-3
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