Nickel-catalyzed direct C-H bond sulfenylation of acylhydrazines

Article abstract of DOI:10.1039/c8ob01481g

A Ni-catalyzed direct C-H bond sulfenylation of acylhydrazines was developed. The reaction used N-(pyridinyl)hydrazine as the bidentate-directing group, which can be smoothly removed through reductive N-N cleavage. This system can bear various important functional groups, providing an efficient route for the preparation of diverse diaryl sulfides.

Full text of DOI:10.1039/c8ob01481g

View Article Online
View Journal
Organic &
Biomol ec ular
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Li, Y. Yu, J.
Weng and G. Lu, Org. Biomol. Chem., 2018, DOI: 10.1039/C8OB01481G.
Volume 14 Number
1
7
January 2016 Pages 1–372
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Organic &
Biomolecular
Chemistry
www.rsc.org/obc
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
author guidelines.
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, outlined
in our author and reviewer resource centre, 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.
ISSN 1477-0520
COMMUNICATION
Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
rsc.li/obc

Page 1 of 9
Or gP al en ai sc e&d Bo i on mo to al ed cj uu ls at r mC ha re gmi ni ss try
View Article Online
DOI: 10.1039/C8OB01481G
Organic & Biomolecular Chemistry
PAPER
Nickel-catalyzed direct C-H bond sulfenylation of acylhydrazines
Jun-Ming Li,‡ Yang Yu,‡ Jiang Weng,* Gui Lu*
DEReceived 00th January 20xx,
Accepted 00th January 20xx
A Ni-catalyzed direct C-H bond sulfenylation of acylhydrazines was developed. The reaction used N-
(
pyridinyl)hydrazine as the bidentate-directing group, which can be smoothly removed through
reductive N N cleavage. This system can bear various important functional groups, providing an efficient
route for the preparation of diverse diaryl sulfides.
DOI: 10.1039/x0xx00000x
-
www.rsc.org/
metal catalysts restricted the application of the reaction. Then,
14
15
our group and Gui’s group developed direct sulfenylation of
2
C(sp )-H bond with copper catalyst and direct methylthiolation
Introduction
Organosulfur
pharmaceuticals, agrochemicals and functional materials.
These compounds are also useful synthetic intermediates in owing to its abundant availability, low cost and relatively low
compounds
are
widely
present
in with cobalt catalyst, respectively. More recently, Ni-catalyzed
1
16
C-H functionalization has attracted tremendous attentions
1
7a
17b
organic chemistry. Among the best-selling drugs in United toxicity. Shi and Lu’s groups have independently realized
States in 2012, organosulfur compounds account for Ni-catalyzed direct sulfenylation of unactived arene C-H bonds
2
approximately 20%. Thus, the formation of C−S bond is with 2-(pyridine-2-yl)isopropylamine (PIP) directing group
1
8
eliciting extensive attention from the industry and academic (Scheme 1a). Shi and other groups also reported Ni-catalyzed
2
direct thiolation of unactived C(sp )-H and C(sp )-H bonds with
3
communities.
The conventional methods for synthesis of aryl sulfides is disulfides directed by aminoquinoline group (Scheme 1b). In
the transition metal-catalyzed/mediated sulfenylation of
1
arylhalides or its equivalent with thiols and its derivatives.
c,3
Previous W ork
However, these traditional coupling reactions usually need
prefunctinalized substrates such as aryl halides, which might
[
Ni]
O
O
PhSSPh
N
H
N
(a)
(b)
3
,4
restricted the applications of these reactions. In view of
sustainable chemistry, the most atom-economic method is the
direct thiolation of arenes through C-H activation/C-S bond
H
N
N
H
O
SPh
[Ni]
O
RXXR
5
N
H
N
formation. In this regard, most C-H functionalization reactions
H
N
N
were well studied and focused on the C-C and C-heteroatom
6
bond forming reactions. Nevertheless, in order to realize
H
XR
R = aryl or alkyl X = S or Se
direct C-H thiolation, it is necessary to overcome the possible
7
sulfide poisoning of transition metal catalyst.
O
O
H
[Ni]
H
N
H
N
RXXR
N
(
c)
N
H
R1
R1
H
8
9
10
11
O
Recently, Yu, Qing, Cheng, and Daugulis have reported
elegant work on Cu-catalyzed direct sulfenylation of
unactivated arenes assisted by directing groups. However,
these routes are largely restricted to the use of stoichiometric
or substoichiometric Cu catalysts. Later, the direct C-S bond-
O
XR
X = S or Se
[Ni]
H
N
H
N
N
N
PhSSPh
(d)
N
N
H
SPh
1
2
13
forming reaction catalyzed by Rh or Pd has also been
developed, but the use of expensive second-row transition
T his W ork
O
[Ni]
O
Me
Me
N
RSSR
N
N
N
H
H
C-H Activation
N
N
SR
H
R = aryl or alkyl
Scheme 1 Direct C-H sulfenylation with different directing
groups
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 9
View Article Online
DOI: 10.1039/C8OB01481G
COMMUNICATION
Journal Name
a
2
016, Liu et al. described the Ni-catalyzed C−H thiolaꢀon of N-
1
Reaction conditions: 1a (0.2 mmol), 2a (0.24 mmol), [Ni] (10 mol%), base
b
(2.0 equiv.), ligand (20 mol%), DMSO (1 mL), 12 h; Yields are based on 1a,
9
benzoyl α-amino acid derivatives (Scheme 1c),
while
1
determined by H NMR analysis of the crude product; Isolated yields are
d
given in the parentheses; DMF (1 mL); DME (1 mL); 24 h.
c
Ackermann’s group used a monodentate pyrimidyl group to
e
f
2
20
assist the direct C(sp )-H thiolation (Scheme 1d).
Recently, we have reported the homo- and cross-coupling
reactions of N’-tosyl arylhydrazines and N’-acyl
arylhydrazines to construct important skeletons with
antiviral, antitumor, anti-malarial, or bactericidal biological
We first investigated the reaction between diphenyl disulfide
(
2a) and N'-methyl-N'-(pyridin-2-yl)benzohydrazide (1a), the
2
1
latter can be easily prepared from 2-(1-methylhydrazinyl)pyri-
dine and carboxylic acid compounds. Fortunately, we found
2
2
activities. In continuation of our interest in arylhydrazines
that the reaction of 1a with 2a (1.2 equiv.) in the presence of
o
(2.0 equiv.) in DMSO at 140 C
and C-H bond functionalization, and inspired by Zhai’s cobalt-
23
NiCl
2
(10 mol%) and Na
2
CO
3
2
catalyzed C(sp )–H bond alkenylation/annulation cascade
gave 67% yield of the desired product 3a after 12 h (Table 1,
with N-(pyridinyl)hydrazine as bidentate directing group, we
envisioned that this kind of directing group might also be used to
promote the nickel-catalyzed C-H sulfenylation. Moreover, the
N-(pyridinyl)hydrazine group can be easily removed via
reductive N-N cleavage, which is quite different from the
removal of other directing groups like 8-aminoquinoline and
PIP through C-N hydrolysis of amide. Herein, we wish to report
a Ni-catalyzed direct C-H bond sulfenylation of arylhydrazines.
entry 1). Through the extensive screening of Ni catalyst, we
2
found that Ni(OTf) was proven to be the most effective
catalyst, and the product yield increased to 77% (entries 2-5).
Importantly, no desired product was obtained in the absence
of Ni catalyst, suggesting that the latter played a significant
role in this reaction (entry 6). Then the effect of phosphine
ligand was investigated. The addition of BINAP was proven to
increase the isolated yield to 87% (entry 9). On the contrary,
the addition of PPh
3
or DPPP slightly decreased the yields
Results and discussion
(entries 7-9). Then we examined the effect of base, and results
a
Table 1 Optimization of reaction conditions
indicated that Na
2
CO
3
was optimal (entries 10-17). A solvent
o
Yield
Entry
[Ni]
Base
T ( C)
Ligand
b
(
%)
67
Me
O
Me
N
O
Me
N
SPh
O
Me
N
1
2
3
4
5
6
7
8
9
NiCl
2
Na
Na
Na
Na
Na
2
2
2
2
2
CO
CO
CO
CO
CO
3
3
3
3
3
140
140
140
140
140
140
140
140
140
140
140
140
140
140
140
140
140
140
140
110
120
130
-
Me
c
N
N
N
H
H
H
Ni(OTf)
2
-
77(70 )
69
N
N
N
SPh
SPh
Me
SPh
NiCl
2
(PPh
3
)
2
-
3a, 84%
3b, 78%
3c, 73%b, mono:di=1:10
.
O
Me
N
O
Me
N
O
Me
N
Ni(OAc)
2
4H
2
O
-
71
Me
Me
MeO
MeO
MeO
.
N
H
N
H
N
NiCl
2
6H
2
O
-
35
H
N
N
N
SPh
SPh
SPh
-
Na CO3
2
-
-
3d, 73%
3e, 65%
3f, 59%
SPh
O
Me
O
Me
O
Me
N
Ni(OTf)2
Na CO3
2
PPh3
DPPP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
76
N
N
N
N
N
H
H
H
Ni(OTf)
Ni(OTf)
Ni(OTf)
Ni(OTf)
Ni(OTf)
Ni(OTf)
Ni(OTf)
Ni(OTf)
2
2
2
2
2
2
2
2
Na
Na
2
CO
CO
3
3
71
N
N
N
SPh
SPh
3h, 81%
SPh
c
a
87(79 )
3g, 73% , mono:di=1:10
3i, 72%
2
t
SPh
O
Me
N
O
Me
N
O
Me
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
KO Bu
75
21
70
<10
32
56
<10
47
43
59
60
65
73
Me
Me
F
N
N
N
N
H
H
H
K
2
CO
3
N
N
N
Ph
SPh
SPh
SPh
NaTFA
DBU
a
a
3l, 63%b
3
j, 77% , mono:di=1:10
3k, 41% , mono:di=2.31:1
SPh
O
Me
SPh
O
Me
N
O
Me
N
N
N
Cs
2
CO
3
N
N
H
H
H
N
N
N
O2N
SPh
F3C
SPh
NaHCO
3
c
3
m, 59% , mono:di=1:3.4
3n, 65%, mono:di=1.56:1
3o, n.d.
Ni(OTf)2
Ni(OTf)2
Ag CO3
2
Me
LiOAc
O
Me
N
d
N
1
8
9
Ni(OTf)
Ni(OTf)
Ni(OTf)
Ni(OTf)
Ni(OTf)
2
2
2
2
2
Na
Na
Na
Na
Na
2
2
2
2
2
CO
CO
CO
CO
CO
3
3
3
3
3
H
SPh
3p, 23%
N
e
f
1
1
2
2
9
0
1
Reaction conditions:
BINAP (20 mol%), Na
1
2
(0.2 mmol), 2a (0.24 mmol), Ni(OTf) (10 mol%),
o
a
f
f
2 3
CO (0.4 mmol), DMSO (1 mL), 140 C, 12 h. 2a (0.4
o c o
b
mmol, 2.0 equiv.); 100 C, 24 h; 2a (0.4 mmol), 100 C, 24 h.
Scheme 2 Scope of benzamides
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 9
Or gP al en ai sc e&d Bo i on mo to al ed cj uu ls at r mC ha re gmi ni ss try
View Article Online
DOI: 10.1039/C8OB01481G
Journal Name
COMMUNICATION
screening revealed that DMSO was superior to other solvent as
DMF and DME (entries 18-19). We also tried to decrease the
temperature while sacrificing reaction time. However, the
starting material couldn’t be converted completely and gave
the desired product with lower yield even after 24 h (entries
19-21).
After identifying the optimal reaction conditions, we next
investigated the substrate scope.
A
wide range of
acylhydrazines were examined (Scheme 2). In general, the
acylhydrazine substrates can bear various substituents on the
phenyl ring and give the desired products in moderate to good
yields. A higher yield can be obtained with the electron-
donating substituent on the phenyl ring of acylhydrazine (3a
). When using the meta-substituted acylhydrazine, thiolation
occurred at less sterically hindered position and gave the
monothiolated product (3b 3d 3f and 3l). By contrast, the
-
3f
,
-
acylhydrazines bearing para-substituents or simple benzamide
derivative gave the mono-thiolated and di-thiolated products Reaction conditions: 1a (0.2 mmol),
mol%), BINAP (20 mol%), Na
2
(0.4 mmol, 2.0 equiv.), DMSO (1 mL), 140
(0.24 mmol, 1.2 equiv.), Ni(OTf) (10
2
2
CO
3
simultaneously (3c, 3g, 3j and 3m-n). Moreover, naphthyl
o
C, 12 h.
substrates 1h and 1i also worked efficiently with exclusive
monothiolated products. We assumed that this regioselectivity
might be related with the steric hindrance. Substrates 1l and
Scheme 3 Scope of disulfides
T
o gain mechanistic insight into this reaction, we carried out
1
m
with fluoro or nitro groups proceeded smoothly to provide
the corresponding thiolated products with moderate yields (3l
). We noticed that halogen and nitro groups might be easily
broken in DMSO under high temperature or in the presence of
the radical scavenger experiments. The addition of radical
scavengers, such as TMEPO and BHT, wasn’t found to inhibit
the thiolated reaction obviously. This result suggested that the
radical might not be involved in this reaction (Scheme 4). Furt-
hermore, the H/D exchange reaction suggested that the C-H
activation step is reversible (Scheme 5).
,
3m
2
4,25
transition metal,
so we performed the reactions of 1l and
o
under lower temperature (100 C). However, the reactions
1m
of bromo- and chloro-substituted substrates were poor even
under lower temperature, probably for the C-F bond was
3
stronger than the C-Br and C-Cl bonds. The unactived C(sp )-H
bond of tert- butylcarboxamide substrate 1k also reacted with
2a successfully and offered the mono- and di-thiolated
products, albeit with a lower yield. This sulfenylations of other
3
C(sp )-H are a bit complicated, for example, substrate 1o with
methylene C-H led to poor result and no desired product was
observed, while substrate 1p afforded unexpected α-thiolation
product 3p in 23% yield. In-depth experiments are still needed to
elucidate the possible mechanism.
Scheme 4 Radical scavenger
Next, we evaluated the substrate scope of various disulfides
(Scheme 3). To our delight, the diaryl disulfides with either an
electron-donating or electron-withdrawing substituents at the
ortho-, meta- or para-positions were found to be well
compatible under the standard reaction conditions (3q-3x). A
wide range of functional groups such as methoxy, methyl, and
halogen in the diaryl disulfides, are well tolerated. Scheme 5 H/D exchange reaction
Furthermore, the dialkyl disulfide also successful gave the
desired product 3y, albeit with a low yield of 23%. W
e
Interestingly, when substrate 1a was reacted with 4-
methylbenzenethiol under the standard reaction, the desired
attributed this to the lower nucleophilic abilities of dialkyl
disulfides than diaryl disulfides.
4
product 3q can also be obtained in 51% yield. The
phenomenon that the thiols can be oxidized to disulfides by
2
6
DMSO has been previously reported, which was consistent
with our control experiment shown in Scheme 6. We also
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 9
View Article Online
DOI: 10.1039/C8OB01481G
COMMUNICATION
Journal Name
detected dimethyl sulfide, a byproduct of DMSO (Figure S1 in
SI) to support the DMSO oxidant.
Based on the above mechanistic studies and previous
1
2-17
reports,
a plausible mechanism has been proposed in
II
Scheme 8. Coordination of amide 1a to a Ni followed by C-H
II
activative process generates the Ni complex
addition of disulfide 2a to followed by reductive elimination
process provided complex . Subsequent ligand exchange
B. Oxidative
1) Ni-catalyzed thiolation with 4
B
D
released the desired thiolation product 3a and benzenethiol
II
with the regeneration of Ni catalyst. As mentioned above,
benzenethiol can be oxidized to disulfide by DMSO and can
participate in the reaction again.
2) Oxidation of thiol 4 to disulfide
Conclusions
In conclusion, we have developed an efficient Ni-catalyzed
thiolation of acylhydrazines with disulfide. In this reaction, we
used inexpensive Ni catalyst and commercially available substrates.
The thiolated products can be hydrolyzed to afford amides which
have potential applications in natural products and medicinal
chemistry. This catalytic system can tolerate various important
functional groups, providing an efficient protocol for the thiolation
Scheme 6 Thiolation with 4 and the oxidation of thiol 4
2
We also conducted a derivatization experiment of the
thiolated product 3q (Scheme 7). The hydrazine structure can
be broken to provide the thiolated amide by using the proper
of unactived C(sp )-H bond.
Experimental section
2
7
reductant as samarium(II) iodide.
General information
All starting materials, which were purchased from commercial
sources, were used without further purification. Solvents for
column chromatography were technical standard. Chromatography
1
13
19
was performed with silica gel 200-400 mesh. H, C and F NMR
spectra were recorded on Burker Avance 400 MHz and 500 MHz
1
spectrometer. Chemical shifts in H NMR spectra are reported in
parts per million (ppm) downfield from the internal standard Me Si
4
1
3
(
TMS). Chemical shifts in C NMR spectra are reported relative to
the central line of the chloroform signal (δ = 77.0 ppm). Peaks were
labeled as singlet (s), doublet (d), triplet (t), quarter (t), and
multiplet (m). High resolution mass spectra were obtained with a
Shimadzu LCMS-IT-TOF mass spectrometer. Analytical TLC was
performed on commercial Merck plates coated with silica gel GF254
Scheme 7 Transformation of hydrazine to amide
(
0.2 mm thick). Acylhydrazines 1a-1p were synthesized according to
2
3
23
literatures. Compounds 1a-1c and 1h were known compounds.
N',3,4-triMethyl-N'-(pyridin-2-yl)benzohydrazide 1d
1
White solid; yield 83%. H NMR (400 MHz, CDCl ) δ: 8.68 (s, 1H),
3
8
7
2
1
1
.17 (d, J = 4.1 Hz, 1H), 7.63 (s, 1H), 7.57 (d, J = 7.8 Hz, 1H), 7.47-
.39 (m, 1H), 7.15 (d, J = 7.8 Hz, 1H), 6.77-6.59 (m, 2H), 3.38 (s, 3H),
.29 (s, 3H), 2.26 (s, 3H). C NMR (101 MHz, CDCl ) δ: 166.8, 159.4,
3
1
3
47.5, 141.4, 137.6, 137.1, 129.9 (d, J = 11.8 Hz), 128.6, 124.7,
14.5, 107.2, 38.7, 19.8 (d, J = 17.3 Hz). HRMS (ESI-TOF) calcd. for
+
C H N O [M+H] : 256.1444, found: 256.1446.
1
5 18 3
3
-Methoxy-N'-methyl-N'-(pyridin-2-yl)benzohydrazide 1e
1
White solid; yield 883%. H NMR (400 MHz, CDCl ) δ: 8.85 (s, 1H),
3
8
7
7
1
1
.18 (d, J = 4.6 Hz, 1H), 7.51-7.44 (m, 1H), 7.40 (d, J = 8.1 Hz, 2H),
.30 (dd, J = 16.2, 8.5 Hz, 1H), 7.10-6.99 (m, 1H), 6.71 (dd, J = 13.0,
1
3
.6 Hz, 2H), 3.81 (s, 3H), 3.39 (s, 3H). C NMR (101 MHz, CDCl
66.5, 159.9, 159.3, 147.6, 137.7, 133.9, 129.7, 119.1, 118.5, 114.7,
16 3 2
12.5, 107.2, 55.4, 38.8. HRMS (ESI-TOF) calcd. for C14H N O
3
) δ:
+
Scheme 8 Plausible reaction mechanism
[
M+H] : 258.1237, found: 258.1236.
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 9
Or gP al en ai sc e&d Bo i on mo to al ed cj uu ls at r mC ha re gmi ni ss try
View Article Online
DOI: 10.1039/C8OB01481G
Journal Name
COMMUNICATION
1
3,4-diMethoxy-N'-methyl-N'-(pyridin-2-yl)benzohydrazide 1f
White solid; yield 76%. H NMR (400 MHz, CDCl ) δ: 9.55 (s, 1H),
3
1
8.19 (d, J = 4.8 Hz, 1H), 7.94 (d, J = 8.1 Hz, 2H), 7.68-7.46 (m, 3H),
White solid; yield 81%. H NMR (400 MHz, CDCl
8
3
) δ: 8.65 (s, 1H),
13
6
1
.90-6.59 (m, 2H), 3.39 (s, 3H). C NMR (101 MHz, CDCl ) δ: 165.3,
3
.21 (d, J = 4.0 Hz, 1H), 7.58-7.48 (m, 1H), 7.48-7.36 (m, 2H), 6.87 (d,
J = 8.3 Hz, 1H), 6.80-6.68 (m, 2H), 3.93 (s, 3H), 3.90 (s, 3H), 3.43 (s,
H). C NMR (101 MHz, CDCl ) δ: 166.2, 159.4, 152.2, 149.0, 147.4,
58.9, 147.4, 138.1, 127.8, 125.7, 125.7, 125.6, 125.6, 115.1, 107.3,
19
13
39.2. F NMR (376 MHz, CDCl
for C14H N OF [M+H] : 296.1005, found: 296.1004.
3
) δ: -63.12 (s). HRMS (ESI-TOF) calcd.
3
+
3
12 3 3
1
(
37.8, 125.0, 120.1, 114.6, 110.7, 110.3, 107.2, 56.0, 39.0. HRMS
+
ESI-TOF) calcd. for C H N O [M+H] : 288.1343, found: 288.1339.
N'-Methyl-N'-(pyridin-2-yl)-2-(p-tolyl)acetohydrazide 1p
1
5 18 3 3
1
N'-Methyl-N'-(pyridin-2-yl)benzohydrazide 1g
White solid; yield 71%. H NMR (400 MHz, CDCl
3
) δ: 8.12 (d, J = 4.0
1
Hz, 1H), 7.44-7.38 (m, 1H), 7.21 (d, J = 8.0 Hz, 2H), 7.16 (d, J = 7.9
Hz, 2H), 7.08 (t, J = 6.8 Hz, 1H), 6.65 (dd, J = 6.8, 5.2 Hz, 1H), 6.52 (d,
J = 8.5 Hz, 1H), 3.58 (s, 2H), 3.26 (s, 3H), 2.34 (s, 3H). C NMR (101
White solid; yield 87%. H NMR (400 MHz, CDCl ) δ: 8.54 (d, J = 36.1
3
Hz, 1H), 8.20 (d, J = 4.0 Hz, 1H), 7.86 (d, J = 7.5 Hz, 2H), 7.68-7.39
m, 4H), 6.92-6.56 (m, 2H), 3.44 (s, 3H). C NMR (101 MHz, CDCl3)
δ: 166.7, 159.3, 147.6, 137.7, 132.6, 132.1, 128.7, 127.3, 114.6,
07.2, 38.8. HRMS (ESI-TOF) calcd. for C H N O [M+H] : 228.1131,
13
1
3
(
MHz, CDCl
3
) δ: 170.1, 159.1, 150.1, 147.7, 137.6, 129.9, 129.3,
+
129.2, 114.6, 106.9, 41.8, 38.6, 21.1. HRMS (ESI-TOF) calcd. for
1
+
1
3 14 3
15 18 3
C H N O [M+H] : 256.1436, found: 256.1444.
found: 228.1129.
General procedure for the thiolation
N'-Methyl-N'-(pyridin-2-yl)-2-naphthohydrazide 1i
1
An oven-dried pressure tube was charged with benzamide 1 (0.2
White solid; yield 89%. H NMR (400 MHz, CDCl
3
) δ: 9.01 (s, 1H),
mmol), disulfide 2 (0.24 mmol), Ni(OTf)
Na CO (42 mg, 0.4 mmol), BINAP (24.88 mg, 0.04 mmol), and
DMSO (2 mL). The tube was then sealed and stirred vigorously at
2
(7.14 mg, 0.02 mmol),
8
7
3
1
1
.36 (s, 1H), 8.21 (dd, J = 4.9, 0.9 Hz, 1H), 7.91-7.77 (m, 4H), 7.60-
.45 (m, 3H), 6.78 (d, J = 8.5 Hz, 1H), 6.71 (dd, J = 6.6, 5.4 Hz, 1H),
.45 (s, 3H). C NMR (101 MHz, CDCl
37.7, 135.0, 132.5, 129.7, 129.0, 128.6, 128.0, 127.9, 127.7, 126.8,
23.6, 114.8, 107.2, 39.0. HRMS (ESI-TOF) calcd. for C17H N O
16 3
2
3
13
3
) δ: 166.7, 159.3, 147.6,
o
1
40 C for 12 h. After cooling to room temperature, the reaction
mixture was diluted with water, extracted with CH Cl (3×10 mL).
2
2
+
The combined phase was then washed with brine and dried over
anhydrous sodium sulfate. After concentration, the resulting residue
[
M+H] : 278.1288, found: 278.1287.
N'-Methyl-N'-(pyridin-2-yl)biphenyl-4-carbohydrazide 1j
2 2
was purified by preparative TLC using CH Cl /EtOAc as the eluent to
afford product 3.
1
White solid; yield 82%. H NMR (400 MHz, CDCl
3
) δ: 9.11 (s, 1H),
8
.20 (d, J = 3.8 Hz, 1H), 7.92 (d, J = 8.2 Hz, 2H), 7.59 (dd, J = 7.5, 5.7 N',2-diMethyl-6-(phenylthio)-N'-(pyridin-2-yl)benzohydrazide 3a
Hz, 4H), 7.47 (dt, J = 12.7, 4.6 Hz, 3H), 7.39 (t, J = 7.2 Hz, 1H), 6.81-
1
1
3
H NMR (400 MHz, CDCl
3
) δ: 8.21 (dd, J = 4.9, 1.0 Hz, 1H), 7.75 (s,
H), 7.52 (ddd, J = 8.8, 7.2, 1.9 Hz, 1H), 7.29-7.26 (m, 2H), 7.23 (t, J =
.7 Hz, 1H), 7.15 (d, J = 8.1 Hz, 3H), 7.08 (dd, J = 13.1, 8.2 Hz, 2H),
6
.64 (m, 2H), 3.41 (s, 3H). C NMR (101 MHz, CDCl
3
) δ: 166.4,
1
7
159.4, 147.6, 144.9, 139.9, 137.7, 131.1, 129.0, 128.1, 127.9, 127.2
(
C
d, J = 7.4 Hz), 114.7, 107.2, 38.9. HRMS (ESI-TOF) calcd. for
+
6.73 (dd, J = 6.8, 5.3 Hz, 1H), 3.50 (s, 3H), 2.50 (s, 3H), 2.35 (s, 3H).
19
H
18
N
3
O [M+H] : 304.1420, found: 304.1422.
13
C NMR (101 MHz, CDCl
Hz), 137.0, 136.6, 133.8, 131.5 (d, J = 9.9 Hz), 130.2 (d, J = 14.5 Hz),
29.8, 129.3, 114.8, 107.7, 77.4, 77.0, 76.7, 38.3, 21.1, 19.5. HRMS
3
) δ: 167.6, 159.3, 147.6, 137.6 (d, J = 8.2
N'-Methyl-N'-(pyridin-2-yl)pivalohydrazide 1k
1
1
White solid; yield 85%. H NMR (400 MHz, CDCl
4
3
) δ: 8.15 (dd, J =
+
(
20 3
ESI-TOF) calcd. for C20H N OS [M+H] : 350.1322, found: 350.1317.
.9, 1.0 Hz, 1H), 7.98 (s, 1H), 7.43 (ddd, J = 8.9, 7.3, 1.9 Hz, 1H), 6.65
(
dd, J = 6.8, 5.3 Hz, 1H), 6.59 (d, J = 8.5 Hz, 1H), 3.27 (s, 3H), 1.24 (s, N',5-diMethyl-2-(phenylthio)-N'-(pyridin-2-yl)benzohydrazide 3b
13
9
1
2
H). C NMR (101 MHz, CDCl
06.8, 38.5, 38.2, 27.3. HRMS (ESI-TOF) calcd. for C11
08.1131, found: 208.1129.
3
) δ: 177.3, 159.5, 147.6, 137.5, 114.3,
1
+
H NMR (400 MHz, CDCl
.67 (s, 1H), 7.45-7.38 (m, 1H), 7.34-7.22 (m, 7H), 6.75 (d, J = 8.5 Hz,
H), 6.68 (dd, J = 6.6, 5.4 Hz, 1H), 3.33 (s, 3H), 2.40 (s, 3H). C NMR
3
) δ: 8.65 (s, 1H), 8.18 (d, J = 4.1 Hz, 1H),
18 3
H N O [M+H] :
7
1
13
3-Fluoro-N'-methyl-N'-(pyridin-2-yl)benzohydrazide 1l
(101 MHz, CDCl
3
) δ: 166.8, 159.3, 147.6, 138.8, 137.6, 136.0 (d, J =
1
3
3.5 Hz), 134.7, 132.5, 130.8, 129.5, 128.6, 127.0, 114.6, 107.4,
8.2, 21.0. HRMS (ESI-TOF) calcd. for C20H N OS [M+H] : 350.1322,
20 3
1
White solid; yield 83%. H NMR (400 MHz, CDCl
3
) δ: 9.82 (d, J = 26.6
+
Hz, 1H), 8.05-7.92 (m, 1H), 7.49-7.24 (m, 3H), 7.15-6.97 (m, 2H),
.53 (ddd, J = 20.0, 10.4, 5.6 Hz, 2H), 3.14 (d, J = 7.2 Hz, 3H).
found: 350.1317.
1
3
6
C
NMR (101 MHz, CDCl
3
) δ: 165.7 (d, J = 2.0 Hz), 163.8, 161.3, 159.1, N',4-diMethyl-2-(phenylthio)-N'-(pyridin-2-yl)benzohydrazide 3c
1
47.3, 137.8, 134.5 (d, J = 6.9 Hz), 130.2 (d, J = 7.8 Hz), 122.9 (d, J =
1
1
9
3
H NMR (400 MHz, CDCl ) δ: 8.64 (s, 1H), 8.16-8.03 (m, 1H), 7.69 (d,
2.7 Hz), 119.1, 118.9, 114.9, 114.6, 107.2, 38.5 (d, J = 5.4 Hz).
F
J = 7.7 Hz, 1H), 7.39-7.31 (m, 1H), 7.26-7.16 (m, 5H), 7.11 (d, J = 9.1
Hz, 2H), 6.65 (d, J = 8.5 Hz, 1H), 6.61 (dd, J = 6.6, 5.4 Hz, 1H), 3.26 (s,
3
NMR (376 MHz, CDCl
calcd. for C13 O [M+H] : 246.1037, found: 246.1037.
3
) δ: -111.51 (d, J = 2.3 Hz). HRMS (ESI-TOF)
+
H
13FN
3
13
3
H), 2.24 (s, 3H). C NMR (101 MHz, CDCl ) δ: 166.7, 159.2, 147.5,
N'-Methyl-4-nitro-N'-(pyridin-2-yl)benzohydrazide 1m
142.2, 137.6, 135.2, 134.3, 132.7 (d, J = 16.2 Hz), 130.2 (d, J = 6.8
Hz), 129.5, 128.8, 127.3, 114.6, 107.4, 38.3, 21.3. HRMS (ESI-TOF)
1
White solid; yield 71%. H NMR (400 MHz, DMSO-d
1
6
) δ: 11.10 (s,
+
calcd. for C20
H N
20 3
OS [M+H] : 350.1322, found: 350.1317.
H), 8.45-8.28 (m, 2H), 8.18 (dd, J = 6.9, 1.9 Hz, 3H), 7.55 (ddd, J =
8
(
.8, 7.2, 1.9 Hz, 1H), 6.80 (d, J = 8.5 Hz, 1H), 6.76-6.67 (m, 1H), 3.36 N',4-diMethyl-2,6-bis(phenylthio)-N'-(pyridin-2-yl) benzohydrazide
1
3
s, 3H). C NMR (101 MHz, DMSO-d
6
) δ: 164.6, 159.8, 149.9, 147.9, 3c’
38.8, 138.0, 129.5, 124.1, 114.5, 107.3, 38.1. HRMS (ESI-TOF)
1
1
+
H NMR (400 MHz, CDCl
3
) δ: 8.07 (d, J = 4.2 Hz, 1H), 7.77-7.51 (m,
13 4 3
calcd. for C13H N O [M+H] : 278.0982, found: 278.0981.
1
H), 7.38-7.16 (m, 11H), 7.09 (d, J = 8.5 Hz, 1H), 6.92 (s, 2H), 6.63-
13
N'-Methyl-N'-(pyridin-2-yl)-4-(trifluoromethyl)benzohydrazide 1n
6.52 (m, 1H), 3.37 (s, 3H), 2.09 (s, 3H). C NMR (101 MHz, CDCl
3
) δ:
1
66.3, 159.4, 147.3, 141.3, 137.6, 136.3, 135.0, 134.6, 132.5, 131.1,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 6 of 9
View Article Online
DOI: 10.1039/C8OB01481G
COMMUNICATION
Journal Name
1
C
29.5, 127.6, 114.7, 108.3, 37.8, 21.2. HRMS (ESI-TOF) calcd. for N'-Methyl-3-(phenylthio)-N'-(pyridin-2-yl)-2-naphthohydrazide 3i
+
26
H
24
N
3
OS
2
[M+H] : 458.1355, found: 458.1364.
1
3
H NMR (400 MHz, CDCl ) δ: 8.81 (s, 1H), 8.40 (s, 1H), 8.19 (d, J = 4.1
N',4,5-triMethyl-2-(phenylthio)-N'-(pyridin-2-yl)benzohydrazide 3d Hz, 1H), 7.96-7.86 (m, 2H), 7.80-7.71 (m, 1H), 7.61-7.52 (m, 2H),
1
7.43 (dd, J = 11.3, 4.3 Hz, 1H), 7.37-7.25 (m, 5H), 6.79-6.65 (m, 2H),
H NMR (400 MHz, CDCl
3
) δ: 8.83 (s, 1H), 8.16 (d, J = 4.4 Hz, 1H),
.72 (s, 1H), 7.42-7.34 (m, 1H), 7.34-7.25 (m, 3H), 7.21 (d, J = 6.6 Hz,
H), 6.66 (dd, J = 10.3, 4.8 Hz, 2H), 3.28 (s, 3H), 2.32 (s, 3H), 2.26 (s,
13
3
1
.32 (s, 3H). C NMR (101 MHz, CDCl ) δ: 166.6, 159.3, 147.6,
37.7, 135.4, 134.5, 133.9, 132.7, 132.0, 131.1, 129.8, 129.7, 128.6,
3
7
2
3
1
1
13
128.4, 127.5, 127.4, 114.7, 107.4, 38.2. HRMS (ESI-TOF) calcd. for
H). C NMR (101 MHz, CDCl ) δ: 166.5, 159.3, 147.6, 141.2, 138.0,
+
3
23 20 3
C H N OS [M+H] : 386.1322, found: 386.1321.
37.5, 136.6, 136.3, 133.8, 132.0, 129.5, 128.6, 127.6, 126.7, 114.5,
07.3, 77.3, 77.0, 76.7, 38.1, 19.6, 19.3. HRMS (ESI-TOF) calcd. for N'-Methyl-3-(phenylthio)-N'-(pyridin-2-yl)biphenyl-4-
+
C
21
H
22
N
3
OS [M+H] : 364.1478, found: 364.1478.
carbohydrazide 3j
1
5-Methoxy-N'-methyl-2-(phenylthio)-N'-(pyridin-2-yl)
H NMR (400 MHz, CDCl ) δ: 8.63 (s, 1H), 8.13 (d, J = 4.2 Hz, 1H),
3
benzohydrazide 3e
7.86 (d, J = 7.9 Hz, 1H), 7.56-7.47 (m, 2H), 7.45-7.24 (m, 10H), 7.19
1
3
1
(s, 1H), 6.70 (d, J = 8.5 Hz, 1H), 6.67-6.59 (m, 1H), 3.30 (s, 3H).
NMR (101 MHz, CDCl ) δ: 165.5, 158.2, 146.6, 143.5, 138.1, 136.6,
33.6, 133.0, 132.6, 130.9, 129.6 (d, J = 5.2 Hz), 128.7, 128.0, 127.3,
126.7, 126.1, 125.4, 113.7, 106.4, 37.4. HRMS (ESI-TOF) calcd. for
C
H NMR (500 MHz, CDCl ) δ: 8.11 (s, 1H), 7.71 (d, J = 4.0 Hz, 1H),
3
3
7
7
6
.58 (d, J = 8.2 Hz, 1H), 7.52 (d, J = 2.3 Hz, 1H), 7.32-7.28 (m, 2H),
.24 (s, 2H), 7.18 (d, J = 5.8 Hz, 2H), 7.04 (dd, J = 18.7, 8.2 Hz, 2H),
1
1
3
.63 (d, J = 0.5 Hz, 1H), 3.82 (s, 3H), 3.38 (s, 3H). C NMR (101 MHz,
) δ: 165.8, 160.9, 159.4, 147.3, 139.0, 137.4, 130.9, 129.4,
28.9 (d, J = 18.6 Hz), 128.5, 127.3, 126.6, 126.0, 123.0, 114.7, N'-Methyl-3,5-bis(phenylthio)-N'-(pyridin-2-yl)biphenyl-4-
+
25 22 3
C H N OS [M+H] : 412.1478, found: 412.1484.
CDCl
3
1
1
13.6, 108.3, 56.4, 37.6. HRMS (ESI-TOF) calcd. for C20
H
20
N
3
OS carbohydrazide 3j’
+
[M+H] : 366.1322, found: 366.1317.
1
3
H NMR (400 MHz, CDCl ) δ: 8.17 (dd, J = 4.9, 1.0 Hz, 1H), 7.71 (s,
4
,5-diMethoxy-N'-methyl-2-(phenylthio)-N'-(pyridin-2-yl)
1H), 7.46-7.42 (m, 4H), 7.38-7.26 (m, 13H), 7.25-7.20 (m, 2H), 6.67
13
benzohydrazide 3f
(dd, J = 6.7, 5.4 Hz, 1H), 3.50 (s, 3H). C NMR (101 MHz, CDCl
166.0, 159.4, 147.4, 143.8, 138.8, 137.6, 137.0, 135.7, 134.6, 131.4,
30.0, 129.6, 129.0, 128.4, 127.9, 127.0, 114.8, 108.3, 37.9. HRMS
3
) δ:
1
3
H NMR (400 MHz, CDCl ) δ: 9.39 (s, 1H), 8.23-8.10 (m, 1H), 7.65 (s,
1
1
7
3
1
1
H), 7.37-7.26 (m, 3H), 7.20 (t, J = 7.4 Hz, 1H), 7.18-7.10 (m, 2H),
.04 (s, 1H), 6.65 (dd, J = 6.8, 5.3 Hz, 1H), 6.58 (d, J = 8.5 Hz, 1H),
.97 (s, 3H), 3.87 (s, 3H), 3.26 (s, 3H). C NMR (101 MHz, CDCl ) δ:
3
65.8, 159.4, 151.4, 149.9, 147.6, 137.5, 136.7, 129.6 (d, J = 8.3 Hz), N',2,2-triMethyl-3-(phenylthio)-N'-(pyridin-2-yl)propanehydrazide
27.3, 126.6, 121.1, 119.0, 114.5, 114.2, 107.2, 56.3, 38.0. HRMS 3k
+
(
ESI-TOF) calcd. for
C
31
H
26
N OS
3 2
[M+H] : 520.1512, found:
1
3
520.1514.
+
(ESI-TOF) calcd. for
C
21
H
22
N
3
O
3
S
[M+H] : 396.1376, found:
1
H NMR (400 MHz, CDCl
.40-7.29 (m, 3H), 7.19 (t, J = 7.5 Hz, 2H), 7.11 (d, J = 7.3 Hz, 1H),
6.67 (d, J = 8.5 Hz, 1H), 6.59 (dd, J = 6.7, 5.2 Hz, 1H), 3.21 (s, 3H),
3
) δ: 8.09 (d, J = 3.9 Hz, 1H), 7.98 (s, 1H),
396.1382.
7
N'-Methyl-2-(phenylthio)-N'-(pyridin-2-yl)benzohydrazide 3g
1
3
1
3.16 (s, 2H), 1.30 (s, 6H). C NMR (101 MHz, CDCl
3
) δ: 174.8, 159.3,
H NMR (400 MHz, CDCl
3
) δ: 8.56 (s, 1H), 8.18 (d, J = 3.8 Hz, 1H),
1
47.6, 137.5, 136.8, 129.7, 129.0, 126.4, 114.5, 107.2, 45.1, 43.4,
7.78 (d, J = 6.7 Hz, 1H), 7.44 (t, J = 7.5 Hz, 1H), 7.30 (dd, J = 26.5, 6.3
+
1
3
38.5, 29.7, 25.0. HRMS (ESI-TOF) calcd. for C17
14.1333, found: 314.1328.
22 3
H N OS [M+H] :
Hz, 8H), 6.79 (d, J = 8.4 Hz, 1H), 6.72-6.61 (m, 1H), 3.36 (s, 3H).
NMR (101 MHz, CDCl
C
3
3
) δ: 166.9, 159.2, 147.5, 137.7, 134.9, 134.6,
1
34.2, 132.8, 131.5, 131.2, 129.6, 127.7, 127.5, 114.7, 107.4, 38.4. N',2-diMethyl-3-(phenylthio)-2-((phenylthio)methyl)-N'-(pyridin-2-
+
HRMS (ESI-TOF) calcd. for C19
36.1165.
H
18
N
3
OS [M+H] : 336.1165, found: yl)propanehydrazide 3k’
3
1
3
H NMR (400 MHz, CDCl ) δ: 8.21-8.15 (m, 1H), 8.10 (s, 1H), 7.44
N'-Methyl-2,6-bis(phenylthio)-N'-(pyridin-2-yl)benzohydrazide 3g’
(ddd, J = 8.8, 7.2, 1.9 Hz, 1H), 7.39 (dt, J = 3.0, 1.9 Hz, 4H), 7.27 (dt, J
= 6.1, 1.6 Hz, 5H), 7.22-7.17 (m, 2H), 6.88 (d, J = 8.5 Hz, 1H), 6.72-
1
3
H NMR (400 MHz, CDCl ) δ: 8.18 (dd, J = 4.8, 0.9 Hz, 1H), 7.58 (s,
6
.65 (m, 1H), 3.45 (d, J = 12.8 Hz, 2H), 3.30 (d, J = 2.3 Hz, 3H), 3.26
1
7
H), 7.43 (ddd, J = 14.8, 8.3, 1.3 Hz, 5H), 7.38-7.30 (m, 5H), 7.24-
.19 (m, 2H), 7.18-7.05 (m, 2H), 6.69 (dd, J = 6.6, 5.4 Hz, 1H), 3.50
13
(
s, 2H), 1.48 (s, 3H). C NMR (126 MHz, CDCl
146.5, 136.6, 135.2, 128.9, 128.1, 125.6, 113.6, 106.6, 47.4, 42.4,
3
) δ: 171.9, 158.2,
1
3
(
1
7
s, 3H). C NMR (101 MHz, CDCl
3
) δ: 166.1, 159.4, 147.4, 137.9,
37.5, 135.5, 134.5, 131.7, 131.0, 130.7, 129.6, 127.9, 114.8, 108.3,
7.4, 77.1, 76.7, 37.9. HRMS (ESI-TOF) calcd. for C25 OS
2
+
3
4
7.5, 20.1. HRMS (ESI-TOF) calcd. for
24.1512, found: 424.1517.
C
23
H
26
N
3
OS
2
[M+H] :
H
22
N
3
+
[M+H] : 444.1499, found: 444.1496.
5-Fluoro-N'-methyl-2-(phenylthio)-N'-(pyridin-2-yl)
benzohydrazide 3l
N'-Methyl-2-(phenylthio)-N'-(pyridin-2-yl)-1-naphthohydrazide 3h
1
1
H NMR (400 MHz, CDCl
.67 (d, J = 7.5 Hz, 1H), 7.54 (dd, J = 7.5, 5.0 Hz, 1H), 7.46 (t, J = 7.8
Hz, 1H), 7.32-7.17 (m, 6H), 6.80 (d, J = 8.4 Hz, 1H), 6.76-6.65 (m,
3
) δ: 8.47 (s, 1H), 8.20 (d, J = 3.4 Hz, 1H),
H NMR (400 MHz, CDCl
8.3 Hz, 1H), 7.97 (s, 1H), 7.80 (dd, J = 15.1, 8.3 Hz, 2H), 7.63-7.56
3
) δ: 8.20 (dd, J = 4.8, 0.9 Hz, 1H), 8.12 (d, J
7
=
(m, 1H), 7.55-7.46 (m, 2H), 7.36 (dd, J = 9.4, 2.3 Hz, 2H), 7.33-7.22
13
1
3
H), 3.38 (s, 3H). C NMR (126 MHz, CDCl ) δ: 165.9 (d, J = 2.9 Hz),
(m, 4H), 7.03 (d, J = 8.5 Hz, 1H), 6.72 (dd, J = 6.8, 5.2 Hz, 1H), 3.53 (s,
13
164.2, 162.2, 159.0, 147.7, 141.0, 137.7, 135.4, 131.6 (d, J = 8.7 Hz),
3
1
1
3
H). C NMR (101 MHz, CDCl ) δ: 167.2, 159.2, 147.6, 137.7, 135.5,
1
3
29.4, 128.0, 126.7, 125.4 (d, J = 3.6 Hz), 118.7, 118.6, 114.9, 107.4,
34.9, 132.4, 131.1, 130.8, 130.7, 130.6, 129.4, 129.4, 128.2, 127.9,
19
8.4. F NMR (376 MHz, CDCl
3
) δ: -102.43 (s). HRMS (ESI-TOF)
27.4, 127.0, 125.1, 114.9, 107.6, 38.5. HRMS (ESI-TOF) calcd. for
+
+
calcd. for C19
H17FN
3
OS [M+H] : 354.1098, found: 354.1069.
C
23
H
20
N
3
OS [M+H] : 386.1322, found: 386.1324.
N'-Methyl-4-nitro-2-(phenylthio)-N'-(pyridin-2-yl) benzohydrazide
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 9
Or gP al en ai sc e&d Bo i on mo to al ed cj uu ls at r mC ha re gmi ni ss try
View Article Online
DOI: 10.1039/C8OB01481G
Journal Name
COMMUNICATION
1
3
3
m
6.74-6.65 (m, 1H), 3.78 (s, 3H), 3.49 (s, 3H), 2.43 (s, 3H). C NMR
(101 MHz, CDCl ) δ: 167.8, 159.9, 159.4, 147.5, 137.6, 136.6, 135.7,
35.2, 134.9, 130.0, 128.5, 127.9, 124.3, 115.2, 114.8, 107.8, 55.4,
1
3
3
H NMR (500 MHz, CDCl ) δ: 8.46 (s, 1H), 8.22 (s, 1H), 8.05 (d, J = 7.0
1
Hz, 1H), 7.91-7.75 (m, 2H), 7.49 (dd, J = 52.5, 27.5 Hz, 6H), 6.99-6.67
-
1
3
38.3, 19.4. HRMS (ESI-TOF) calcd. for C21
found: 378.1276.
20 3 2
H N O S [M-H] : 378.1282,
(m, 2H), 3.47 (s, 3H). C NMR (126 MHz, CDCl
3
) δ: 165.6, 158.8,
1
7
49.4, 147.7, 140.5, 138.1, 137.9, 134.0, 131.0, 130.3, 129.7 (d, J =
.8 Hz), 124.1, 120.6, 115.4, 107.5, 39.1. HRMS (ESI-TOF) calcd. for 2-((4-Fluorophenyl)thio)-N',6-dimethyl-N'-(pyridin-2-yl)
+
C H N O S [M+H] : 381.1016, found: 381.1014.
benzohydrazide 3s
1
9 17 4 3
1
N'-Methyl-4-nitro-2,6-bis(phenylthio)-N'-(pyridin-2-yl)
3
H NMR (400 MHz, CDCl ) δ: 8.20-8.09 (m, 1H), 7.96 (s, 1H), 7.48
benzohydrazide 3m’
(ddd, J = 8.9, 7.2, 1.9 Hz, 1H), 7.35 (dd, J = 8.8, 5.2 Hz, 2H), 7.22-7.17
(m, 1H), 7.11 (d, J = 7.2 Hz, 1H), 7.04 (d, J = 7.8 Hz, 1H), 7.02-6.93
(m, 3H), 6.72-6.61 (m, 1H), 3.45 (s, 3H), 2.44 (s, 3H). C NMR (101
1
H NMR (500 MHz, CDCl
3
) δ: 8.15 (s, 1H), 7.94 (t, J = 53.5 Hz, 1H),
13
1
3
7.56-7.36 (m, 10H), 7.37-7.11 (m, 4H), 6.69 (s, 1H), 3.51 (s, 3H). C
MHz, CDCl
3
) δ: 167.5, 163.7, 161.2, 159.3, 147.5, 137.6, 137.0,
NMR (101 MHz, CDCl
3
) δ: 164.5, 159.1, 149.0, 147.5, 140.2, 138.8,
1
36.8, 133.7, 133.6, 133.5, 130.7, 130.3, 130.2, 129.8, 129.6, 116.7,
137.7, 133.9, 133.0, 131.1, 130.2, 129.9, 129.7, 121.6, 115.3, 108.1,
19
+
116.4, 114.9, 107.7, 77.4, 77.1, 76.7, 38.3, 19.4. F NMR (376 MHz,
CDCl ) δ: -113.72 (s). HRMS (ESI-TOF) calcd. for C H FN OS [M-H] :
38.4. HRMS (ESI-TOF) calcd. for C25
H
21
N
4
O
3
S
2
[M+H] : 489.1050,
-
3
20 17
3
found: 489.1056.
3
66.1082, found: 366.1074.
N'-Methyl-2-(phenylthio)-N'-(pyridin-2-yl)-4-(trifluoromethyl)
benzohydrazide 3n
2
-((4-Chlorophenyl)thio)-N',6-dimethyl-N'-(pyridin-2-yl)
benzohydrazide 3t
1
H NMR (400 MHz, CDCl
3
) δ: 8.53 (s, 1H), 8.20 (dd, J = 4.9, 0.9 Hz,
1
H NMR (400 MHz, CDCl
3
) δ: 8.16 (dd, J = 4.9, 1.0 Hz, 1H), 7.82 (s,
1
H), 7.84 (d, J = 8.0 Hz, 1H), 7.51 (dd, J = 12.2, 5.2 Hz, 2H), 7.46-7.31
1
3
1H), 7.49 (ddd, J = 8.7, 7.3, 1.9 Hz, 1H), 7.29-7.21 (m, 5H), 7.21-7.15
m, 2H), 6.98 (d, J = 8.5 Hz, 1H), 6.71 (dd, J = 6.8, 5.3 Hz, 1H), 3.44 (s,
(m, 6H), 6.90-6.61 (m, 2H), 3.42 (s, 3H). C NMR (101 MHz, CDCl
3
)
(
3
δ: 166.0, 158.9, 147.7, 137.9, 137.5, 132.7, 132.3, 130.0, 129.7,
13
3
H), 2.48 (s, 3H). C NMR (101 MHz, CDCl ) δ: 167.4, 159.2, 147.6,
1
28.9, 127.6, 127.6, 127.6, 123.5, 123.4, 123.4, 123.3, 115.2, 107.4,
1
9
137.7 (d, J = 17.3 Hz), 137.2, 134.6, 133.2, 131.9, 131.5, 131.2, 130.3
(d, J = 5.5 Hz), 129.5, 115.0, 107.7, 38.4, 19.5. HRMS (ESI-TOF) calcd.
for C20
38.8. F NMR (376 MHz, CDCl
3
) δ: -63.26 (s). HRMS (ESI-TOF) calcd.
S [M+H] : 404.1039, found: 404.1037.
+
for C20
H N
16 3
OF
3
-
H17ClN
3
OS [M-H] : 382.0786, found: 382.0780.
N'-Methyl-2,6-bis(phenylthio)-N'-(pyridin-2-yl)-4-(trifluoromethyl)
benzohydrazide 3n’
2
-((4-Bromophenyl)thio)-N',6-dimethyl-N'-(pyridin-2-yl)
benzohydrazide 3u
1
H NMR (400 MHz, CDCl
3
) δ: 8.21 (d, J = 4.8 Hz, 1H), 7.54-7.47 (m,
1
3
H NMR (400 MHz, CDCl ) δ: 8.16 (d, J = 4.1 Hz, 1H), 7.90 (s, 1H),
5
2
CDCl
H), 7.45-7.37 (m, 6H), 7.28 (s, 1H), 7.24 (d, J = 8.5 Hz, 1H), 7.18 (s,
1
3
7.54-7.44 (m, 1H), 7.38 (d, J = 8.5 Hz, 2H), 7.26 (d, J = 7.5 Hz, 1H),
7
1
159.2, 147.5, 138.0, 137.6, 137.3, 135.5, 132.4, 131.5 (d, J = 13.3
Hz), 130.4 (d, J = 6.0 Hz), 121.0, 115.0, 107.7, 77.4, 77.0, 76.7, 38.4,
H), 6.74 (dd, J = 6.7, 5.4 Hz, 1H), 3.56 (s, 3H). C NMR (101 MHz,
) δ: 165.1, 159.1, 147.4, 138.3, 137.8, 132.9, 132.3, 130.0,
29.0, 125.2, 115.1, 108.2, 38.2. HRMS (ESI-TOF) calcd. for
.21-7.11 (m, 4H), 6.97 (d, J = 8.5 Hz, 1H), 6.71 (dd, J = 6.8, 5.2 Hz,
3
13
3
H), 3.43 (s, 3H), 2.48 (s, 3H). C NMR (101 MHz, CDCl ) δ: 167.4,
1
+
26 20 3 3 2
C H N OF S [M+H] : 512.1073, found: 512.1072.
+
N'-Methyl-2-(phenylthio)-N'-(pyridin-2-yl)-2-(p-tolyl)acetohydrazi-
de 3p
19.5. HRMS (ESI-TOF) calcd. for C20
found: 450.0232.
H
18BrN
3
OSNa [M+Na] : 450.0246,
1
H NMR (400 MHz, CDCl
3
) δ: 8.59 (s, 1H), 8.12 (d, J = 5.7 Hz, 1H), N',2-diMethyl-N'-(pyridin-2-yl)-6-(o-tolylthio)benzohydrazide 3v
7
7
.47 (d, J = 7.0 Hz, 2H), 7.42 (d, J = 8.0 Hz, 2H), 7.37-7.27 (m, 4H),
.20 (d, J = 7.9 Hz, 2H), 6.64 (dd, J = 6.8, 5.2 Hz, 1H), 6.20 (d, J = 8.5
1
H NMR (400 MHz, CDCl
7.48-7.39 (m, 1H), 7.25-7.11 (m, 6H), 6.95 (dd, J = 14.6, 8.1 Hz, 2H),
.68 (dd, J = 6.7, 5.2 Hz, 1H), 3.42 (s, 3H), 2.47 (s, 3H), 2.38 (s, 3H).
3
) δ: 8.15 (d, J = 4.0 Hz, 1H), 7.83 (s, 1H),
13
Hz, 1H), 5.08 (s, 1H), 3.18 (s, 3H), 2.36 (s, 3H). C NMR (101 MHz,
CDCl ) δ: 168.1, 159.0, 147.5, 138.5, 137.5, 134.1, 132.2, 130.5,
29.8, 129.4, 128.1, 127.6, 114.7, 107.0, 55.6, 38.2, 21.2. HRMS
6
3
13
C NMR (101 MHz, CDCl
137.1, 136.6, 134.2, 132.7, 131.4, 130.7, 130.2, 129.3 (d, J = 2.3 Hz),
27.7, 127.0, 114.8, 107.7, 38.1, 20.5, 19.5. HRMS (ESI-TOF) calcd.
3
) δ: 167.6, 159.3, 147.5, 138.9, 137.6,
1
-
21 3
(ESI-TOF) calcd. for C21H N OS [M-H] : 364.1478, found: 364.1473.
1
-
N',2-diMethyl-N'-(pyridin-2-yl)-6-(p-tolylthio)benzohydrazide 3q
20 3
for C21H N OS [M-H] : 362.1333, found: 362.1326.
1
H NMR (400 MHz, CDCl
3
) δ: 8.21 (dd, J = 4.9, 1.0 Hz, 1H), 7.75 (s, N',2-diMethyl-N'-(pyridin-2-yl)-6-(m-tolylthio)benzohydrazide 3w
1
7
6
H), 7.52 (ddd, J = 8.8, 7.2, 1.9 Hz, 1H), 7.29-7.26 (m, 2H), 7.23 (t, J =
.7 Hz, 1H), 7.15 (d, J = 8.1 Hz, 3H), 7.08 (dd, J = 13.1, 8.2 Hz, 2H),
.73 (dd, J = 6.8, 5.3 Hz, 1H), 3.50 (s, 3H), 2.50 (s, 3H), 2.35 (s, 3H).
1
H NMR (400 MHz, CDCl
H), 7.47 (ddd, J = 8.8, 7.3, 1.8 Hz, 1H), 7.23 (dd, J = 13.8, 6.2 Hz,
3
) δ: 8.16 (dd, J = 4.9, 0.9 Hz, 1H), 7.76 (s,
1
1
3
1H), 7.19-7.11 (m, 4H), 7.09 (d, J = 7.7 Hz, 1H), 7.02 (dd, J = 14.7, 7.9
Hz, 2H), 6.69 (dd, J = 6.6, 5.2 Hz, 1H), 3.44 (s, 3H), 2.47 (s, 3H), 2.29
C NMR (101 MHz, CDCl
Hz), 137.0, 136.6, 133.8, 131.5 (d, J = 9.9 Hz), 130.2 (d, J = 14.5 Hz),
29.8, 129.3, 114.8, 107.7, 77.4, 77.0, 76.7, 38.3, 21.1, 19.5. HRMS
3
) δ: 167.6, 159.3, 147.6, 137.6 (d, J = 8.2
13
(
3
s, 3H). C NMR (101 MHz, CDCl ) δ: 167.6, 159.3, 147.5, 139.3,
1
-
137.6, 137.1 (d, J = 15.4 Hz), 135.4, 132.8, 131.1, 130.7, 130.2,
29.7, 129.3, 128.1, 127.6, 114.8, 107.7, 38.2, 21.3, 19.5. HRMS
(ESI-TOF) calcd. for C21
H
20
N
3
OS [M-H] : 362.1301, found: 362.1396.
1
-
2-((4-Methoxyphenyl)thio)-N',6-dimethyl-N'-(pyridin-2-yl)
(ESI-TOF) calcd. for C21
20 3
H N OS [M-H] : 362.1333, found: 362.1328.
benzohydrazide 3r
2
-((2-Fluorophenyl)thio)-N',6-dimethyl-N'-(pyridin-2-yl)
1
H NMR (400 MHz, CDCl
3
) δ: 8.16 (d, J = 4.1 Hz, 1H), 8.01 (s, 1H), benzohydrazide 3x
7
.49 (t, J = 7.2 Hz, 1H), 7.38 (d, J = 8.6 Hz, 2H), 7.13 (t, J = 7.7 Hz,
1
H NMR (400 MHz, CDCl
H), 7.47 (ddd, J = 8.8, 7.2, 1.9 Hz, 1H), 7.27-7.18 (m, 3H), 7.13 (dd, J
3
) δ: 8.15 (dd, J = 4.9, 1.0 Hz, 1H), 7.93 (s,
1H), 7.05 (dd, J = 11.0, 8.3 Hz, 2H), 6.88 (dd, J = 15.2, 8.3 Hz, 3H),
1
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 8 of 9
View Article Online
DOI: 10.1039/C8OB01481G
COMMUNICATION
Journal Name
1
=
3
1
1
16.2, 7.5 Hz, 2H), 7.09-6.99 (m, 3H), 6.72-6.64 (m, 1H), 3.44 (s, to afford product 2b, which was confirmed by H NMR spectrum.
1
3
H), 2.46 (s, 3H). C NMR (101 MHz, CDCl
59.3, 147.5, 137.6, 137.5, 137.2, 133.0, 131.2, 130.6, 130.2, 130.1,
29.5, 129.5, 125.0, 125.0, 123.0, 122.8, 116.1, 115.9, 114.8, 107.7, To a solution of 3q (72 mg, 0.2 mmol) in THF/MeOH (20 mL, 4:1
3
) δ: 167.5, 162.1, 159.7,
Hydrolysis of hydrazine to amide
1
9
3
8.1, 19.4. F NMR (376 MHz, CDCl ) δ: -109.21 (s). HRMS (ESI-TOF) V/V) under N was added SmI (5 mL, 0.1 M in THF) dropwise. Upon
3
2 2
+
calcd. for C20
H
19FN
3
OS [M+H] : 368.1227, found: 368.1222.
addition, the blue color of the SmI solution was decolorized. After
2
complete addition, the reaction was allowed to stir for 30 min. The
reaction was then concentrated on a Rotovap, and the resulting
N',2-diMethyl-6-(propylthio)-N'-(pyridin-2-yl)benzohydrazide 3y
1
3 2 2
H NMR (500 MHz, CDCl ) δ: 8.12 (s, 1H), 7.65 (s, 1H), 7.45 (t, J = 7.4 residue was purified by preparative TLC using CH Cl /EtOAc as the
1
Hz, 1H), 7.20 (t, J = 9.8 Hz, 2H), 7.05 (dd, J = 18.4, 7.3 Hz, 2H), 6.65 eluent to afford product 5. White solid, yield 63%. H NMR (400
(
3
s, 1H), 3.44 (s, 3H), 2.83 (d, J = 6.2 Hz, 2H), 2.36 (s, 3H), 1.68-1.52 MHz, CDCl ) δ: 7.24 (s, 1H), 7.13 (dt, J = 17.8, 8.4 Hz, 4H), 7.05 (d, J =
13
13
(m, 2H), 0.93 (dd, J = 6.5, 5.3 Hz, 3H). C NMR (126 MHz, CDCl ) δ: 7.7 Hz, 1H), 5.95 (s, 1H), 5.67 (s, 1H), 2.40 (s, 3H), 2.32 (s, 3H).
C
3
3
167.0, 158.4, 146.5, 136.5, 136.2, 135.6, 132.8, 128.7, 127.8 (d, J = NMR (126 MHz, CDCl ) δ: 169.5, 137.2, 136.6, 134.6, 131.9, 130.7,
1
5.6 Hz), 113.8, 106.8, 37.1, 36.6, 21.6, 18.4, 12.4. HRMS (ESI-TOF) 130.5, 129.1, 128.5, 128.3, 128.0, 20.1, 18.4.
+
22 3
calcd. for C17H N OS [M+H] : 316.1478, found: 316.1475.
Conflicts of interest
General procedures for the radical trapping
An oven-dried pressure tube was charged with benzamide 1a (48.2
There are no conflicts of interest to declare.
mg, 0.2 mmol), disulfide 2a (52.32 mg, 0.24 mmol), Ni(OTf)
2
(7.14
mg, 0.02 mmol), Na CO (42 mg, 0.4 mmol), BINAP (24.88 mg, 0.04
2
3
mmol), TEMPO (93.6 mg, 0.6 mmol) and DMSO (1.0 mL). The tube Acknowledgements
o
was then sealed and stirred vigorously at 140 C for 12 h. After
cooling to room temperature, the reaction mixture was diluted with
water, extracted with CH Cl (3×10 mL). The combined phase was
2 2
then washed with brine and dried over anhydrous sodium sulfate.
After concentration, the resulting residue was purified by
This work was financially supported by the National Science and
Technology Major Project of the Ministry of Science and Technology
of China (2018ZX09735010), Guangdong Provincial Key Laboratory
preparative TLC using CH
a (43.9 mg, 63%).
2
Cl
2
/EtOAc as the eluent to afford product of Construction Foundation (No. 2017B030314030) and Science and
3
Technology Program of Guangzhou (No. 201607010118).
An oven-dried pressure tube was charged with benzamide 1a
(
48.2 mg, 0.2 mmol), disulfide 2a (52.32 mg, 0.24 mmol), Ni(OTf)
2
(
0
7.14 mg, 0.02 mmol), Na CO (42 mg, 0.4 mmol), BINAP (24.88 mg, Notes and references
2
3
.04 mmol), BHT (132.0 mg, 0.6 mmol) and DMSO (1.0 mL). The
o
tube was then sealed and stirred vigorously at 140 C for 12 h. After
cooling to room temperature, the reaction mixture was diluted with
water, extracted with CH Cl (3×10 mL). The combined phase was
then washed with brine and dried over anhydrous sodium sulfate.
After concentration, the resulting residue was purified by
1
(a) S. V. Ley and A. W. Thomas, Angew. Chem., Int. Ed. 2003,
, 5400; (b) G. Liu, J. R. Huth, E. T. Olejniczak, R. Mendoza,
4
2
2
2
P. DeVries, S. Leitza, E. B. Reilly, G. F. Okasinski, S. W. Fesik
and T. W. von Geldern, J. Am. Chem. Soc. 2001, 44, 1202; (c)
T. Kondo and T.-a. Mitsudo, Chem. Rev. 2000, 100, 3205; (d)
A. Gangjee, Y. Zeng, T. Talreja, J. J. McGuire, R. L. Kisliuk and
S. F. Queener, J. Am. Chem. Soc. 2007, 50, 3046; (e) M.-L.
Alcaraz, S. Atkinson, P. Cornwall, A. C. Foster, D. M. Gill, L. A.
Humphries, P. S. Keegan, R. Kemp, E. Merifield, R. A. Nixon,
A. J. Noble, D. O'Beirne, Z. M. Patel, J. Perkins, P. Rowan, P.
Sadler, J. T. Singleton, J. Tornos, A. J. Watts and I. A.
2 2
preparative TLC using CH Cl /EtOAc as the eluent to afford product
3a (49.6 mg, 71%).
Ni-catalyzed thiolation with 4
To a Schlenk tube was added benzamide 1a (48.2 mg, 0.2 mmol), 4-
methylbenzenethiol 4 (52.32 mg, 0.24 mmol), Ni(OTf) (7.14 mg,
.01 mmol), Na CO3 (42 mg, 0.4 mmol), BINAP (24.88 mg, 0.04
mmol) and DMSO (1.0 mL). The mixture was stirred at 140 °C for 12
h. The mixture was then cooled to room temperature, diluted with
2
Woodland, Org. Process Res. Dev. 2005, 9, 555.
E. A. Ilardi, E. Vitaku and J. T. Njardarson, J. Am. Chem. Soc.
2014, 57, 2832.
0
2
3
2
(a) M. Murata and S. L. Buchwald, Tetrahedron 2004, 60
,
7
2
397; (b) F. Gendre, M. Yang and P. Diaz, Org. Lett. 2005, 7,
719; (c) C. Uyeda, Y. Tan, G. C. Fu and J. C. Peters, J. Am.
2 2
water, extracted with CH Cl (3×10 mL). The combined phase was
then washed with brine and dried over anhydrous sodium sulfate.
After concentration, the resulting residue was purified by
preparative TLC using CH Cl /EtOAc as the eluent to afford product
Chem. Soc. 2013, 135, 9548; (d) M. A. Fernández-Rodríguez,
Q. Shen and J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 2180;
2
2
(
7
e) P. Zhao, H. Yin, H. Gao and C. Xi, J. Am. Chem. Soc. 2013,
, 5001.
3q (37.0 mg, 51%).
8
4
5
C. C. Eichman and J. P. Stambuli, Molecules 2011, 16, 590.
C. Shen, P. Zhang, Q. Sun, S. Bai, T. S. A. Hor and X. Liu, Chem.
Soc. Rev. 2015, 44, 291.
Oxidation of thiol 4 to form disulfide
To a Schlenk tube was added 4-methylbenzenethiol 4 (0.2 mmol),
Ni(OTf) (7.14 mg, 0.02 mmol), Na CO (42 mg, 0.4 mmol), BINAP
6
For selected reviews, see: (a) T. G. Saint-Denis, R. Y. Zhu, G.
Chen, Q. F. Wu and J. Q. Yu, Science, 2018, 359, 759; (b) E. V.
Verbitskiy, G. L. Rusinov, O. N. Chupakhin and V. N.
Charushin, Synthesis, 2018, 50, 193; (c) J. G. Kim, K. Shin and
S. Chang, in C-H Bond Activation and Catalytic
Functionalization I, ed. By P. H. Dixneuf and H. Doucet,
Springer International Publishing, 2015, pp. 29-51; (d) C.-L.
Sun, B.-J. Li and Z.-J. Shi, Chem. Rev. 2011, 111, 1293; (e) Z.
2
2
3
(
24.88 mg, 0.04 mmol) and DMSO (1.0 mL). The mixture was stirred
at 140 °C for 8 h. Then the mixture was cooled to room
temperature, diluted with water, extracted with CH Cl (3×10 mL).
2
2
The combined phase was then washed with brine and dried over
anhydrous sodium sulfate. After concentration, the resulting residue
was purified by preparative TLC using petroleum ether as the eluent
8
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 9
Or gP al en ai sc e&d Bo i on mo to al ed cj uu ls at r mC ha re gmi ni ss try
View Article Online
DOI: 10.1039/C8OB01481G
Journal Name
COMMUNICATION
Dong, Z. Ren, S. J. Thompson, Y. Xu and G. Dong, Chem. Rev.
Delcros, Y. Arlot-Bonnemains and M. Baudy-Floc'h, J. Am.
Chem. Soc. 2005, 48, 330; (c) L.-W. Zheng, L.-L. Wu, B.-X.
Zhao, W.-L. Dong and J.-Y. Miao, Bioorg. Med. Chem. 2009,
17, 1957; (d) S. Lian, H. Su, B.-X. Zhao, W.-Y. Liu, L.-W. Zheng
and J.-Y. Miao, Bioorg. Med. Chem. 2009, 17, 7085; (e) C. D.
Duarte, J. L. M. Tributino, D. I. Lacerda, M. V. Martins, M. S.
Alexandre-Moreira, F. Dutra, E. J. H. Bechara, F. S. De-Paula,
M. O. F. Goulart, J. Ferreira, J. B. Calixto, M. P. Nunes, A. L.
Bertho, A. L. P. Miranda, E. J. Barreiro and C. A. M. Fraga,
Bioorg. Med. Chem. 2007, 15, 2421.
2
2
017, 117, 9333; (f) W. Liu and L. Ackermann, ACS Catal.
016, , 3743; (g) C. Borie, L. Ackermann and M. Nechab,
6
Chem. Soc. Rev. 2016, 45, 1368; (h) R. Shang, L. Ilies and E.
Nakamura, Chem. Rev. 2017, 117, 9086.
(a) C. Li, T. Yano, N. Ishida and M. Murakami, Angew. Chem.,
Int. Ed. 2013, 52, 9801; (b) X. Mi, M. Huang, J. Zhang, C.
Wang and Y. Wu, Org. Lett. 2013, 15, 6266; (c) C.-G. Feng, M.
7
8
Ye, K.-J. Xiao, S. Li and J.-Q. Yu, J. Am. Chem. Soc. 2013, 135
322; (d) K. Baba, M. Tobisu and N. Chatani, Angew. Chem.,
Int. Ed. 2013, 52, 11892.
,
9
23 S. Zhai, S. Qiu, X. Chen, J. Wu, H. Zhao, C. Tao, Y. Li, B. Cheng,
H. Wang and H. Zhai, Chem. Commun. 2018, 54, 98.
24 (a) M. R. Yadav, M. Nagaoka, M. Kashihara, R.-L. Zhong, T.
Miyazaki, S. Sakaki and Y. Nakao, J. Am. Chem. Soc. 2017, 139
9423; (b) F. Inoue, M. Kashihara, M. R. Yadav and Y. Nakao,
X. Chen, X.-S. Hao, C. E. Goodhue and J.-Q. Yu, J. Am. Chem.
Soc. 2006, 128, 6790.
L. Chu, X. Yue and F.-L. Qing, Org. Lett. 2010, 12, 1644.
0 S. Zhang, P. Qian, M. Zhang, M. Hu and J. Cheng, J. Org.
Chem. 2010, 75, 6732.
9
1
,
Angew. Chem., Int. Ed. 2017, 56, 13307; (c) B. P. Fors and S. L.
Buchwald, J. Am. Chem. Soc. 2009, 131, 12898; (d) X. Zheng, J.
Ding, J. Chen, W. Gao, M. Liu and H. Wu, Org. Lett. 2011, 13,
1
1
1 L. D. Tran, I. Popov and O. Daugulis, J. Am. Chem. Soc. 2012,
134, 18237.
2 (a)Y. Yang, W. Hou, L. Qin, J. Du, H. Feng, B. Zhou and Y. Li,
Chem. Eur. J. 2014, 20, 416; (b) S. Yang, B. Feng and Y. Yang,
J. Org. Chem. 2017, 82, 12430.
1726; (e) J. Zhang, J. Chen, M. Liu, X. Zheng, J. Ding and H.
Wu, Green Chem. 2012, 14, 912; (f) S. S. Bahekar, A. P.
Sarkate, V. M. Wadhai, P. S. Wakte and D. B. Shinde, Catal.
Commun. 2013, 41, 123.
1
3 (a) M. Iwasaki, M. Iyanaga, Y. Tsuchiya, Y. Nishimura, W. Li, Z.
Li and Y. Nishihara, Chem. Eur. J. 2014, 20, 2459; (b) M. 25 (a) A. S. Guram, R. A. Rennels and S. L. Buchwald, Angew.
Iwasaki, W. Kaneshika, Y. Tsuchiya, K. Nakajima and Y.
Nishihara, J. Am. Chem. Soc. 2014, 79, 11330; (c) M. Iwasaki,
Chem., Int. Ed. 1995, 34, 1348; (b) J. Louie and J. F. Hartwig,
Tetrahedron Lett. 1995, 36, 3609; (c) J. H. Tidwell, A. J. Peat
and S. L. Buchwald, J. Am. Chem. Soc. 1994, 59, 7164; (d) T.
Ishiyama, M. Murata and N. Miyaura, J. Am. Chem. Soc. 1995,
60, 7508; (e) K. Masanori, K. Masayuki and M. Toshihiko,
Chem. Lett. 1983, 12, 927.
Y. Tsuchiya, K. Nakajima and Y. Nishihara, Org. Lett. 2014, 16
,
4
8
920; (d) P. Saravanan and P. Anbarasan, Org. Lett. 2014, 16,
48; (e) X. Zhao, E. Dimitrijević and V. M. Dong, J. Am. Chem.
Soc. 2009, 131, 3466; (f) X. Zhao and V. M. Dong, Angew.
Chem., Int. Ed. 2011, 50, 932.
4 Y.-S. Xiong, Y. Yu, J. Weng and G. Lu, Org. Chem. Front. 2018,
26 (a) C. N. Yiannios and J. V. Karabinos, J. Am. Chem. Soc. 1963,
28, 3246; (b) T. J. Wallace, J. Am. Chem. Soc. 1964, 86, 2018;
1
1
1
5
, 982.
5 L. Hu, X. Chen, L. Yu, Y. Yu, Z. Tan, G. Zhu and Q. Gui, Org.
Chem. Front. 2018, , 216.
(c) W. E. Fristad and J. R. Peterson, Synth. Commun. 1985, 15
1.
,
5
27 (a) M. Mentel, M. J. Beier and R. Breinbauer, Synthesis, 2009,
1463; (b) M. J. Burk and J. E. Feaster, J. Am. Chem. Soc. 1992,
114, 6266; (c) M. J. Burk, J. P. Martinez, J. E. Feaster and N.
Cosford, Tetrahedron, 1994, 50, 4399; (d) C. F. Sturino and A.
G. Fallis, J. Am. Chem. Soc. 1994, 116, 7447; (e) L. E.
Overman, B. N. Rogers, J. E. Tellew and W. C. Trenkle, J. Am.
Chem. Soc. 1997, 119, 7159; (f) S. Kobayashi and R.
Hirabayashi, J. Am. Chem. Soc. 1999, 121, 6942; (g) D. Enders
6 (a) H. Shiota, Y. Ano, Y. Aihara, Y. Fukumoto and N. Chatani, J.
Am. Chem. Soc. 2011, 133, 14952; (b) Y. Aihara and N.
Chatani, J. Am. Chem. Soc. 2014, 136, 898; (c) M. Li, J. Dong,
X. Huang, K. Li, Q. Wu, F. Song and J. You, Chem. Commun.
2
014, 50, 3944; (d) W. Song, S. Lackner and L. Ackermann,
Angew. Chem., Int. Ed. 2014, 53, 247; (e) X. Wu, Y. Zhao and
H. Ge, J. Am. Chem. Soc. 2014, 136, 1789; (f) X. Wu, Y. Zhao
and H. Ge, Chem. Eur. J. 2014, 20, 9530; (g) X. Cong, Y. Li, Y.
Wei and X. Zeng, Org. Lett. 2014, 16, 3926; (h) M. Iyanaga, Y.
Aihara and N. Chatani, J. Am. Chem. Soc. 2014, 79, 11933; (i)
A. Yokota, Y. Aihara and N. Chatani, J. Am. Chem. Soc. 2014,
and K. Funabiki, Org. Lett. 2001,
Friestad, Org. Lett. 2004, , 637.
3, 1575; (h) H. Ding and G. K.
6
79, 11922; (j) Y. Aihara, M. Tobisu, Y. Fukumoto and N.
Chatani, J. Am. Chem. Soc. 2014, 136, 15509.
1
1
7 (a) S.-Y. Yan, Y.-J. Liu, B. Liu, Y.-H. Liu and B.-F. Shi, Chem.
Commun. 2015, 51, 4069; (b) K. Yang, Y. Wang, X. Chen, A. A.
Kadi, H.-K. Fun, H. Sun, Y. Zhang and H. Lu, Chem. Commun.
2
015, 51, 3582.
8 (a) S.-Y. Yan, Y.-J. Liu, B. Liu, Y.-H. Liu, Z.-Z. Zhang and B.-F.
Shi, Chem. Commun. 2015, 51, 7341; (b) X. Ye, J. L. Petersen
and X. Shi, Chem. Commun. 2015, 51, 7863; (c) X. Wang, R.
Qiu, C. Yan, V. P. Reddy, L. Zhu, X. Xu and S.-F. Yin, Org. Lett.
2015, 17, 1970; (d) V. P. Reddy, R. Qiu, T. Iwasaki and N.
Kambe, Org. Biomol. Chem. 2015, 13, 6803.
1
9 F. Gao, W. Zhu, D. Zhang, S. Li, J. Wang and H. Liu, J. Org.
Chem. 2016, 81, 9122.
2
2
0 T. Muller and L. Ackermann, Chem. Eur. J. 2016, 22, 14151.
1 (a) J.-B. Liu, L. Nie, H. Yan, L.-H. Jiang, J. Weng and G. Lu, Org.
Biomol. Chem. 2013, 11, 8014; (b) J.-B. Liu, H. Yan, H.-X. Chen,
Y. Luo, J. Weng and G. Lu, Chem. Commun. 2013, 49, 5268; (c)
J.-Q. Zhang, G.-B. Huang, J. Weng, G. Lu and A. S. C. Chan,
Org. Biomol. Chem. 2015, 13, 2055; (d) J.-Q. Zhang, Y.-S.
Xiong, A. S. C. Chan and G. Lu, RSC Adv. 2016, 6, 84587.
2 (a) M. Mishra, K. Tiwari, P. Mourya, M. M. Singh and V. P.
Singh, Polyhedron 2015, 89, 29; (b) S. Aubin, B. Martin, J.-G.
2
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins