Ligand-Free, Quinoline N-Assisted Copper-Catalyzed Nitrene Transfer Reaction to Synthesize 8-Quinolylsulfimides

Article abstract of DOI:10.1021/acs.joc.9b00281

An efficient copper-catalyzed, quinolyl N-directed nitrene transfer reaction to 8-quinolylsulfides was described. A variety of 8-quinolylsulfimides with different functional groups were synthesized in moderate to high yields. The obtained 8-quinolylsulfimides were proved to be promising novel type of bidentate ligands in Pd(II)-catalyzed allylic alkylation.

Full text of DOI:10.1021/acs.joc.9b00281

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Article
Ligand-free, Quinoline N-assisted Copper-catalyzed Nitrene
Transfer Reaction to Synthesize 8-quinolylsulfimides
Xinsheng Xiao, Sanping Huang, Shanshan Tang, Guokai Jia, Guangchuan Ou, and Yangyan Li
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00281 • Publication Date (Web): 24 May 2019
Downloaded from http://pubs.acs.org on May 25, 2019
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Page 1 of 19
The Journal of Organic Chemistry
Ligand-free, Quinoline N-assisted Copper-catalyzed Nitrene Transfer
1
2
Reaction to Synthesize 8-quinolylsulfimides
3
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Xinsheng Xiao,* Sanping Huang, Shanshan Tang, Guokai Jia, Guangchuan Ou, and Yangyan Li*
7
8
9
Key Laboratory of Comprehensive Utilization of Advantage Plants Resources in Hunan South, College of Chemistry and
Bioengineering, Hunan University of Science and Engineering, Yongzhou 425199, China
R1
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O
N3
u
mo
N 10 l
C C
%
R1
(
)
N
S
R3
O
N
D
E 100 o
C C
,
S
O
N
R2
S
R3
S
.
e
rs exam es o u no su
th fi l l lfi id
R2
O
-
o u no ne
- rec e
li N di t d
8 Thi
i
q
.
an - ree
li
g
d f
.
m
es
t
l
p
f
i
Q
y
ABSTRACT: An efficient copper-catalyzed, quinolyl N-directed nitrene transfer reaction to 8-quinolylsulfides was described. A variety
of 8-quinolylsulfimides with different functional groups were synthesized in moderate to high yields. The obtained 8-quinolylsulfimides
were proved to be a promising novel type of bidentate ligands in Pd(II)-catalyzed allylic alkylation.
INTRODUCTION
Sulfilimines1 (or sulfimides), which are the mono-nitrogen equivalent of sulfoxides2, have been widely used as reagents in organic syn-
thesis or chiral auxiliaries in asymmetric catalysis. For example, the chiral S-N bond of a sulfimide can serve as a chiral auxiliary in the
preparation of optically active epoxides3 through methylene transfer reactions. [2,3]-sigmatropic rearrangement of chiral allylic sulfimide
provided an efficient route to enantioenriched allylic sulfenamides.4 By taking full advantage of Pummerer (ene) reaction of this 1,2-
diplolar functionality, a series of fascinating transformations to synthesize aza-heterocycles, natural products or drug molecules have been
carried out by Padwa et al.5 Studies also indicated that they have not only been explored as ligands in transition metal catalysis6, but also
have been used as cationic reagents in electrochemical reactions.7 In addition to its great role in organic synthesis, the molecules that com-
prise this structural unit themselves possess interesting bioactivities.8 Furthermore, oxidation of this simple functionality provides another
important kind of sulfur-containing compouds, the highly heteroatomized sulfoximines9, which have exhibited significant biological activi-
ties in crop protection10 and medicinal chemistry8a, 11. As their sulfur(IV) precursors (sulfilimines), the sulfoximines have been frequenly
used as ligands in metal catalysis,12 or reagents13 in organic synthesis as well. However, compared with sulfoxides and sulfoximines, the
sulfimides are still a relatively poorly studied class of sulfur ylides. Preparation of the ones that consist of specific substitution patterns and
application of them as ligands in transition-metal catalyzed reaction are especially highly desired.
Due to the significant role that the sulfimides play in organic synthesis and life science, preparation of this type of 1,2-dipolar com-
pounds especially the asymmetric catalytic variant have drawed a great of interests in the past few decades.14 The straightforward amina-
tion of thioethers with electrophilic nitrogen reagents is the oldest and most widely reported method to prepare sulfimides, among which
transition-metal promoted sulfimidations are very efficient conversions as they can not only conducted the transformations in relatively
mild reaction conditions, but also provide possible approaches to enantiomer enriched products with the assistance of proper chiral ligands.
Various metal catalyzed procedures, such as Cu,4d, 4e Mn,15 Ru,16 Rh17 Ag18 and Fe4a, 19, were presumably proceeding via the formation of
metal nitrene species20 with the use of iminoiodinanes, azides etc. as the imidating agents. In recently years, breakthrough in preparation of
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optically active sulfimides via novel means has also been made (Scheme 1). For example, the group of Lebel delineated a Rh-catalyzed
stereoselective amination of thioethers with the use of chiral N-mesyloxycarbamate as the nitrogen source in 2014.21 Arnold et al. dis-
closed an enzyme-catalyzed amination of aromatic thioethers at the same year.22 Despite great progress has been made in this field, the
preparation of simple 8-quinolyl sulfides have never been covered in any imidation reactions before. The fact that the lewis basic nitrogen
atom is probably poisonous to the metal catalyst and would devitalize the corresponding catalytic activity might be the main reason for this
absence. As quinolyl nitrogen atom have frequently served as directing group in numerous metal catalyzed C-H bond functionalizations,23
encouraged by these delighting reaserch works, we put forword a similar 8-quinolyl nitrogen assisted straightforward synthetic strategy to
prepare the target 8-quinolylsulfimides. Herein, we describe the first synthesis of 8-quinolylsulfimides with a variety of functional groups
via Cu(I)-catalyzed, ligand-free nitrene transfer reaction to 8-quinolylsulfides and the application as a novel type of bidentate ligand in
Pd(II)-catalyzed allylic alkylation.
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Scheme 1. Metal-catalyzed Nitrene Transfer Reaction to Sulfilimine
Previous works:
R2
N3 R2
N
S
S
Fe, Ru, Cu, Rh,
Ag
R1
or
(1)
R1
R3I=NR2
This work:
CuCN
DCE,
(10 mol%)
R1
R1
N3 R2
.
100 o
C
(2)
N
N
O
S
S
S
N-directed
N
.
8-thioquinoline
ligand-free
R2
sulfimides
R2
R3
.
O
the first
of
examples 8-quinolyl
RESULTS AND DISCUSSION
Initially, in order to verify the feasibility of the ligand-free nitrene transfer process for the preparation of 8-quinolyl alkyl sulfimide, 8-
(methylthio)quinoline (1a) and 4-methylbenzenesulfonyl azide (TsN3, 2a) were chosen as the templet substrates for investigation. When
we employed 10 mol% CuBr as the catalyst, and conducted the reaction in toluene at 80 °C under argon atmosphere in a sealed reaction
tube, the expected 8-quinolyl alkyl sulfimide 3aa was produced in 23% yield (Table 1, entry 1). Encouraged by this preliminary result, a
series of Cu(I) catalysts were subsequently tested (Table 1, entries 2-4), and the outcome indicated that CuCN was slightly superior to CuI
and CuCl. Replacement of CuBr with other metal catalysts, such as Pd(OAc)2, [Rh2(OAc)4], [RuCl2(p-Cym)]2, FeSO4 and Fe(acac)3 (Table
1,entries 5-9), or with the absence of CuBr (Table 1,entry 10), the same reaction to form 8-quinolyl alkyl sulfimide 3aa could not occur.
Thus, CuCN was chosen as the catalyst for solvent screening (Table 1, entries 11-18). We found that changes in the solvent have a signifi-
cant effect on the reaction yield. Among the solvents tested, DCE appeared to be the most suitable reaction media, giving the target product
in 66% yield (Table 1, entry 18). Gratifyingly, the reaction yield could be further improved to 87% by elevating the reaction temperature
from 80 °C to 100 oC (Table 1, entry19). However, excessive higher reaction temperature did no help to the reaction, as a futher increase
from 100 oC to 120 oC led no further increase of yield (Table 1,entry 20).
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The Journal of Organic Chemistry
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Table 1. Optimization of the Reaction Parameters a
3
4
catalyst (10 mol%)
Ts N3
N
T
solvent,
N
S
Ts
5
6
7
8
S
N
1a
2a
3aa
Catalyst
(mol%)
CuBr
Yield
(%)c
Entry
Solv.b
T (oC)
1
2
3
4
5
6
toluene
toluene
toluene
toluene
toluene
toluene
80
80
80
80
80
80
23
27
20
33
0
9
CuI
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
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27
28
29
30
31
32
33
34
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36
37
38
39
CuCl
CuCN
Pd(OAc)2
[Rh2(OAc)4]
0
[RuCl2(p-
Cym)]2
7
toluene
80
0
8
FeSO4
toluene
toluene
80
80
80
80
80
80
80
80
80
80
80
100
120
0
9
Fe(acac)3
0
10
11
12
13
14
15
16
17
18
19
20
-
toluene
0
CuCN
1,4-dioxane
44
21
32
54
25
36
17
66
87
85
CuCN
CuCN
CuCN
CuCN
CuCN
CuCN
CuCN
CuCN
CuCN
MeOH
THF
CHCl3
DMSO
CH3CN
EA
DCE
DCE
DCE
aUnless otherwise noted, all the reactions were performed with 8-(methylthio)quinoline
(1a) (0.20 mmol) and 4-methylbenzenesulfonyl azide (2a) (0.24 mmol) with metal cata-
lysts (10 mol%) in solvent (1.0 mL) at the setting temperature for 12 h under Ar in a
sealed reaction tube. bTHF = tetrahydrofuran, DMSO = dimethyl sulfoxide, EA = ethyl
acetate , DCE = 1,2-dichloroethane. c Isolated yield.
With the optimized reaction conditions in hand (Table 1, entry 19), various sulfonyl azides were explored to investigate the generality of
this Cu(I)-catalyzed nitrene transfer reaction, and the results are summarized in Scheme 2. The substrate scope of sulfonyl azides is quite
general, benzenesulfonyl azide (2b) and various para-substituted benzenesulfonyl azides bearing both electron-withdrawing and electron-
donating groups could smoothly react with the 8-(methylthio)quinoline (1a), providing the expected sulfimides in moderate to good yield
(3ac-3ag, 62-93%). Ortho- and meta-methyl substituted benzenesulfonyl azide also worked well in this reaction to furnish the correspond-
ing sulfimide 3ah and 3ai in 91% and 73% yield respectively. However, the steric congested 2,3,5,6-tetramethyl benzenesulfonyl azide (2j)
seemed a reluctant reactant in the reaction as only 49% yield could be obtained. In addition, naphthylsulfonyl azide (2k), 2-
thiophenesulfonyl azide (2l), phenylmethanesulfonyl azide (2m) and methanesulfonyl azide (2n) were compatible in the reaction as well,
producing the corresponding sulfimidation products 3ak-3an in 86-93% yields. Except sulfonyl azides, other types of organic azides, such
as benzyl, aryl and Boc azide, have also been examined as the nitrogen source, but unfortunately no targeted imidated product formed.
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Scheme2. Substrate Scope for the Sulfonyl Azidea, b
1
2
3
4
O
N3
CuCN
(10 mol%)
N
S
N
R
100 o
DCE,
C
O
S
O
N
S
S
R
5
O
1a
2
3
6
7
8
9
N
N
N
e
M
S
S
O
S
O
S
S
O
S
N
N
N
e
M
10
11
12
13
14
15
16
17
18
19
20
21
22
23
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40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
O
O
O
R
a
a
3
h
1
3
i
7
9
%
3%
,
,
aa
=
C
H
3
3
3
3
3
3
3
R
R
R
R
R
8
7
%
,
,
3
a
ac
=
=
=
=
b
H
2
%
8
,
,
,
C ,
l
8
5
%
N
N
a
d
r
88%
,
F
B
C
,
,
e
S
M
S
O
S
O
ae
N
93%
,
N
3
e
M
S
a
f
=
O
M
e
R
R
6
2
%
,
,
O
O
a
g
=
C
H
3CO , 9
NH 2
%
,
e
M
e
M
a
3
4
9%
,
j
a
3
k
86%
,
N
N
N
S
S
S
O
O
O
N
N
N
S
S
S
S
e
M
O
O
O
an
3
90
%
,
am
3
93%
,
a
3
l
86%
,
aUnless otherwise noted, all the reactions were performed with 8-(methylthio)quinoline (1a) (0.20 mmol)
and sulfonyl azide (2) (0.24 mmol) with CuCN (10 mol%) in DCE (1.0 mL) at the 100℃ for 12 h under Ar
in a sealed reaction tube. bIsolated yield.
Scheme 3. Substrate Scope for the Sulfides a, b
R1
u
mo
l%
R1
C CN 10
(
)
s
T
N
N3
DCE 100 o
,
C
N
s
T
S
R2
N
S
R2
a
2
1
3
N
N
N
N
s
s
Ph
T
S
T
s
S
T
s
S
T
S
n
N
Et
N
u
B
N
N
C12H25
ea
3
a
,
78
%
3b
ca
3
,
83%
a
,
7
8%
,
3d
0%
Et
Ph
e
N
M
N
N
N
s
T
s
T
S
S
s
T
S
s
T
S
N
N
N
N
a
a
,
a
,
3f
2
9 %
3
3i
90%
a
,
88%
,
g
3h
89%
e
M
S
e
M
e
OM
N
S
N
N
N
s
T
S
s
T
s
T
s
T
S
S
N
S
N
N
N
ma
3
7
9%
a
a
3l
,
,
3
2
9 %
a
,
,
3
k
72
85
%
%
j
aUnless otherwise noted, all the reactions were performed with sulfide (1) (0.20 mmol) and sulfonyl
azide (2a) (0.24 mmol) with CuCN (10 mol%) in DCE (1.0 mL) at the 100℃ for 12 h under Ar in a
sealed reaction tube. bIsolated yield.
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1
The Journal of Organic Chemistry
The scope of sulfides was also evaluated, and the results are exhibited in Scheme 3. 8-Quinolyl sulfide with short chain alkyl, such as
ethyl (1b) and butyl (1c) could smoothly reacted with the 4-methylbenzenesulfonyl azide 2a, furnishing the targeted sulfimidation product
3ba and 3ca in 83% and 78% yield respectively. However, variation of the alkyl substitution of the alkyl 8-quinolyl sulfide from short
chain to longer one, such as dodecyl (1d), the same sulfimidation reaction could not be obseved. In addition to alkyl group, benzyl 8-
quinolyl sulfide (1e) and phenyl 8-quinolyl sulfide (1f) were tolerated in this sulfimidation reaction, giving the corresponding sulfilimine in
high or moderate yield. Next, various substituted 8-quinolyl methyl sulfide were tested. As revealed by the results of the reations of 2-
methyl (1g), 3-ethyl (1h), 3-phenyl (1i), 6-methyl (1j), 6-methoxyl (1k) substituted 8-quinolyl methyl sulfide, various substitution patterns
were compatible in the reaction, leading to the corresponding sulfimides in moderate to high yield. Except 8-quinolyl, similar 9-methyl-4-
(methylthio)acridine (1l) was also applicable, affording the corresponding sulfimide 3la in 85% yield. Noteworthy, for the multi methyl-
thio-substituted substrate, such as 2,6,8-tris(methylthio)quinoline (1m), chemoselective sulfimidation occured only at the 8-position,
providing the mono-sulimide 3ma in 79% yield.
2
3
4
5
6
7
8
9
10
11
12
13
14
15
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Scheme 4. Synthetic Application of the 8-Quinolyl Sulfimide
cat.
mol%
)
)
Pd(II)
(2.5
)
KOAc mol%
(1
CH(CO2Me)2
Ph
OAc
Ph
O
O
3aa
10 mol%
(
(1)
Ph
Ph
MeO
OMe
rt
BSA, toluene,
6a
η-C H
5a
4a
:
92%
yield
[Pd(
5)Cl]2
3
:
PdCl2 88%
yield
cat.
KOAc mol%
(1
mol%
)
Pd(II)
(2.5
)
OAc
Ph
O
O
CH(CO2Me)2
Ph
Ph
Ph
(2)
MeO
OMe
rt
BSA, toluene,
5a
4a
6a
:
η-C H
15%
yield
[Pd(
5)Cl]2
yield
3
:
PdCl2 0%
In view of synthetic application of the produced 8-quinolyl sulfimides, we envisaged that this type of compounds could function as a
novel type of bidentate ligands in the Pd(II)-catalyzed allylic substitution. The result of the reaction of 1,3-diphenyl-3-acetoxy-1-propene
(a) with dimethyl malonate in the presence of a catalytic amount of Pd(II) catalyst showed that the allylated product 6a was obtained in
good or high yield when the sulfimide 3aa was employed as the ligand (Scheme 4, Equ (1)). However, with the absence of the sulfimide
3aa, the yield for [Pd(η-C3H5)Cl]2-catalyzed allylic substitution dramatically decreased from 92% to 15%. In ligand-free conditions, the
same allylic substitution even did not occur when PdCl2 was used as catalyst (Scheme 4, Equ (2)). Furthermore, the reaction of allylic ace-
tate 4 with a wide range of 1, 3-dicarbonyl compounds was investigated to examine the generality of the palladium-3aa catalyzed allylic
substitution. As shown in Scheme 5, except dimethyl malonate 5a, diethyl malonate 5b, methy-substituted diethyl malonate 5c, 1, 3-
diketone (including cyclic 1,3-cyclohexanedione 5d and acyclic acetylacetone 5e), ethyl acetoacetate 5f and ethyl benzoylacetate 5g were
all compatible in the catalytic system, evolving corresponding alkylated products 6 in good to high yields (84-91%).
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Scheme 5. Substrate Scope of the 1, 3-Dicarbonyl Compounds for the Pd(II)-
3aa Catalyzed Allylic Alkylation a,b
1
2
3
4
PdCl2
mol%
(2.5
)
O
O
KOAc mol%
(1
10 mol%
)
)
OAc
Ph
O
O
3aa
R1
R2
(
C
R1
R2
R3
Ph
Ph
toluene
BSA,
R3
5
Ph
6
5
6
4a
7
8
O
O
O
O
O
O
9
e
e
M
O
Et
Et
O
M
O
O
Et
Et
O
O
O
O
O
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
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34
35
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37
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41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Ph
Ph
90%
Ph
Ph
Ph
Ph
Ph
Ph
86%
a
6
c
9 %
,
6b
6
1
88%
,
,
6d
,
O
O
O
O
O
Ph
Et
O
Et
O
Ph
Ph
Ph
Ph
Ph
Ph
e
r
. :
1 1 1
6f
5
r
. :
1 2 1
6
1
9 %
8 % d
6
g
,
,
84
%,
d
,
,
aUnless otherwise noted, all the reactions were performed with 1,3-diphenyl-3-acetoxy-1-propene (4a)
(0.10 mmol) , 1,3-dicarbonyl compound (5) and N,O-Bis(trimethylsilyl)acetamide (0.44 mL, 1.8 mmol)
with PdCl2 (2.5 mol%) in toluene (1.0 mL) at the room temperature for 12 h under N2 in a reaction tube.
bIsolated yield.
Scheme 6. Controlled Experiments
2a
CuCN
DCE,
,
(10 mol%)
100 o
(1)
(2)
S
Ts
C
N
S
7
1n
(not observed)
2a
CuCN
DCE,
,
(10 mol%)
100 o
C
S
Ts
N
S
1o
8
(not observed)
N
2a
2a
CuCN
DCE,
,
(10 mol%)
100 o
N
(3)
C
S
Ts
N
S
9
1p
(not observed)
O
N
O
CuCN
DCE,
,
(10 mol%)
100 o
(4)
N
H
C
H
S
Ts
S
N
10
, 67%
1q
yield
In order to shed some light on the mechanism of the present sulfimidation reaction, several controlled experiments were conducted. The
reaction of methyl(phenyl)sulfane (1n) and methyl(naphthalen-1-yl)sulfane (1o) with 4-methylbenzenesulfonyl azide (2a) was performed
under the standard conditions, respectively, and no sulfimidation products were produced (Scheme 6, Equ (1) and (2)). These results obvi-
ously implied that the quinoline nitrogen played a key role in the chelation-directed sulfimidation process. Moreover, 2-
(methylthio)pyridine (1p) which could hardly chelate with the copper catalyst was identified still inert in this reaction (Scheme 6, Equ (3)).
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Subsequently, a sulfide substrate N-(2-(methylthio)phenyl)propionamide (1q) which could similarly chelate with the copper catalyst was
exposed to the ligand-free catalytic system, and to our delight, the corresponding sulfimidation product 10 was obtained in 67% yield.
On the basis of the results of the above controlled experiment, a plausible mechanism for this ligand-free nitrene-transfer reaction was
proposed as below (Scheme 7). Firstly, chelation of the Cu(I) salt with the 8-quinolyl sulfide generated a Cu(I)-quinoline complex A; sub-
sequently, Cu(I)-promoted decomposition of sulfonyl azide accompanied by the extrusion of N2 gas resulted in the formation of the Cu-
nitrene intermediate B; finally, nitrene transfer to the sulfide with concurrently release of the Cu(I) catalyst delivered 8-quinolylsulfimide.
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Scheme 7. Possible Mechanism for the Cu(I)-Catalyzed
Nitrene Transfer Reaction
u
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T N3
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uIII
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T N
B
CONCLUSION
In summary, we disclosed herein the first efficient synthesis of a variety of 8-quinolylsulfimides with different functional groups from
readily accessible sulfonyl azides and 8-quinolyl thioethers via Cu(I)-catalyzed nitrene transfer reaction. This synthetic method is featured
by environmentally friendly as not only ligand-free cheap metal catalysis was adoptted, but also the nonhazardous nitrogen gas was the
only by-product. Quinolyl nitrogen atom played a crucial role in the catalytic process probably though chelating with the Cu(I) catalyst to
assist the nitrene transformation. The obtained 8-quinolylsulfimides proved to be a promising novel type of bidentate ligands in Pd(II)-
catalyzed allylic alkylation. Further studies on the enantioselective synthesis of 8-quinolylsulfimides and applications of this nascent type
of compounds in organic synthesis and transition-metal catalysis are currently in progress in our laboratory.
EXPERIMENTAL SECTION
General Methods. All reactions were carried out in flame-dried sealed tubes with magnetic stirring. Unless otherwise noted, all experi-
ments were performed under argon atmosphere. All reagents were purchased from TCI, Acros or Strem. Solvents were treated with 4 Å
molecular sieves or sodium and distilled prior to use. Purifications of reaction products were carried out by flash chromatography using
Qingdao Haiyang Chemical Co. Ltd silica gel (200-300 mesh). Infrared spectra (IR) were recorded on a Brucker TENSOR 27 FTIR spec-
trophotometer and are reported as wavelength numbers (cm -1). Infrared spectra were recorded by preparing a KBr pellet containing the
title compound. 1H NMR and 13C{1H} NMR spectra were recorded with tetramethylsilane (TMS) as internal standard at ambient tempera-
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ture unless otherwise indicated on a Bruker Avance III HD 400 fourier Transform spectrometer operating at 400 MHz for H NMR and
100 MHz for 13C{1H} NMR. Chemical shifts are reported in parts per million (ppm) and coupling constants are reported as Hertz (Hz).
Splitting patterns are designated as singlet (s), broad singlet (bs), doublet (d), triplet (t). Splitting patterns that could not be interpreted or
easily visualized are designated as multiple (m). Low resolution mass spectra were recorded using a Waters HPLC/ZQ4000 Mass Spec-
trometer. High resolution mass spectra (HRMS) were recorded on an IF-TOF spectrometer (Micromass). Gas chromatograph mass spectra
were obtained with a SHIMADZU model GCMS-QP5000 spectrometer. Crystal data were collected on a Bruker D8 Advance employing
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graphite monochromated Mo - Kα radiation (λ = 0.71073 Å) at 293(2) K and operating in the φ-ω scan mode. The structure was solved by
direct methods SHELXS-97. The starting materials The starting materials 8-(Thio)quinoline Substrates (1a-1m, 1p), 24 sulfonyl azides25
and (rac)-(E)-1,3-Diphenyl allyl acetate (4a) 26were prepared according to the previously reported procedures.
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Typical Procedure for the Preparation of the 8-(Thio)quinoline Substrates (1a-1m, 1p). All of the substrates (1a-1m, 1p) were prepared
according to the previously reported procedures.24 To a solution of 1.12 g (20 mmol) KOH in anhydrous DMSO (20 mL) were added 50
mmol of R2SNa and 10 mmol of 8-bromoquinoline derivatives. The resulting mixture was stirred under inert atmosphere (N2) for 5 h at RT
and overnight at 80 °C. Water (50 mL) was then added, and the reaction products were extracted by Et2O (50 mL). The organic solution
was dried over MgSO4 (6 h), filtered, and dried under vacuum. The purification of the crude product was achieved by flash chromatog-
raphy through a silica column with ethyl acetate/petroleum as eluent.
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8-(Methylthio)quinoline(1a).27 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 20:1, v/v) affords
the title compound as a white solid. 1.61g, 92% yield. 1H NMR (400 MHz, CDCl3) δ 8.92 (dd, J = 4.2, 1.6 Hz, 1H), 8.09 (dd, J = 8.3, 1.5
Hz, 1H), 7.52 (d, J = 8.1 Hz, 1H), 7.45 (t, J = 7.7 Hz, 1H), 7.41 – 7.35 (m, 2H), 2.55 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 149.1,
145.4, 139.9, 136.3, 128.1, 126.6, 123.5, 122.8, 121.6, 14.2. MS (ESI): m/z= 175.1 [M]+.
8-(Ethylthio)quinoline(1b).28 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 20:1, v/v) affords the
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title compound as a white solid. 1.72 g, 91% yield. H NMR (400 MHz, CDCl3) δ 8.93 (s, 1H), 8.10 (d, J = 8.2 Hz, 1H), 7.53 (d, J = 2.0
Hz, 1H), 7.46 – 7.37 (m, 3H), 3.08 (d, J = 7.2 Hz, 2H), 1.46 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 149.17, 145.5, 138.8,
136.4, 128.3, 126.6, 123.9, 123.7, 121.6, 25.0, 13.4. MS (ESI): m/z= 189.1 [M]+.
8-(Butylthio)quinoline(1c). Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 20:1, v/v) affords the
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title compound as a colorless oil. 1.78 g, 82% yield. H NMR (400 MHz, CDCl3) δ 8.93 (s, 1H), 8.10 (d, J = 8.2 Hz, 1H), 7.53 (d, J = 4.4
Hz, 1H), 7.45 (d, J = 3.7 Hz, 2H), 7.41 (dd, J = 8.1, 4.1 Hz, 1H), 3.06 (t, J = 7.3 Hz, 2H), 1.85 – 1.78 (m, 2H), 1.57 (dd, J = 14.7, 7.4 Hz,
2H), 0.97 (t, J = 7.3 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 149.2, 145.6, 139.1, 136.4, 128.3, 126.6, 123.8, 123.6, 121.6, 30.6, 30.4,
22.3, 13.7. HR-MS (ESI) calcd for [M+H]+: C13H16NS: 218.0998, found: 218.0997; IR (KBr): 2924, 2860, 1599, 1524, 1462, 1170, 810,
751 cm-1.
8-(Dodecylthio)quinoline(1d). Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 20:1, v/v) affords
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the title compound as a colorless oil. 2.63 g, 80% yield. H NMR (400 MHz, CDCl3) δ 8.94 (d, J = 4.1 Hz, 1H), 8.12 (d, J = 8.2 Hz, 1H),
7.58 – 7.52 (m, 1H), 7.46 (d, J = 4.9 Hz, 2H), 7.42 (dd, J = 8.2, 4.2 Hz, 1H), 3.06 (t, J = 7.3 Hz, 2H), 1.86 – 1.78 (m, 2H), 1.58 – 1.49 (m,
2H), 1.26 (s, 16H), 0.88 (t, J = 6.7 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 149.2, 145.6, 139.2, 136.3, 128.3, 126.6, 123.8, 123.6,
121.6, 31.9, 31.0, 29.6, 29.6, 29.6, 29.5, 29.3, 29.3, 29.2, 28.4, 22.7, 14.1. HR-MS (ESI) calcd for [M+H]+: C21H32NS: 330.2250, found:
330.2251; IR (KBr): 3031, 2923, 2861, 1600, 1519, 14612, 1284, 816, 751 cm-1.
8-(Benzylthio)quinoline(1e).29 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 10:1, v/v) affords
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the title compound as a colorless oil. 2.36 g, 94% yield. H NMR (400 MHz, CDCl3) δ 8.96 – 8.90 (m, 1H), 8.10 (d, J = 8.2 Hz, 1H), 7.55
(d, J = 8.0 Hz, 1H), 7.49 – 7.38 (m, 5H), 7.31 – 7.22 (m, 3H), 4.30 (s, 2H). 13C{1H} NMR (100 MHz, CDCl3) δ 149.3, 145.6, 138.4, 136.7,
136.4, 129.0, 128.5, 128.3, 127.2, 126.6, 124.9, 124.3, 121.6, 36.2. MS (ESI): m/z= 251.1 [M]+.
8-(Phenylthio)quinoline(1f).30 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 10:1, v/v) affords
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the title compound as a colorless oil. 2.08 g, 88% yield. H NMR (400 MHz, CDCl3) δ 8.97 (dd, J = 4.2, 1.6 Hz, 1H), 8.12 (dd, J = 8.3, 1.5
Hz, 1H), 7.69 – 7.61 (m, 2H), 7.54 (d, J = 8.1 Hz, 1H), 7.44 (dd, J = 7.7, 3.0 Hz, 4H), 7.29 (t, J = 7.8 Hz, 1H), 7.06 – 6.99 (m, 1H). 13C{1H}
NMR (100 MHz, CDCl3) δ 149.4, 144.8, 140.1, 136.3, 135.6, 132.0, 129.7, 128.9, 128.3, 126.7, 125.5, 124.4, 121.8. MS (ESI): m/z= 237.1
[M]+.
2-Methyl-8-(methylthio)quinoline(1g).24 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 20:1, v/v)
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affords the title compound as a white solid. 1.78 g, 94% yield. H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 8.4 Hz, 1H), 7.47 (d, J = 7.9 Hz,
1H), 7.39 (t, J = 7.6 Hz, 1H), 7.32 (d, J = 7.3 Hz, 1H), 7.26 (d, J = 8.3 Hz, 1H), 2.75 (s, 3H), 2.53 (s, 3H). 13C{1H} NMR (101 MHz,
CDCl3) δ 158.1, 144.9, 139.1, 136.2, 126.1, 125.7, 123.2, 122.6, 122.5, 25.4, 14.2. MS (ESI): m/z= 189.1 [M]+.
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3-Ethyl-8-(methylthio)quinoline(1h). Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 20:1, v/v) af-
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fords the title compound as a white solid. mp 113-115℃. 1.84 g, 90% yield. H NMR (400 MHz, CDCl3) δ 8.80 (s, 1H), 7.86 (s, 1H), 7.51
– 7.41 (m, 2H), 7.30 (d, J = 7.1 Hz, 1H), 2.81 (q, J = 7.6 Hz, 2H), 2.55 (s, 3H), 1.31 (t, J = 7.6 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3)
δ 150.5, 143.9, 139.6, 137.3, 133.7, 128.0, 126.6, 123.1, 121.9, 26.2, 15.2, 14.2. HR-MS (ESI) calcd for [M+H]+: C12H14NS: 204.0842,
found: 204.0841; IR (KBr): 2923, 2860, 1601, 1525, 1462, 1288, 814, 750 cm-1.
8-(Methylthio)-3-phenylquinoline(1i). Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 20:1, v/v)
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affords the title compound as a white solid. mp 137-139℃. 2.19 g, 87% yield. H NMR (400 MHz, CDCl3) δ 9.22 (s, 1H), 8.28 (s, 1H),
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7.72 (d, J = 7.5 Hz, 2H), 7.63 (d, J = 8.1 Hz, 1H), 7.54 (t, J = 5.9 Hz, 3H), 7.44 (dd, J = 21.0, 7.3 Hz, 2H), 2.62 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3) δ 148.5, 139.9, 137.7, 134.4, 133.5, 129.2, 128.2, 127.9, 127.4, 127.1, 123.7, 122.8, 116.7, 14.3. HR-MS (ESI) calcd
for [M+H]+: C16H14NS: 252.0842, found: 252.0844; IR (KBr): 3032, 2928, 2861, 1524, 1463, 1189, 820 cm-1.
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6-Methyl-8-(methylthio)quinoline(1j). Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 20:1, v/v)
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affords the title compound as a white solid. mp 104-106℃. 1.75 g, 92% yield. H NMR (400 MHz, CDCl3) δ 8.85 (d, J = 4.0 Hz, 1H), 8.02
(d, J = 8.2 Hz, 1H), 7.37 (dd, J = 8.2, 4.2 Hz, 1H), 7.30 (s, 1H), 7.21 (s, 1H), 2.56 (s, 3H), 2.52 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3)
δ 148.3, 144.1, 139.4, 136.5, 135.6, 128.2, 125.1, 122.6, 121.6, 21.9, 14.3. HR-MS (ESI) calcd for [M+H]+: C11H12NS: 190.0685, found:
190.0683; IR (KBr): 3030, 2926, 2864, 1599, 1462, 1189, 749 cm-1.
6-Methoxy-8-(methylthio)quinoline(1k). 30 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 3:1, v/v)
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affords the title compound as a white solid. 1.74 g, 85% yield. H NMR (400 MHz, CDCl3) δ 8.79 – 8.71 (m, 1H), 7.97 (d, J = 8.3 Hz, 1H),
7.34 (dd, J = 8.2, 4.2 Hz, 1H), 7.01 (s, 1H), 6.76 (s, 1H), 3.89 (s, 3H), 2.52 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 157.9, 146.6, 141.8,
135.0, 129.0, 121.9, 115.6, 100.7, 55.4, 14.2. MS (ESI): m/z= 205.1 [M]+.
9-Methyl-4-(methylthio)acridine (1l). Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 10:1, v/v) af-
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fords the title compound as a white solid. mp 136-138℃. 2.09 g, 87% yield. H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.7 Hz, 1H), 8.23
(d, J = 8.8 Hz, 1H), 7.99 (d, J = 8.7 Hz, 1H), 7.77 – 7.73 (m, 1H), 7.59 – 7.54 (m, 1H), 7.49 (t, J = 7.9 Hz, 1H), 7.39 (d, J = 7.0 Hz, 1H),
3.11 (s, 3H), 2.61 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 147.3, 145.8, 142.3, 141.0, 130.8, 129.4, 125.9, 125.7, 125.2, 124.2, 122.1,
120.0, 14.4, 13.9. HR-MS (ESI) calcd for [M+H]+: C15H14NS: 240.0842, found: 240.0846; IR (KBr): 2929, 2860, 1603, 1522, 1463, 1289,
814, 749 cm-1.
2,6,8-Tris(methylthio)quinoline(1m). Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 4:1, v/v) af-
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fords the title compound as a white solid. mp 164-166℃. 1.77 g, 66% yield. H NMR (400 MHz, CDCl3) δ 8.85 (d, J = 8.3 Hz, 2H), 7.51
(dd, J = 8.4, 4.3 Hz, 1H), 7.22 (s, 1H), 2.61 (d, J = 3.7 Hz, 6H), 2.31 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 147.9, 145.0, 143.7,
142.7, 134.0, 129.9, 123.3, 122.9, 118.3, 18.6, 15.8, 14.2. HR-MS (ESI) calcd for [M+H]+: C12H14NS3: 268.0283, found: 268.0286; IR
(KBr): 3032, 2928, 2861, 1603, 1515, 1462, 1189, 810, 720 cm-1.
Methyl(naphthalen-1-yl)sulfane(1p).31 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 10:1, v/v)
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affords the title compound as a colorless oil. 1.55 g, 89% yield. H NMR (400 MHz, CDCl3) δ 8.26 (d, J = 8.2 Hz, 1H), 7.81 – 7.76 (m,
1H), 7.61 (d, J = 8.0 Hz, 1H), 7.48 (dtd, J = 13.3, 6.8, 5.5 Hz, 2H), 7.39 – 7.30 (m, 2H), 2.50 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ
135.9, 133.7, 131.7, 128.6, 126.3, 126.2, 125.8, 125.8, 124.4, 123.5, 16.2. MS (ESI): m/z= 174.1 [M]+.
Procedure for the preparation of N-(2-(methylthio)phenyl)propionamide (1q).32 2-Methylthioaniline (3.0 g, 21.5 mmol) and Et3N (3.1
mL, 22.2 mmol) were dissolved in dichloromethane (20 mL) followed by dropwise addition of propionic acid anhydride (2.8 mL, 21.5
mmol). The resulting mixture was stirred overnight. The reaction mixture was diluted with dichloromethane and washed twice with 1M
HCl, once with saturated aqueous NaHCO3, and once with water. Organic layer was dried over MgSO4. Evaporation of solvent gave 4.11 g
(99% yield) of white crystals 2-Methylthio-N-propionylaniline(1q).1H NMR (400 MHz, CDCl3) δ 8.33 (d, J = 7.6 Hz, 2H), 7.46 (d, J = 7.6
Hz, 1H), 7.33 – 7.24 (m, 1H), 7.05 (t, J = 7.5 Hz, 1H), 2.47 (q, J = 7.5 Hz, 2H), 2.37 (s, 3H), 1.28 (t, J = 7.6 Hz, 3H). 13C{1H} NMR (100
MHz, CDCl3) δ 172.1, 138.4, 132.9, 128.9, 125.1, 124.2, 120.6, 31.1, 18.9, 9.7.
General Procedure for the Preparation of Sulfonyl Azides.25 To a solution of sodium azide (1.95 g, 30.0 mmol) in water (10 mL) was
added dropwise over 1 h a solution of sulfonyl chloride (20.0 mmol) in acetone (20 mL) at 0 °C. The reaction mixture was warmed up to
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room temperature and stirred for 12 h. Acetone was removed under reduced pressure and the reaction mixture was extracted with EtOAc
(30 mL × 3). The combined organic layers were dried over MgSO4 and solvent was removed under reduced pressure. Crude product was
used without further purification.
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Procedure for the preparation of (rac)-(E)-1,3-Diphenyl allyl acetate(4a).26 In an oven dried, one neck, 50 mL round bottom flask
equipped with a magnetic stir bar and septum, was placed (rac)-(E)-1,3-diphenyl allyl alcohol (1.0 g, 4.76 mmol) followed by dichloro-
methane (10 mL) and triethylamine (1.33 mL, 9.52 mmol) via syringe, under argon. The flask was placed into an ice-water bath and acetic
anhydride (0.90 mL, 9.52 mmol) was slowly added via syringe. The reaction was allowed to stir overnight at room temperature, when TLC
showed no remaining alcohol. The organic layer was extracted with saturated NaHCO3 (1 x 10 mL), water (1 x 10 mL), brine (1 x 10 mL),
dried (Na2SO4) and concentrated to yield a dark yellow oil that was purified by flash chromatography to yield (rac)-(E)-1,3-diphenyl allyl
acetate (4a) (1.03 g, 4.25 mmol, 90%) as a clear oil. (rac)-(E)-1,3-Diphenyl allyl acetate (4a), 1.03 g, yield 90%. 1H NMR (400 MHz,
CDCl3) δ 7.50 – 7.41 (m, 6H), 7.37 (ddd, J = 9.6, 6.8, 1.5 Hz, 3H), 7.32 – 7.28 (m, 1H), 6.70 (d, J = 15.8 Hz, 1H), 6.51 (d, J = 6.7 Hz, 1H),
6.47 – 6.38 (m, 1H), 2.19 (d, J = 2.6 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 170.1, 139.3, 136.2, 132.6, 128.7, 128.6, 128.2, 128.1,
127.5, 127.1, 126.7, 76.2, 21.4.
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Typical Procedure for the Quinoline N-assisted Cu(I)-Catalyzed Nitrene Transfer Reactions (3aa-3ma). All of the products (3aa-3ma)
were obtained according to the following procedure. To a screw capped vial with a spinvane triangular-shaped Teflon stir bar were added
8-(thio)quinoline (0.20 mmol), azide (0.24 mmol), CuCN (1.8 mg, 0.01 mmol, 10 mol %) and 1, 2-dichloroethane (1.0 mL) under Ar at-
mosphere conditions. The reaction mixture was stirred at 100 oC for 12 h, filtered through a pad of celite and then washed with ethyl ace-
tate (10 mL × 3). Organic solvents were removed under reduced pressure and the residue was purified by chromatography on silica gel
with ethyl acetate/petroleum as the eluent to give the desired products. All of the yields are isolated yield.
S-Methyl S-(quinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3aa). Purification by column chromatography on silica gel (petroleum
ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 112-114℃. 59.8 mg, 87% yield. 1H NMR (400 MHz,
CDCl3) δ 8.89 (dd, J = 4.2, 1.5 Hz, 1H), 8.53 (dd, J = 7.4, 0.8 Hz, 1H), 8.27 (dd, J = 8.3, 1.4 Hz, 1H), 8.03 – 7.97 (m, 1H), 7.86 (d, J = 8.2
Hz, 2H), 7.70 (t, J = 7.8 Hz, 1H), 7.54 (dd, J = 8.3, 4.3 Hz, 1H), 7.21 (d, J = 8.0 Hz, 2H), 3.04 (s, 3H), 2.36 (s, 3H). 13C{1H} NMR (100
MHz, CDCl3) δ 150.6, 143.8, 141.6, 141.6, 136.6, 133.9, 131.6, 129.3, 128.5, 128.5, 126.9, 126.4, 122.6, 38.6, 21.4. HR-MS (ESI) calcd
for [M+H]+: C17H17N2O2S2: 345.0726, found: 345.0732; IR (KBr): 3028, 2927, 1598, 1484, 1250, 1197, 1163, 809, 780, 756, 731, 672,
664 cm-1.
S-Methyl S-(quinolin-8-yl) N-(benzenesulfonyl)sulfimide (3ab). Purification by column chromatography on silica gel (petroleum
ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 108-110℃. 54.1 mg, 82% yield. 1H NMR (400 MHz,
CDCl3) δ 8.90 (d, J = 3.9 Hz, 1H), 8.50 (d, J = 7.4 Hz, 1H), 8.27 (d, J = 8.3 Hz, 1H), 7.99 (t, J = 8.9 Hz, 3H), 7.69 (t, J = 7.8 Hz, 1H), 7.55
(dd, J = 8.1, 4.1 Hz, 1H), 7.43 (d, J = 6.4 Hz, 3H), 3.05 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 150.6, 144.4, 143.7, 136.6, 133.8,
131.7, 131.2, 128.7, 128.5, 128.4, 126.9, 126.3, 122.6, 38.6. HR-MS (ESI) calcd for [M+H]+: C16H15N2O2S2: 331.0569, found: 331.0571;
IR (KBr): 3012, 2926, 1590, 1572, 1483, 1285, 1260, 1193, 758, 698 cm-1.
S-Methyl S-(quinolin-8-yl) N-(4-chlorobenzenesulfonyl) sulfimide (3ac). Purification by column chromatography on silica gel (petrole-
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um ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 137-139℃. 62.1 mg, 85% yield. H NMR (400 MHz,
CDCl3) δ 8.91 (d, J = 1.6 Hz, 1H), 8.50 (d, J = 7.4 Hz, 1H), 8.29 (d, J = 8.3 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 7.91 (d, J = 8.5 Hz, 2H),
7.72 (t, J = 7.8 Hz, 1H), 7.60 – 7.53 (m, 1H), 7.39 (d, J = 8.4 Hz, 2H), 3.07 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 150.7, 143.7,
143.0, 137.4, 136.6, 133.6, 131.8, 128.9, 128.6, 128.3, 127.9, 126.9, 122.7, 38.7. HR-MS (ESI) calcd for [M+H]+: C16H14ClN2O2S2:
365.0180, found: 365.0183; IR (KBr): 3023, 2940, 1601, 1485, 1455, 1402, 1275,1232, 1163, 1094, 1074, 1033, 830, 794, 714, 641 cm-1.
S-Methyl S-(quinolin-8-yl) N-(4-bromobenzenesulfonyl) sulfimide (3ad). Purification by column chromatography on silica gel (petrole-
um ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 142-143℃.72.0 mg, 88% yield. 1H NMR (400 MHz,
CDCl3) δ 8.92 (d, J = 4.1 Hz, 1H), 8.50 (d, J = 7.4 Hz, 1H), 8.29 (d, J = 8.3 Hz, 1H), 8.03 (d, J = 8.2 Hz, 1H), 7.84 (d, J = 8.0 Hz, 2H),
7.73 (t, J = 7.8 Hz, 1H), 7.56 (t, J = 7.6 Hz, 3H), 3.07 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 150.7, 143.8, 143.5, 136.6, 133.6, 131.9,
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131.82, 128.6, 128.4, 128.0, 126.9, 125.8, 122.7, 38.7. HR-MS (ESI) calcd for [M+H]+: C16H14BrN2O2S2: 408.9675, found: 408.9675; IR
(KBr): 3022, 2980, 1501, 1460, 1270, 1179, 1153, 831, 810, 725, 691, 638 cm-1.
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S-Methyl S-(quinolin-8-yl) N-(4-trifluoromethylbenzenesulfonyl) sulfimide (3ae). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 132-134℃. 74.0 mg, 93% yield. 1H NMR (400
MHz, CDCl3) δ 8.94 – 8.88 (m, 1H), 8.48 (d, J = 7.4 Hz, 1H), 8.30 (d, J = 8.3 Hz, 1H), 8.11 (d, J = 8.1 Hz, 2H), 8.04 (d, J = 8.2 Hz, 1H),
7.71 (dd, J = 14.2, 7.9 Hz, 3H), 7.57 (dd, J = 8.3, 4.3 Hz, 1H), 3.09 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 150.8, 147.981, 143.7,
136.7, 133.4, 132.9(d, J = 32.0 Hz), 131.9, 128.6, 128.2, 126.8, 125.8(q, J = 3.0 Hz) , 123.5(d, J = 271.0 Hz) 122.8, 38.7. HR-MS (ESI)
calcd for [M+H]+: C17H14F3N2O2S2: 399.0443, found: 399.0439; IR (KBr):2923, 2853, 1612, 1513, 1281, 1157, 1108, 844, 804, 741, 710,
618 cm-1.
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S-Methyl S-(quinolin-8-yl) N-(4-methoxybenzenesulfonyl)sulfimide (3af). Purification by column chromatography on silica gel (petrole-
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um ether/ethyl acetate = 1:1, v/v) affords the title compound as a white solid. m.p. 145-147℃. 44.6 mg, 62% yield. H NMR (400 MHz,
CDCl3) δ 8.91 (d, J = 4.0 Hz, 1H), 8.54 (d, J = 7.4 Hz, 1H), 8.27 (d, J = 8.3 Hz, 1H), 8.01 (d, J = 8.2 Hz, 1H), 7.91 (d, J = 8.3 Hz, 2H),
7.72 (t, J = 7.8 Hz, 1H), 7.55 (dd, J = 8.2, 4.2 Hz, 1H), 6.90 (d, J = 8.3 Hz, 2H), 3.82 (s, 3H), 3.04 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3) δ161.8, 150.6, 143.8, 136.6, 136.5, 134.0, 131.6, 128.5, 128.5, 128.3, 126.9, 122.6, 113.8, 55.5, 38.6. HR-MS (ESI) calcd for
[M+H]+: C17H17N2O3S2: 361.0675, found: 361.0673; IR (KBr): 2981, 2935, 1502, 1463, 1271, 1231, 1179, 1104, 1069, 832, 810, 724, 690
cm-1.
S-Methyl S-(quinolin-8-yl) N-(4-acetamidobenzenesulfonyl) sulfimide (3ag). Purification by column chromatography on silica gel (petro-
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leum ether/ethyl acetate = 1:1, v/v) affords the title compound as a white solid. m.p. 125-127℃. 71.4 mg, 92% yield. H NMR (400 MHz,
DMSO) δ 10.19 (s, 1H), 9.02 – 8.95 (m, 1H), 8.54 (d, J = 8.3 Hz, 1H), 8.34 (d, J = 7.4 Hz, 1H), 8.25 (d, J = 8.1 Hz, 1H), 7.85 (t, J = 7.8
Hz, 1H), 7.71 (dt, J = 15.8, 8.5 Hz, 5H), 3.05 (s, 3H), 2.07 (s, 3H). 13C{1H} NMR (100 MHz, DMSO) δ 168.7, 151.3, 142.9, 141.7, 138.4,
136.9, 133.6, 132.0, 128.2, 127.6, 126.7, 123.0, 118.4, 37.6, 24.0. HR-MS (ESI) calcd for [M+H]+: C18H18N3O3S2: 388.0784, found:
388.0787; IR (KBr): 3024, 2982, 2846, 1711, 1494, 1452, 1387, 1151, 1017, 785, 734, 697 cm-1.
S-Methyl S-(quinolin-8-yl) N-(2-methylbenzene sulfonyl) sulfimide (3ah). Purification by column chromatography on silica gel (petrole-
um ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 106-108℃. 62.6 mg, 91% yield. 1H NMR (400 MHz,
CDCl3) δ 8.90 – 8.83 (m, 1H), 8.59 (d, J = 7.4 Hz, 1H), 8.26 (d, J = 8.3 Hz, 1H), 8.02 (dd, J = 16.8, 8.0 Hz, 2H), 7.71 (t, J = 7.8 Hz, 1H),
7.52 (dd, J = 8.1, 4.1 Hz, 1H), 7.34 (t, J = 7.4 Hz, 1H), 7.24 (dt, J = 15.2, 6.9 Hz, 2H), 3.02 (s, 3H), 2.82 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3) δ 150.6, 143.7, 142.1, 136.8, 136.6, 134.1, 132.0, 131.7, 131.4, 128.5, 128.1, 126.9, 125.6, 122.6, 38.4, 20.7. HR-MS (ESI) calcd
for [M+H]+: C17H17N2O2S2: 345.0726, found: 345.0724; IR (KBr):3313, 3059, 2324, 2099, 1663, 1591, 1539, 1324, 1074, 1021, 961 cm-1.
S-Methyl S-(quinolin-8-yl) N-(3-methylbenzene sulfonyl) sulfimide (3ai). Purification by column chromatography on silica gel (petrole-
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um ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 115-117℃. 50.2 mg, 73% yield. H NMR (400 MHz,
CDCl3) δ 8.93 – 8.87 (m, 1H), 8.52 (d, J = 7.4 Hz, 1H), 8.27 (d, J = 8.3 Hz, 1H), 8.01 (d, J = 8.2 Hz, 1H), 7.83 – 7.74 (m, 2H), 7.70 (t, J =
7.8 Hz, 1H), 7.55 (dd, J = 8.2, 4.2 Hz, 1H), 7.30 (t, J = 7.3 Hz, 1H), 7.25 (d, J = 7.5 Hz, 1H), 3.05 (s, 3H), 2.36 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3) δ 150.6, 144.3, 143.7, 138.6, 136.6, 133.9, 132.0, 131.7, 128.6, 128.5, 128.4, 126.8, 126.8, 123.4, 122.6, 38.6, 21.3.
HR-MS (ESI) calcd for [M+H]+: C17H17N2O2S2: 345.0726, found: 345.0732; IR (KBr): 3022, 2980, 1631, 1445, 1367, 1257, 1213, 1087,
1029, 838, 726, 685 cm-1.
S-Methyl S-(quinolin-8-yl) N-( 2,3,5,6-tetramethylbenzene sulfonyl) sulfimide (3aj). Purification by column chromatography on silica gel
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(petroleum ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 122-124℃. 37.8 mg, 49% yield. H NMR (400
MHz, CDCl3) δ 8.89 (d, J = 4.2 Hz, 1H), 8.65 (d, J = 7.4 Hz, 1H), 8.26 (d, J = 8.3 Hz, 1H), 8.00 (d, J = 8.2 Hz, 1H), 7.75 (t, J = 7.8 Hz,
1H), 7.54 (dd, J = 8.3, 4.2 Hz, 1H), 7.04 (s, 1H), 3.03 (s, 3H), 2.69 (s, 6H), 2.25 (s, 6H). 13C{1H} NMR (100 MHz, CDCl3) δ150.5, 143.9,
142.5, 136.5, 135.2, 134.7, 134.4, 134.3, 131.5, 128.9, 128.5, 127.0, 122.4, 38.4, 20.9, 18.4. HR-MS (ESI) calcd for [M+H]+:
C20H23N2O2S2: 387.1195, found: 387.1197; IR (KBr): 3012, 2927, 1534, 1361, 1256, 1217, 821 cm-1.
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S-Methyl S-(quinolin-8-yl) N-(naphthalen-1-ylsulfonyl) sulfimide (3ak). Purification by column chromatography on silica gel (petroleum
ether/ethyl acetate = 3:1, v/v) affords the title compound as a white solid. m.p. 134-136℃. 65.4 mg, 86% yield. 1H NMR (400 MHz,
CDCl3) δ 8.87 (d, J = 4.2 Hz, 1H), 8.55 (d, J = 7.4 Hz, 1H), 8.51 (s, 1H), 8.23 (d, J = 8.3 Hz, 1H), 8.01 (d, J = 8.6 Hz, 1H), 7.96 (d, J = 8.2
Hz, 1H), 7.89 (t, J = 6.9 Hz, 2H), 7.84 (d, J = 7.7 Hz, 1H), 7.67 (t, J = 7.8 Hz, 1H), 7.57 – 7.50 (m, 3H), 3.03 (s, 3H). 13C{1H} NMR (100
MHz, CDCl3) δ 150.6, 143.7, 141.3, 136.5, 134.3, 133.8, 132.3, 131.7, 129.1, 129.0, 128.5, 128.5, 127.9, 127.7, 127.0, 126.8, 126.7, 122.8,
122.6, 38.6. HR-MS (ESI) calcd for [M+H]+: C20H17N2O2S2: 381.0726, found: 381.0722; IR (KBr): 3014, 2920, 1591, 1347, 1263, 1213,
1089, 1034, 973, 822, 727 cm-1.
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S-Methyl S-(quinolin-8-yl) N-(thiophen-2-ylsulfonyl) sulfimide (3al). Purification by column chromatography on silica gel (petroleum
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ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 110-112℃. 57.8 mg, 86% yield. H NMR (400 MHz,
CDCl3) δ 8.91 (d, J = 4.1 Hz, 1H), 8.53 (d, J = 7.4 Hz, 1H), 8.29 (d, J = 8.3 Hz, 1H), 8.03 (d, J = 8.2 Hz, 1H), 7.72 (t, J = 7.8 Hz, 1H), 7.62
– 7.53 (m, 2H), 7.42 (d, J = 4.9 Hz, 1H), 6.97 (t, J = 4.3 Hz, 1H), 3.09 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 150.7, 146.0, 143.7,
136.6, 133.3, 131.8, 129.9, 129.8, 128.5, 128.4, 126.9, 126.8, 122.7, 38.6. HR-MS (ESI) calcd for [M+H]+: C14H13N2O2S3: 337.0134,
found: 337.0137; IR (KBr): 3013, 2927, 1591, 1252, 1211, 1097, 1028, 831 cm-1.
S-Methyl S-(quinolin-8-yl) N-(benzylsulfonyl) sulfimide (3am). Purification by column chromatography on silica gel (petroleum
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ether/ethyl acetate = 3:1, v/v) affords the title compound as a white solid. m.p. 124-126℃. 64.0 mg, 93% yield. H NMR (400 MHz,
CDCl3) δ 8.86 – 8.80 (m, 1H), 8.47 (d, J = 7.4 Hz, 1H), 8.24 (d, J = 8.3 Hz, 1H), 7.98 (d, J = 8.1 Hz, 1H), 7.70 (t, J = 7.8 Hz, 1H), 7.55 –
7.49 (m, 1H), 7.46 (d, J = 7.0 Hz, 2H), 7.27 (d, J = 5.7 Hz, 3H), 4.45 – 4.35 (m, 2H), 2.79 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ
150.4, 143.5, 136.4, 134.9, 131.5, 131.2, 130.8, 128.4, 128.3, 128.2, 128.1, 126.8, 122.5, 60.7, 38.3. HR-MS (ESI) calcd for [M+H]+:
C17H17N2O2S2: 345.0726, found: 345.0729; IR (KBr): 2927, 1601, 1507, 1262, 1208, 1156, 1021, 834, 755, 687 cm-1.
S-Methyl S-(quinolin-8-yl) N-(methylsulfonyl) sulfimide (3an). Purification by column chromatography on silica gel (petroleum
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ether/ethyl acetate = 3:1, v/v) affords the title compound as a white solid. m.p. 101-103℃. 48.2 mg, 90% yield. H NMR (400 MHz,
CDCl3) δ 8.91 – 8.84 (m, 1H), 8.51 (d, J = 7.4 Hz, 1H), 8.23 (d, J = 8.3 Hz, 1H), 7.98 (d, J = 8.2 Hz, 1H), 7.71 (t, J = 7.7 Hz, 1H), 7.51 (dd,
J = 8.1, 4.1 Hz, 1H), 3.09 (s, 3H), 2.98 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 150.7, 143.8, 136.6, 134.6, 131.7, 128.6, 128.1, 127.0,
122.7, 42.6, 39.1. HR-MS (ESI) calcd for [M+H]+: C11H13N2O2S2: 269.0413, found: 269.0411; IR (KBr):2923, 2853, 1593, 1502, 1462,
1325, 1168, 1135, 836, 754, cm-1.
S-Ethyl S-(quinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3ba). Purification by column chromatography on silica gel (petroleum
ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 111-113℃. 59.4 mg, 83% yield. 1H NMR (400 MHz,
CDCl3) δ 8.90 (d, J = 2.3 Hz, 1H), 8.50 (d, J = 7.3 Hz, 1H), 8.26 (d, J = 8.3 Hz, 1H), 7.99 (d, J = 8.1 Hz, 1H), 7.86 (d, J = 7.7 Hz, 2H),
7.71 (t, J = 7.7 Hz, 1H), 7.54 (dd, J = 7.9, 4.0 Hz, 1H), 7.21 (d, J = 7.7 Hz, 2H), 3.47 (dd, J = 13.1, 6.8 Hz, 1H), 3.17 (dd, J = 13.1, 6.8 Hz,
1H), 2.36 (s, 3H), 1.17 (t, J = 7.2 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 150.5, 144.1, 141.6, 141.5, 136.5, 132.1, 131.5, 129.4,
129.2, 128.5, 126.8, 126.4, 122.5, 46.0, 21.4, 7.4. HR-MS (ESI) calcd for [M+H]+: C18H19N2O2S2: 359.0882, found: 359.0883; IR (KBr):
2920, 2834, 1603, 1511, 1246, 1170, 1033, 816, 751 cm-1.
S-Butyl S-(quinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3ca). Purification by column chromatography on silica gel (petroleum
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ether/ethyl acetate = 3:1, v/v) affords the title compound as a white solid. m.p. 104-106℃. 60.2 mg, 78% yield. H NMR (400 MHz,
CDCl3) δ 8.92 – 8.86 (m, 1H), 8.51 (d, J = 7.4 Hz, 1H), 8.26 (d, J = 8.3 Hz, 1H), 7.98 (d, J = 8.1 Hz, 1H), 7.87 (d, J = 8.0 Hz, 2H), 7.70 (t,
J = 7.8 Hz, 1H), 7.53 (dd, J = 8.3, 4.2 Hz, 1H), 7.21 (d, J = 8.0 Hz, 2H), 3.46 (dt, J = 12.4, 8.1 Hz, 1H), 3.11 – 3.02 (m, 1H), 2.37 (s, 3H),
1.75 – 1.68 (m, 1H), 1.48 – 1.40 (m, 1H), 1.31 (dd, J = 12.7, 7.0 Hz, 2H), 0.80 (t, J = 7.3 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ
150.5, 144.0, 141.6, 141.5, 136.5, 133.0, 131.4, 129.1, 128.9, 128.4, 126.9, 126.4, 122.5, 52.1, 25.0, 21.4, 21.1, 13.4. HR-MS (ESI) calcd
for [M+H]+: C20H23N2O2S2: 387.1195, found: 387.1193; IR (KBr): 3191, 2982, 1529, 1161, 1032, 953, 738, 689 cm-1.
S-Benzyl S-(quinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3ea). Purification by column chromatography on silica gel (petroleum
ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 122-124℃. 65.5 mg, 78% yield. 1H NMR (400 MHz,
CDCl3) δ 8.97 (s, 1H), 8.44 – 8.34 (m, 1H), 8.30 – 8.19 (m, 1H), 8.03 – 7.92 (m, 1H), 7.68 – 7.51 (m, 4H), 7.21 (d, J = 4.9 Hz, 1H), 7.15 –
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6.92 (m, 6H), 4.74 (dd, J = 12.3, 3.8 Hz, 1H), 4.24 (dd, J = 12.4, 4.0 Hz, 1H), 2.32 (d, J = 3.8 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ
150.6, 144.1, 141.3, 141.1, 136.6, 132.4, 131.5, 130.7, 129.5, 129.0, 128.8, 128.7, 128.4, 126.9, 126.2, 122.5, 57.6, 21.4. HR-MS (ESI)
calcd for [M+H]+: C23H21N2O2S2: 421.1039, found: 421.1044; IR (KBr): 3191, 2954, 2926, 1446, 1170, 1123, 734, 688 cm-1.
S-Phenyl S-(quinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3fa). Purification by column chromatography on silica gel (petroleum
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ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 112-114℃. 74.7 mg, 92% yield. H NMR (400 MHz,
CDCl3) δ 8.81 (dd, J = 4.2, 1.5 Hz, 1H), 8.70 (dd, J = 7.4, 0.8 Hz, 1H), 8.18 (dd, J = 8.3, 1.4 Hz, 1H), 7.97 (d, J = 8.1 Hz, 1H), 7.79 (d, J =
8.2 Hz, 2H), 7.72 (dt, J = 7.8, 4.0 Hz, 3H), 7.45 (dd, J = 8.3, 4.3 Hz, 1H), 7.35 – 7.25 (m, 3H), 7.12 (d, J = 8.1 Hz, 2H), 2.31 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3) δ 150.6, 143.9, 141.7, 141.4, 138.0, 136.2, 134.1, 131.9, 131.7, 129.3, 129.1, 128.7, 128.5, 127.7, 126.8,
126.4, 122.5, 21.3. HR-MS (ESI) calcd for [M+H]+: C22H19N2O2S2: 407.0882, found: 407.0878; IR (KBr): 3052, 1603, 1511, 1445, 1151,
1038, 830, 770, 734, 687 cm-1.
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S-Methyl S-(2-methylquinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3ga). Purification by column chromatography on silica gel (petrole-
um ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 110-112℃. 64.4 mg, 90% yield. 1H NMR (400 MHz,
CDCl3) δ 8.43 (d, J = 7.4 Hz, 1H), 8.11 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 8.1 Hz, 1H), 7.85 (d, J = 7.7 Hz, 2H), 7.61 (t, J = 7.8 Hz, 1H), 7.39
(d, J = 8.4 Hz, 1H), 7.21 (d, J = 7.8 Hz, 2H), 3.06 (s, 3H), 2.72 (s, 3H), 2.36 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 160.1, 143.4,
141.8, 141.5, 136.3, 132.9, 131.2, 129.2, 128.1, 126.7, 126.3, 125.9, 123.4, 38.9, 25.3, 21.4. HR-MS (ESI) calcd for [M+H]+:
C18H19N2O2S2: 359.0882, found: 359.0880; IR (KBr): 3193, 1590, 1482, 1243, 1085, 1051, 805, 739, 693 cm-1.
S-Methyl S-(3- ethyl quinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3ha). Purification by column chromatography on silica gel (petrole-
um ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 114-116℃. 66.2 mg, 89% yield. 1H NMR (400 MHz,
CDCl3) δ 8.76 (s, 1H), 8.42 (d, J = 7.3 Hz, 1H), 8.03 (s, 1H), 7.95 (d, J = 8.1 Hz, 1H), 7.85 (d, J = 7.7 Hz, 2H), 7.64 (t, J = 7.7 Hz, 1H),
7.20 (d, J = 7.7 Hz, 2H), 3.03 (s, 3H), 2.86 (q, J = 7.4 Hz, 2H), 2.35 (s, 3H), 1.35 (t, J = 7.5 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ
152.0, 142.1, 141.6, 141.5, 138.5, 133.9, 133.4, 131.3, 129.2, 128.5, 127.3, 126.7, 126.3, 38.6, 26.2, 21.4, 15.0. HR-MS (ESI) calcd for
[M+H]+: C19H21N2O2S2: 373.1039, found: 373.1038; IR (KBr): 2918, 2834, 1607, 1512, 1447, 1168, 1032, 816, 751 cm-1.
S-Methyl S-(3-phenylquinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3ia). Purification by column chromatography on silica gel (petrole-
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um ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 158-160℃. 76.4 mg, 88% yield. H NMR (400 MHz,
CDCl3) δ 9.15 (s, 1H), 8.51 (d, J = 7.3 Hz, 1H), 8.39 (s, 1H), 8.06 (d, J = 8.1 Hz, 1H), 7.87 (d, J = 7.8 Hz, 2H), 7.71 (dd, J = 16.4, 7.9 Hz,
3H), 7.54 (t, J = 7.4 Hz, 2H), 7.50 – 7.44 (m, 1H), 7.21 (d, J = 7.8 Hz, 2H), 3.07 (s, 3H), 2.36 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ
150.1, 142.7, 141.6, 141.6, 136.8, 135.5, 133.9, 133.4, 131.7, 129.4, 129.2, 128.8, 128.4, 128.2, 127.5, 127.3, 126.4, 38.7, 21.4. HR-MS
(ESI) calcd for [M+H]+: C23H21N2O2S2: 421.1039, found: 421.1044; IR (KBr): 3302, 2964, 1447, 1162, 1017, 939, 750, 732, 697 cm-1.
S-Methyl S-(6-methylquinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3ja). Purification by column chromatography on silica gel (petrole-
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um ether/ethyl acetate = 2:1, v/v) affords the title compound as a white solid. m.p. 125-127℃. 65.9 mg, 92% yield. H NMR (400 MHz,
CDCl3) δ 8.81 (s, 1H), 8.26 (s, 1H), 8.16 (d, J = 8.2 Hz, 1H), 7.86 (d, J = 8.0 Hz, 2H), 7.73 (s, 1H), 7.49 (dd, J = 7.8, 4.1 Hz, 1H), 7.21 (d,
J = 7.9 Hz, 2H), 3.01 (s, 3H), 2.54 (s, 3H), 2.37 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 149.6, 142.3, 141.7, 141.6, 137.4, 135.8,
133.2, 130.4, 130.2, 129.3, 128.7, 126.4, 122.5, 38.6, 21.6, 21.4. HR-MS (ESI) calcd for [M+H]+: C18H19N2O2S2: 359.0882, found:
359.0880; IR (KBr): 2965, 2926, 1447, 1170, 1117, 1023, 954, 734, 689 cm-1.
S-Methyl S-(6-methoxyquinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3ka). Purification by column chromatography on silica gel (petro-
leum ether/ethyl acetate = 1:1, v/v) affords the title compound as a white solid. m.p. 128-130℃. 57.7 mg, 72% yield. 1H NMR (400 MHz,
CDCl3) δ 8.70 (d, J = 3.9 Hz, 1H), 8.17 (s, 1H), 8.13 (d, J = 8.4 Hz, 1H), 7.85 (d, J = 7.7 Hz, 2H), 7.45 (dd, J = 8.1, 4.1 Hz, 1H), 7.22 (d, J
= 7.0 Hz, 3H), 3.92 (s, 3H), 3.02 (s, 3H), 2.37 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 157.9, 147.9, 141.6, 139.5, 135.4, 135.2, 129.9,
129.3, 126.4, 122.7, 120.8, 109.5, 56.1, 38.6, 21.4. HR-MS (ESI) calcd for [M+H]+: C18H19N2O3S2: 375.0832, found: 375.0815; IR (KBr):
3065, 3024, 1598, 1509, 1356, 1261, 1083, 749, 691cm-1.
S-Methyl S-(9-methylacridin-4-yl) N-(p-toluenesulfonyl)sulfimide (3la). Purification by column chromatography on silica gel (petroleum
ether/ethyl acetate = 3:1, v/v) affords the title compound as a white solid. m.p. 136-138℃. 69.4 mg, 85% yield. 1H NMR (400 MHz,
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CDCl3) δ 8.57 (d, J = 7.1 Hz, 1H), 8.41 (d, J = 8.8 Hz, 1H), 8.28 (d, J = 8.9 Hz, 1H), 8.17 (d, J = 8.7 Hz, 1H), 7.94 – 7.78 (m, 3H), 7.74 –
7.57 (m, 2H), 7.22 (d, J = 7.8 Hz, 4H), 3.16 (s, 6H), 2.37 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 147.7, 143.9, 143.7, 141.9, 141.5,
134.4, 131.1, 130.0, 129.6, 129.2, 128.4, 126.6, 126.4, 126.1, 125.6, 125.0, 124.6, 39.0, 21.4, 14.1. HR-MS (ESI) calcd for [M+H]+:
C22H21N2O2S2: 409.1039, found: 409.1036; IR (KBr):2924, 2853, 1591, 1484, 1252, 1158, 1084, 835, 750, 695 cm-1.
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S-Methyl S-(2,6-bis(methylthio)quinolin-8-yl) N-(p-toluenesulfonyl)sulfimide (3ma). Purification by column chromatography on silica
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gel (petroleum ether/ethyl acetate = 1:2, v/v) affords the title compound as a white solid. m.p. 145-147℃. 68.9 mg, 79% yield. H NMR
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(400 MHz, CDCl3) δ 8.90 (d, J = 8.6 Hz, 1H), 8.80 (d, J = 4.0 Hz, 1H), 8.36 (s, 1H), 7.84 (d, J = 7.6 Hz, 2H), 7.59 (dd, J = 8.4, 3.9 Hz,
1H), 7.23 (d, J = 7.7 Hz, 2H), 3.10 (s, 3H), 2.60 (s, 3H), 2.38 (d, J = 5.5 Hz, 6H). 13C{1H} NMR (100 MHz, CDCl3) δ 149.0, 147.0, 141.8,
141.7, 141.5, 135.5, 134.3, 132.1, 130.9, 129.3, 126.3, 123.8, 123.6, 38.4, 21.4, 18.2, 15.6. HR-MS (ESI) calcd for [M+H]+: C19H21N2O2S4:
437.0480, found: 437.0477; IR (KBr): 3097, 1500, 1447, 1236, 1090, 1054, 1032, 960, 825, 727, 689 cm-1.
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Synthetic Application of This Transformation. Procedure for the Pd(II)-catalyzed Allylic Substitution. To a stirring solution of
[Pd2(η3-C3H5)2Cl2] or PdCl2 (0.008 mmol) in toluene (1.5 mL) was added the sulfimide ligand (3aa) (10.3 mg, 0.03 mmol) under a nitro-
gen atmosphere. After 30 min, 1,3-diphenyl-3-acetoxy-1-propene (4a) (76 mg, 0.30 mmol) was added. The solution was then stirred for 30
min. N,O-Bis( trimethylsilyl)acetamide (0.44 mL, 1.8 mmol), dimethylmalonate (0.21 mL, 1.8 mmol), and potassium acetate (3.0 mg, 0.03
mmol) were added in that order. The reaction was monitored by TLC. After the solvent was evaporated under reduced pressure, silica gel
column chromatography of the residue yielded the pure 6a.
Typical Procedure for the PdCl2-Catalyzed Allylic Substitution (6a-6g). All of the products (6a-6g) were obtained according to the fol-
lowing procedure. To a stirring solution of PdCl2 (0.008 mmol) in toluene (1.5 mL) was added the sulfimide ligand (3aa) (10.3 mg, 0.03
mmol) under a nitrogen atmosphere. After 30 min, 1,3-diphenyl-3-acetoxy-1-propene (4a) (76 mg, 0.30 mmol) was added. The solution
was then stirred for 30 min. N,O-Bis( trimethylsilyl)acetamide (0.44 mL, 1.8 mmol), 1, 3-dicarbonyl compounds (1.8 mmol), and potassi-
um acetate (3.0 mg, 0.03 mmol) were added in that order. The reaction was monitored by TLC. Organic solvents were removed under re-
duced pressure and the residue was purified by chromatography on silica gel with ethyl acetate/petroleum as the eluent to give the desired
products. All of the yields are isolated yield.
(E)-Dimethyl 2-(1,3-diphenylallyl)malonate (6a).33 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate =
5:1, v/v) affords the title compound as a Colorless oil. In the presence of ligand 3aa, the yields were 92%(89.4 mg) for [Pd2(η3-C3H5)2Cl2]
and 88%(85.5 mg) for PdCl2. Without adding the ligand 3aa, the yield was 15%(14.6 mg) for [Pd2(η3-C3H5)2Cl2] and no product was
found using PdCl2 as catalyst. 1H NMR (400 MHz, CDCl3) δ 7.38 – 7.23 (m, 10H), 6.52 (d, J = 15.8 Hz, 1H), 6.37 (dd, J = 15.7, 8.6 Hz,
1H), 4.31 (dd, J = 10.8, 8.7 Hz, 1H), 4.00 (d, J = 10.9 Hz, 1H), 3.74 (s, 3H), 3.55 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 168.2, 167.8,
140.2, 136.8, 131.9, 129.1, 128.7, 128.5, 127.9, 127.6, 127.2, 126.4, 57.6, 52.6, 52.5, 49.2. MS (ESI): m/z= 324.1 [M]+.
(E)-Diethyl 2-(1,3-diphenylallyl)malonate (6b).34 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate =
10:1, v/v) affords the title compound as a Colorless oil. 95.1 mg, 90% yield. 1H NMR (400 MHz, CDCl3) δ 7.32 – 7.21 (m, 10H), 6.47 (d,
J = 15.7 Hz, 1H), 6.34 (dd, J = 15.8, 8.5 Hz, 1H), 4.26 – 4.21 (m, 1H), 4.17 (q, J = 7.1 Hz, 2H), 3.97 (qd, J = 7.2, 1.6 Hz, 2H), 1.20 (t, J =
7.1 Hz, 3H), 1.01 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 167.9, 167.4, 140.3, 136.9, 131.7, 129.4, 128.6, 128.5, 128.0,
127.5, 127.1, 126.4, 61.6, 61.4, 57.8, 49.2, 14.1, 13.8. MS (ESI): m/z= 352.2 [M]+.
(E)-diethyl 2-(1,3-diphenylallyl)-2-methylmalonate (6c).35 Purification by column chromatography on silica gel (petroleum ether/ethyl
acetate = 10:1, v/v) affords the title compound as a Colorless oil. 100.0 mg, 91% yield. 1H NMR (400 MHz, CDCl3) δ 7.37 – 7.31 (m, 4H),
7.28 (dt, J = 7.4, 3.5 Hz, 4H), 7.24 – 7.16 (m, 2H), 6.70 (dd, J = 15.7, 8.9 Hz, 1H), 6.44 (d, J = 15.7 Hz, 1H), 4.29 (d, J = 8.9 Hz, 1H), 4.18
(td, J = 7.1, 2.2 Hz, 2H), 4.08 (q, J = 7.1 Hz, 2H), 1.47 (s, 3H), 1.22 (t, J = 7.1 Hz, 3H), 1.16 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (100 MHz,
CDCl3) δ 171.2, 170.9, 139.5, 137.4, 132.6, 129.6, 128.9, 128.4, 128.2, 127.3, 127.1, 126.3, 61.4, 61.3, 58.9, 53.7, 18.8, 14.0, 14.0. MS
(ESI): m/z= 366.2 [M]+.
(E)-2-(1,3-diphenylallyl)cyclohexane-1,3-dione (6d).36 Purification by column chromatography on silica gel (petroleum ether/ethyl ace-
tate = 2:1, v/v) affords the title compound as a white solid. 78.5 mg, 86% yield. 1H NMR (400 MHz, CDCl3) δ 7.35 (d, J = 7.6 Hz, 2H),
7.26 (dt, J = 7.8, 5.6 Hz, 6H), 7.18 (t, J = 7.3 Hz, 2H), 6.80 (dd, J = 15.9, 7.8 Hz, 1H), 6.41 (d, J = 15.9 Hz, 1H), 5.18 (d, J = 7.7 Hz, 1H),
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2.35 (t, J = 6.4 Hz, 4H), 1.91 – 1.81 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3) δ 142.7, 137.4, 131.5, 130.8, 128.5, 128.4, 127.8, 127.3,
126.3, 126.2, 117.6, 42.2, 20.6. MS (ESI): m/z= 304.1 [M]+.
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(E)-3-(1,3-diphenylallyl)pentane-2,4-dione (6e).37 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate =
20:1, v/v) affords the title compound as a white solid. 79.7 mg, 91% yield. 1H NMR (400 MHz, CDCl3) δ 7.31 – 7.18 (m, 10H), 6.42 (d, J
= 15.9 Hz, 1H), 6.19 (ddd, J = 15.8, 5.5, 2.5 Hz, 1H), 4.38 – 4.28 (m, 2H), 2.23 (s, 3H), 1.91 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ
202.8, 202.6, 140.2, 136.6, 131.7, 129.3, 129.1, 128.6, 128.0, 127.7, 127.3, 126.4, 74.5, 49.2, 30.1, 29.8. MS (ESI): m/z= 292.1 [M]+.
(E)-ethyl 2-acetyl-3,5-diphenylpent-4-enoate (6f).37 Purification by column chromatography on silica gel (petroleum ether/ethyl acetate
= 5:1, v/v) affords the title compound as a Colorless oil. 82.2 mg, 85% yield. 1H NMR (400 MHz, CDCl3) δ 7.34 – 7.15 (m, 10H), 6.44 (t,
J = 15.4 Hz, 1H), 6.27 (ddd, J = 20.5, 15.8, 8.3 Hz, 1H), 4.34 – 4.24 (m, 1H), 4.21 – 4.05 (m, 2H), 3.92 (q, J = 7.1 Hz, 1H), 2.28 (s, 1.42H),
2.02 (s, 1.54H), 1.19 (t, J = 7.1 Hz, 1.56H), 0.96 (t, J = 7.1 Hz, 1.43H). 13C{1H} NMR (100 MHz, CDCl3) δ 201.7, 201.4, 168.0, 167.6,
140.4, 140.2, 136.9, 136.7, 131.9, 131.5, 129.6, 129.4, 128.9, 128.7, 128.5, 128.1, 128.0, 127.6, 127.6, 127.2, 127.1, 126.4, 126.4, 65.6,
65.3, 61.6, 61.4, 49.0, 48.8, 30.0, 29.9, 14.2, 13.8. MS (ESI): m/z= 322.2 [M]+.
(E)-ethyl 2-benzoyl-3,5-diphenylpent-4-enoate (6g).38 Purification by column chromatography on silica gel (petroleum ether/ethyl ace-
tate = 5:1, v/v) affords the title compound as a Colorless oil. 96.8 mg, 84% yield. 1H NMR (400 MHz, CDCl3) δ 8.13 – 8.04 (m, 1.12H),
7.98 – 7.89 (m, 0.92H), 7.52 – 7.08 (m, 13H), 6.58 – 6.19 (m, 2H), 5.03 (dd, J = 10.9, 4.8 Hz, 1H), 4.68 – 4.54 (m, 1H), 4.15 – 4.04 (m,
0.88H), 3.90 – 3.78 (m, 1.10H), 1.10 (t, J = 7.1 Hz, 1.41H), 0.88 (d, J = 7.1 Hz, 1.62H). 13C{1H} NMR (100 MHz, CDCl3) δ 193.2, 192.7,
168.1, 167.6, 141.0, 140.5, 137.0, 137.0, 137.0, 136.7, 133.7, 133.6, 131.9, 131.7, 130.0, 129.9, 128.9, 128.8, 128.7, 128.7, 128.7, 128.6,
128.4, 128.0, 127.6, 127.4, 127.2, 126.9, 126.4, 126.3, 61.8, 61.5, 59.9, 59.7, 49.1, 49.0, 14.2, 13.8. MS (ESI): m/z= 384.2 [M]+.
Control Experiments for the Mechanism Studies. Procedure for the Cu(I)-Catalyzed nitrene transfer reactions of methyl(phenyl) sul-
fane (1n) with TsN3 (2a). To a screw capped vial with a spinvane triangular-shaped Teflon stir bar were added methyl(phenyl)sulfane (1o)
(0.2 mmol), 4-methylbenzenesulfonyl azide (2a) (0.4 mmol), CuCN (1.8 mg, 0.02 mmol, 10 mol %) and 1, 2-dichloroethane (1.0 mL)
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under Ar atmosphere conditions. The reaction mixture was stirred at 100 C for 12 h. The reaction mixture was detected by TLC and no
new spot was found.
Procedure for the Cu(I)-Catalyzed Nitrene Transfer Reactions of 2-(Methylthio)pyridine(1o) with TsN3 (2a). To a screw capped vial
with a spinvane triangular-shaped Teflon stir bar were added methyl(naphthalen-1-yl)sulfane (1o) (0.2 mmol), 4-methylbenzenesulfonyl
azide (2a) (0.24 mmol), CuCN (1.8 mg, 0.02 mmol, 10 mol %) and 1, 2-dichloroethane (1.0 mL) under Ar atmosphere conditions. The
reaction mixture was stirred at 100 oC for 12 h. The reaction mixture was detected by TLC and no new spot was found.
Procedure for the Cu(I)-Catalyzed Nitrene Transfer Reactions of Methyl(naphthalen-1-yl)sulfane (1p) with TsN3 (2a). To a screw
capped vial with
a spinvane triangular-shaped Teflon stir bar were added 2-(methylthio)pyridine (1p) (0.2 mmol), 4-
methylbenzenesulfonyl azide (2a) (0.24 mmol), CuCN (1.8 mg, 0.02 mmol, 10 mol %) and 1, 2-dichloroethane (1.0 mL) under Ar atmos-
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phere conditions. The reaction mixture was stirred at 100 C for 12 h. The reaction mixture was detected by TLC and no new spot was
found.
Procedure for the Cu(I)-Catalyzed Nitrene Transfer Reactions of N-(2-(methylthio)phenyl)propionamide (1q) with TsN3 (2a). The prod-
ucts 9 was obtained according to the following procedure. To a screw capped vial with a spinvane triangular-shaped Teflon stir bar were
added N-(2-(methylthio)phenyl)propionamide (1q, 0.2 mmol), 4-methylbenzenesulfonyl azide (2a) (0.24 mmol), CuCN (1.8 mg, 0.02
mmol, 10 mol %) and 1, 2-dichloroethane (1.0 mL) under Ar atmosphere conditions. The reaction mixture was stirred at 100 oC for 12 h,
filtered through a pad of celite and then washed with ethyl acetate (10 mL × 3). Organic solvents were removed under reduced pressure
and the residue was purified by chromatography on silica gel with petroleum / ethyl acetate (1:1, v/v) as the eluent to give the desired
products 10.
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(E)-N-(2-(S-methyl-N-tosylsulfinimidoyl)phenyl)propionamide (10).White solid. m.p. 114-116℃. 48.7mg, 67% yield. H NMR (400
MHz, CDCl3) δ 9.89 – 9.77 (m, 1H), 7.82 (dd, J = 15.0, 7.6 Hz, 1H), 7.70 – 7.65 (m, 2H), 7.65 – 7.60 (m, 1H), 7.46 (ddd, J = 8.0, 3.5, 2.1
Hz, 1H), 7.20 (t, J = 7.7 Hz, 1H), 7.16 (d, J = 7.8 Hz, 2H), 2.99 (s, 3H), 2.47 – 2.39 (m, 2H), 2.36 (s, 3H), 1.27 – 1.21 (m, 3H).13C{1H}
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NMR (100 MHz, CDCl3) δ 173.8, 142.1, 140.6, 138.1, 133.7, 129.3, 127.7, 126.0, 125.7, 124.6, 36.1, 30.4, 21.4, 9.6. HR-MS (ESI) calcd
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for [M+H]+: C17H21N2O3S2: 365.0987, found: 365.0989; IR (KBr):2923, 1746, 1590, 1484, 1250, 1158, 1084, 954, 820, 750, 696 cm-1.
ASSOCIATED CONTENT
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Supporting Information
Copies of 1H and 13C{1H} NMR spectra for all isolated compounds, and the single crystal data of 3ia. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
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Corresponding Authors
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*E-mail: 58022849@qq.com
*E-mail: liyangyan2@163.com
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The authors thank the HNNSF (No. 2018JJ2143 & 2018JJ3195), the NSFC (No. 201801075 & 51772091), the Opening Project of Key
Laboratory of Comprehensive Utilization of Advantage Plants Resources in Hunan south, Hunan University of Science and Engineering
(XNZW17C10) and the construct program of applied characteristic discipline in Hunan University of Science and Engineering for finan-
cial support.
REFERENCES
(1) (a) Pichierri, F. Theoretical characterization of the sulfilimine bond: Double or single? Chem. Phys. Lett. 2010, 487, 315-319. (b) Senthil, K. P.;
Parminder, S.; Punam, U.; V., B. P. Electronic Structure of Sulfimides: A Theoretical Study. Bull. Chem. Soc. Jpn. 2005, 78, 1417-1424. (c) Taylor, P. C.
Sulfimides (Sulfilimines): Applications in Stereoselective Synthesis. Sulfur Reports 1999, 21, 241-280. (d) Gilchrist, T. L.; Moody, C. J. The chemistry of
sulfilimines. Chem. Rev. 1977, 77, 409-435.
(2) (a) Wu, X.-F.; Natte, K. The Applications of Dimethyl Sulfoxide as Reagent in Organic Synthesis. Adv. Synth. Catal. 2016, 358, 336-352. (b) Trost, B.
M.; Rao, M. Development of Chiral Sulfoxide Ligands for Asymmetric Catalysis. Angew.Chem.Int.Ed. 2015, 54, 5026-5043. (c) Wojaczyńska, E.;
Wojaczyński, J. Enantioselective Synthesis of Sulfoxides: 2000−2009. Chem. Rev. 2010, 110, 4303-4356. (d) Fernández, I.; Khiar, N. Recent
Developments in the Synthesis and Utilization of Chiral Sulfoxides. Chem. Rev. 2003, 103, 3651-3706.
(3) (a) Baird, C. P.; Taylor, P. C. Asymmetric synthesis of epoxides using chiral sulfimides. J. Chem. Soc., Chem. Commun. 1995, 893-894. (b) Johnson,
C. R.; Katekar, G. F. Chemistry of sulfoxides and related compounds. XXVIII. Nucleophilic methylene transfer reagents. Anions of N-p-toluenesulfonyl
sulfoximines. J. Am. Chem. Soc. 1970, 92, 5753-5754.
(4) (a) Wang, J.; Frings, M.; Bolm, C. Enantioselective Nitrene Transfer to Sulfides Catalyzed by a Chiral Iron Complex. Angew.Chem.Int.Ed. 2013, 52,
8661-8665. (b) Murakami, M.; Katsuki, T. Chiral (OC)Ru(salen)-catalyzed tandem sulfimidation and [2,3]sigmatropic rearrangement: asymmetric C  N
bond formation. Tetrahedron Lett. 2002, 43, 3947-3949. (c) Bach, T.; Körber, C. Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-
Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines. J. Org. Chem. 2000, 65, 2358-2367. (d)
Takada, H.; Nishibayashi, Y.; Ohe, K.; Uemura, S.; Baird, C. P.; Sparey, T. J.; Taylor, P. C. Catalytic Asymmetric Sulfimidation. J. Org. Chem. 1997, 62,
6512-6518. (e) Takada, H.; Nishibayashi, Y.; Ohe, K.; Uemura, S. Novel asymmetric catalytic synthesis of sulfimides. Chem. Commun. 1996, 931-932.
(5) (a) Raghavan, S.; Kumar, C. N. A stereoselective synthesis of the hexahydroazepine core of (−)-balanol. Tetrahedron Lett. 2006, 47, 1585-1588. (b)
Padwa, A.; Nara, S.; Wang, Q. Additive Pummerer reaction of heteroaromatic sulfilimines with carbon nucleophiles. Tetrahedron Lett. 2006, 47, 595-597.
(c) Wang, Q.; Nara, S.; Padwa, A. A New Synthesis of γ-Lactams Based on the Reaction of Vinyl Sulfilimines with Dichloroketene. Org. Lett. 2005, 7, 839-
841. (d) Padwa, A.; Nara, S.; Wang, Q. Dichloroketene-Induced Cyclizations of Vinyl Sulfilimines:ꢀ Application of the Method in the Synthesis of (±)-
Desoxyeseroline. J. Org. Chem. 2005, 70, 8538-8549.
(6) (a) Thakur, V. V.; Ramesh Kumar, N. S. C.; Sudalai, A. Sulfilimine palladacycles: stable and efficient catalysts for carbon–carbon coupling reactions.
Tetrahedron Lett. 2004, 45, 2915-2918. (b) Takada, H.; Oda, M.; Oyamada, A.; Ohe, K.; Uemura, S. Catalytic diastereoselective sulfimidation of diaryl
sulfides and application of chiral sulfimides to asymmetric allylic alkylation. Chirality 2000, 12, 299-312.
16
ACS Paragon Plus Environment

Page 17 of 19
1
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(7) (a) Hayashi, R.; Shimizu, A.; Song, Y.; Ashikari, Y.; Nokami, T.; Yoshida, J.-i. Metal-Free Benzylic C−H Amination via Electrochemically Generated
Benzylaminosulfonium Ions. Chem. Eur. J. 2017, 23, 61-64. (b) Hayashi, R.; Shimizu, A.; Yoshida, J.-i. The Stabilized Cation Pool Method: Metal- and
Oxidant-Free Benzylic C–H/Aromatic C–H Cross-Coupling. J. Am. Chem. Soc. 2016, 138, 8400-8403.
2
3
4
5
6
(8) (a) Vanacore, R.; Ham, A.-J. L.; Voehler, M.; Sanders, C. R.; Conrads, T. P.; Veenstra, T. D.; Sharpless, K. B.; Dawson, P. E.; Hudson, B. G. A
Sulfilimine Bond Identified in Collagen IV. Science 2009, 325, 1230-1234. (b) Andersen, K. K.; Bhattacharyya, J.; Mukhopadhyay, S. K. Antimalarial
sulfilimines and sulfoximines related to diaminodiphenyl sulfoxide and sulfone. J. Med. Chem. 1970, 13, 759-760.
(9)Pandey, A.; Bolm, C. Metal-Free Synthesis of N-Cyano-Substituted Sulfilimines and Sulfoximines. Synthesis 2010, 2922-2925.
7
8
9
(10) (a) Sparks, T. C.; DeBoer, G. J.; Wang, N. X.; Hasler, J. M.; Loso, M. R.; Watson, G. B. Differential metabolism of sulfoximine and neonicotinoid
insecticides by Drosophila melanogaster monooxygenase CYP6G1. Pestic. Biochem. Physiol. 2012, 103, 159-165. (b) Zhu, Y.; Loso, M. R.; Watson, G. B.;
Sparks, T. C.; Rogers, R. B.; Huang, J. X.; Gerwick, B. C.; Babcock, J. M.; Kelley, D.; Hegde, V. B.; Nugent, B. M.; Renga, J. M.; Denholm, I.; Gorman, K.;
DeBoer, G. J.; Hasler, J.; Meade, T.; Thomas, J. D. Discovery and Characterization of Sulfoxaflor, a Novel Insecticide Targeting Sap-Feeding Pests. J.
Agric. Food Chem. 2011, 59, 2950-2957.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(11) (a) Park, S. J.; Baars, H.; Mersmann, S.; Buschmann, H.; Baron, J. M.; Amann, P. M.; Czaja, K.; Hollert, H.; Bluhm, K.; Redelstein, R.; Bolm, C. N-
Cyano Sulfoximines: COX Inhibition, Anticancer Activity, Cellular Toxicity, and Mutagenicity. Chemmedchem 2013, 8, 217-220. (b) Lücking, U.
Sulfoximines: A Neglected Opportunity in Medicinal Chemistry. Angew.Chem.Int.Ed. 2013, 52, 9399-9408. (c) Weiss, S. J. Tying the collagen-sulfilimine
knot. Nat. Chem. Biol. 2012, 8, 740-741. (d) Chen, X. Y.; Park, S. J.; Buschmann, H.; De Rosa, M.; Bolm, C. Syntheses and biological activities of
sulfoximine-based acyclic triaryl olefins. Bioorg. Med. Chem. Lett. 2012, 22, 4307-4309. (e) Chen, X. Y.; Buschmann, H.; Bolm, C. Sulfoximine- and
Sulfilimine-Based DAPSON Analogues; Syntheses and Bioactivities. Synlett 2012, 23, 2808-2810. (f) Park, S. J.; Buschmann, H.; Bolm, C. Bioactive
sulfoximines: Syntheses and properties of Vioxx® analogs. Bioorg. Med. Chem. Lett. 2011, 21, 4888-4890. (g) Lu, D.; Vince, R. Discovery of potent HIV-
1 protease inhibitors incorporating sulfoximine functionality. Bioorg. Med. Chem. Lett. 2007, 17, 5614-5619. (h) Kahraman, M.; Sinishtaj, S.; Dolan, P. M.;
Kensler, T. W.; Peleg, S.; Saha, U.; Chuang, S. S.; Bernstein, G.; Korczak, B.; Posner, G. H. Potent, Selective and Low-Calcemic Inhibitors of CYP24
Hydroxylase:ꢀ 24-Sulfoximine Analogues of the Hormone 1α,25-Dihydroxyvitamin D3. J. Med. Chem. 2004, 47, 6854-6863.
(12) (a) Frings, M.; Thomé, I.; Bolm, C. Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis. Beilstein J.
Org. Chem. 2012, 8, 1443-1451. (b) Frings, M.; Atodiresei, I.; Wang, Y.; Runsink, J.; Raabe, G.; Bolm, C. C1-Symmetric Aminosulfoximines in Copper-
Catalyzed Asymmetric Vinylogous Mukaiyama Aldol Reactions. Chem. Eur. J. 2010, 16, 4577-4587. (c) Frings, M.; Bolm, C. Enantioselective
Halogenation of β-Oxo Esters Catalyzed by a Chiral Sulfoximine–Copper Complex. Eur. J. Org. Chem. 2009, 4085-4090. (d) Sedelmeier, J.; Hammerer, T.;
Bolm, C. C1-Symmetric Oxazolinyl Sulfoximines as Ligands in Copper-Catalyzed Asymmetric Mukaiyama Aldol Reactions. Org. Lett. 2008, 10, 917-920.
(e) Lu, S.-M.; Bolm, C. Synthesis of Sulfoximine-Derived P,N Ligands and their Applications in Asymmetric Quinoline Hydrogenations. Adv. Synth. Catal.
2008, 350, 1101-1105. (f) Langner, M.; Bolm, C. C1-Symmetric Sulfoximines as Ligands in Copper-Catalyzed Asymmetric Mukaiyama-Type Aldol
Reactions. Angew.Chem.Int.Ed. 2004, 43, 5984-5987. (g) Hiroaki, O.; Carsten, B. Sulfoximines: Synthesis and Catalytic Applications. Chem. Lett. 2004, 33,
482-487.
(13) (a) Yadav, M. R.; Rit, R. K.; Sahoo, A. K. Sulfoximines: A Reusable Directing Group for Chemo- and Regioselective ortho C H Oxidation of
Arenes. Chem. Eur. J. 2012, 18, 5541-5545. (b) Virolleaud, M.-A.; Sridharan, V.; Mailhol, D.; Bonne, D.; Bressy, C.; Chouraqui, G.; Commeiras, L.;
Coquerel, Y.; Rodriguez, J. Consecutive reactions with sulfoximines: a direct access to 2-sulfonimidoylylidene tetrahydrofurans and 6-sulfonimidoylmethyl-
3,4-dihydro-2H-pyrans. Tetrahedron 2009, 65, 9756-9764. (c) Reddy, L. R.; Gais, H.-J.; Woo, C.-W.; Raabe, G. Asymmetric Synthesis of anti-
Homopropargylic Alcohols from Aldehydes and Chiral Sulfonimidoyl Substituted Bis(allyl)titanium Complexes through Generation and Elimination of
Novel Chiral Alkylidenecarbene (Dimethylamino)sulfoxonium Ylides. J. Am. Chem. Soc. 2002, 124, 10427-10434. (d) Bolm, C.; Kesselgruber, M.; Muñiz,
K.; Raabe, G. Diastereoselective Synthesis of Ferrocenyl Sulfoximines with Planar and Central Chirality. Organometallics 2000, 19, 1648-1651. (e)
Harmata, M.; Pavri, N. A One-Pot, One-Operation [3+3] Annulation Approach to Benzothiazines. Angew.Chem.Int.Ed. 1999, 38, 2419-2421. (f) Reggelin,
M.; Heinrich, T. Metalated 2-Alkenylsulfoximides in Asymmetric Synthesis: Diastereoselective Preparation of Highly Substituted Pyrrolidine Derivatives.
Angew.Chem.Int.Ed. 1998, 37, 2883-2886. (g) Paquette, L. A.; Gao, Z.; Ni, Z.; Smith, G. F. Total Synthesis of Spinosyn A. 1. Enantioselective
Construction of a Key Tricyclic Intermediate by a Multiple Configurational Inversion Scheme. J. Am. Chem. Soc. 1998, 120, 2543-2552. (h) Boßhammer,
S.; Gais, H.-J. Synthesis and Alkylation of Cyclic α-Sulfonimidoyl Carbanions: Non-transferable Chiral Carbanionic Ligands in Copper-Mediated
Enantioselective Conjugate Addition. Synthesis 1998, 919-927. (i) Pyne, S. G.; Dong, Z.; Skelton, B. W.; White, A. H. Cyclopropanation Reactions of
Enones with Lithiated Sulfoximines:ꢀ Application to the Asymmetric Synthesis of Chiral Cyclopropanes. J. Org. Chem. 1997, 62, 2337-2343. (j) Jiang, H.;
Tang, X.; Xu, Z.; Wang, H.; Han, K.; Yang, X.; Zhou, Y.; Feng, Y.-L.; Yu, X.-Y.; Gui, Q. TBAI-catalyzed selective synthesis of sulfonamides and β-aryl
sulfonyl enamines: coupling of arenesulfonyl chlorides and sodium sulfinates with tert-amines. Org. Biomol. Chem. 2019, 17, 2715-2720.
(14) Bizet, V.; Hendriks, C. M. M.; Bolm, C. Sulfur imidations: access to sulfimides and sulfoximines. Chem. Soc. Rev. 2015, 44, 3378-3390.
17
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Page 18 of 19
(15) (a) Ohta, C.; Katsuki, T. Mn(salen)-catalyzed sulfimidation: what are the real active species in sulfimidation? Tetrahedron Lett. 2001, 42, 3885-3888.
(b) Nishikori, H.; Katsuki, T. Mn-salen catalyzed enantioselective sulfimidation. Appl. Catal. A-Gen 2000, 194-195, 475-477. (c) Nishikori, H.; Ohta, C.;
Oberlin, E.; Irie, R.; Katsuki, T. Mn-salen catalyzed nitrene transfer reaction: Enantioselective imidation of alkyl aryl sulfides. Tetrahedron 1999, 55,
13937-13946.
1
2
3
4
(16) (a) Uchida, T.; Tamura, Y.; Ohba, M.; Katsuki, T. Mechanism of asymmetric sulfimidation with N-alkoxycarbonyl azide in the presence of
(OC)Ru(salen) complex. Tetrahedron Lett. 2003, 44, 7965-7968. (b) Tamura, Y.; Uchida, T.; Katsuki, T. Highly enantioselective (OC)Ru(salen)-catalyzed
sulfimidation using N-alkoxycarbonyl azide as nitrene precursor. Tetrahedron Lett. 2003, 44, 3301-3303. (c) Murakami, M.; Uchida, T.; Saito, B.; Katsuki,
T. Ru(salen)-catalyzed asymmetric sulfimidation and subsequent [2,3]sigmatropic rearrangement. Chirality 2003, 15, 116-123. (d) Murakami, M.; Uchida,
T.; Katsuki, T. Ru(salen)-catalyzed asymmetric sulfimidation using arylsulfonyl azide. Tetrahedron Lett. 2001, 42, 7071-7074.
(17) (a) Miao, J.; Richards, N. G. J.; Ge, H. Rhodium-catalyzed direct synthesis of unprotected NH-sulfoximines from sulfoxides. Chem. Commun. 2014,
50, 9687-9689. (b) Collet, F.; Dodd, R. H.; Dauban, P. Stereoselective Rhodium-Catalyzed Imination of Sulfides. Org. Lett. 2008, 10, 5473-5476. (c)
Okamura, H.; Bolm, C. Rhodium-Catalyzed Imination of Sulfoxides and Sulfides:ꢀ Efficient Preparation of N-Unsubstituted Sulfoximines and Sulfilimines.
Org. Lett. 2004, 6, 1305-1307.
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(18)Cho, G. Y.; Bolm, C. Silver-Catalyzed Imination of Sulfoxides and Sulfides. Org. Lett. 2005, 7, 4983-4985.
(19) (a) Schäfer, S.; Wirth, T. A Versatile and Highly Reactive Polyfluorinated Hypervalent Iodine(III) Compound. Angew.Chem.Int.Ed. 2010, 49, 2786-
2789. (b) Liu, Y.; Che, C.-M. [FeIII(F20-tpp)Cl] Is an Effective Catalyst for Nitrene Transfer Reactions and Amination of Saturated Hydrocarbons with
Sulfonyl and Aryl Azides as Nitrogen Source under Thermal and Microwave-Assisted Conditions. Chem. Eur. J. 2010, 16, 10494-10501. (c) Mancheño, O.
G.; Dallimore, J.; Plant, A.; Bolm, C. Iron(II) Triflate as an Efficient Catalyst for the Imination of Sulfoxides. Org. Lett. 2009, 11, 2429-2432. (d)
Strekowski, L.; Henary, M.; Kim, N.; Michniak, B. B. N-(4-Bromobenzoyl)-S,S-dimethyliminosulfurane, a potent dermal penetration enhancer. Bioorg.
Med. Chem. Lett. 1999, 9, 1033-1034. (e) Wang, J.; Frings, M.; Bolm, C. Iron-Catalyzed Imidative Kinetic Resolution of Racemic Sulfoxides. Chem. Eur. J.
2014, 20, 966-969. (f) Yu, H.; Li, Z.; Bolm, C. Iron(II)-Catalyzed Direct Synthesis of NH Sulfoximines from Sulfoxides. Angew.Chem.Int.Ed. 2018, 57,
324-327. (g) Lebel, H.; Piras, H.; Borduy, M. Iron-Catalyzed Amination of Sulfides and Sulfoxides with Azides in Photochemical Continuous Flow
Synthesis. ACS Catalysis 2016, 6, 1109-1112. (h) Mancheño, O. G.; Bolm, C. Iron-Catalyzed Imination of Sulfoxides and Sulfides. Org. Lett. 2006, 8, 2349-
2352. (i) Bach, T.; Korber, C. Iron(II)-mediated Nitrene transfer from t-butyloxycarbonyl azide (BocN3) to sulfoxides, sulfides, and ketene acetals.
Tetrahedron Lett. 1998, 39, 5015-5016. (j) Bach, T.; Körber, C. The Preparation of N-tert-Butyloxycarbonyl-(Boc-)Protected Sulfoximines and Sulfimines
by an Iron(II)-Mediated Nitrene Transfer from BocN3 to Sulfoxides and Sulfides. Eur. J. Org. Chem. 1999, 1033-1039.
(20) (a) Ochiai, M.; Naito, M.; Miyamoto, K.; Hayashi, S.; Nakanishi, W. Imination of Sulfides and Sulfoxides with Sulfonylimino-λ3-Bromane under
Mild, Metal-Free Conditions. Chem. Eur. J. 2010, 16, 8713-8718. (b) Mancheño, O. G.; Dallimore, J.; Plant, A.; Bolm, C. Synthesis of Sulfoximines and
Sulfilimines with Aryl and Pyrazolylmethyl Substituents. Adv. Synth. Catal. 2010, 352, 309-316. (c) Armstrong, A.; Emmerson, D. P. G. Enantioselective
Synthesis of Allenamides via Sulfimide [2,3]-Sigmatropic Rearrangement. Org. Lett. 2009, 11, 1547-1550. (d) Marzinzik, A. L.; Sharpless, K. B. A Simple
Method for the Preparation of N-Sulfonylsulfilimines from Sulfides. J. Org. Chem. 2001, 66, 594-596.
(21) (a) Lebel, H.; Piras, H. Stereoselective Synthesis of Chiral Sulfilimines from N-Mesyloxycarbamates: Metal-Nitrenes versus Metal-Nitrenoids
Species. J. Org. Chem. 2015, 80, 3572-3585. (b) Lebel, H.; Piras, H.; Bartholoméüs, J. Rhodium-Catalyzed Stereoselective Amination of Thioethers with
N-Mesyloxycarbamates: DMAP and Bis(DMAP)CH2Cl2 as Key Additives. Angew.Chem.Int.Ed. 2014, 53, 7300-7304.
(22)Farwell, C. C.; McIntosh, J. A.; Hyster, T. K.; Wang, Z. J.; Arnold, F. H. Enantioselective Imidation of Sulfides via Enzyme-Catalyzed Intermolecular
Nitrogen-Atom Transfer. J. Am. Chem. Soc. 2014, 136, 8766-8771.
(23) (a) Wei, J.; Jiang, J.; Xiao, X.; Lin, D.; Deng, Y.; Ke, Z.; Jiang, H.; Zeng, W. Copper-Catalyzed Regioselective C–H Sulfonylation of 8-
Aminoquinolines. J. Org. Chem. 2016, 81, 946-955. (b) Hwang, H.; Kim, J.; Jeong, J.; Chang, S. Regioselective Introduction of Heteroatoms at the C-8
Position of Quinoline N-Oxides: Remote C–H Activation Using N-Oxide as a Stepping Stone. J. Am. Chem. Soc. 2014, 136, 10770-10776. (c) Kwak, J.;
Kim, M.; Chang, S. Rh(NHC)-Catalyzed Direct and Selective Arylation of Quinolines at the 8-Position. J. Am. Chem. Soc. 2011, 133, 3780-3783. (d) Xie,
L.-Y.; Qu, J.; Peng, S.; Liu, K.-J.; Wang, Z.; Ding, M.-H.; Wang, Y.; Cao, Z.; He, W.-M. Selectfluor-mediated regioselective nucleophilic functionalization
of N-heterocycles under metal- and base-free conditions. Green Chem. 2018, 20, 760-764. (e) Xie, L.-Y.; Peng, S.; Tan, J.-X.; Sun, R.-X.; Yu, X.; Dai, N.-N.;
Tang, Z.-L.; Xu, X.; He, W.-M. Waste-Minimized Protocol for the Synthesis of Sulfonylated N-Heteroaromatics in Water. ACS Sustainable Chemistry &
Engineering 2018, 6, 16976-16981. (f) Xie, L.-Y. ; Li, Y. -J.; Qu, J.; Duan, Y.; Hu, J.; Liu, K.-J.; Cao, Z.; He, W.-M. A base-free, ultrasound accelerated one-
pot synthesis of 2-sulfonylquinolines in water. Green Chem. 2017, 19, 5642-5646. (g) Xiao, X.; Jia, G.; Liu, F.; Ou, G.; Xie, Y. RuHCl(CO)(PPh3)3-
Catalyzed Direct Amidation of Arene C–H Bond with Azides. J. Org. Chem. 2018, 83, 13811-13820.
(24)Luciano Canovese, †; Fabiano Visentin; Gavino Chessa; Paolo Uguagliati; Carlo Levi, A.; Dolmella§, A. Attack of Substituted Alkynes on Olefin
Palladium(0) Derivatives of Pyridylthioethers. The First Kinetic Study on the Mechanism of Formation of Palladacyclopentadiene Complexes.
Organometallics 2005, 24, 5537-5548.
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Page 19 of 19
1
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(25)Kang, T.; Kim, Y.; Lee, D.; Wang, Z.; Chang, S. Iridium-Catalyzed Intermolecular Amidation of sp3 C–H Bonds: Late-Stage Functionalization of an
Unactivated Methyl Group. J. Am. Chem. Soc. 2014, 136, 4141-4144.
2
3
4
5
(26)Watson, I. D. G.; Yudin, A. K. New Insights into the Mechanism of Palladium-Catalyzed Allylic Amination. J. Am. Chem. Soc. 2005, 127, 17516-
17529.
(27)Canovese, L.; Visentin, F.; Biz, C.; Scattolin, T.; Santo, C.; Bertolasi, V. Oxidative addition of allyl and propargyl halides on palladium(0) complexes
bearing bidentate ligands with quinolinic structure. J. Organomet. Chem. 2015, 786, 21-30.
6
(28)Su, C.-Y.; Liao, S.; Wanner, M.; Fiedler, J.; Zhang, C.; Kang, B.-S.; Kaim, W. The copper(i)/copper(ii) transition in complexes with 8-
alkylthioquinoline based multidentate ligands. Dalton Trans. 2003, 189-202.
7
8
9
(29)Kita, M.; Abiko, S.-i.; Fuyuhiro, A.; Yamanari, K.; Murata, K.; Yamashita, S. Synthesis and crystal structures of palladium(II) complexes containing
benzyl 8-quinolyl sulfide and phenethyl 8-quinolyl sulfide. Polyhedron 2002, 21, 843-848.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(30)Luo, Q.; Dai, Z.; Cong, H.; Li, R.; Peng, T.; Zhang, J. Oxidant-free synthesis of benzimidazoles from alcohols and aromatic diamines catalysed by
new Ru(ii)-PNS(O) pincer complexes. Dalton Trans. 2017, 46, 15012-15022.
(31)Luo, F.; Pan, C.; Li, L.; Chen, F.; Cheng, J. Copper-mediated methylthiolation of aryl halides with DMSO. Chem. Commun. 2011, 47, 5304-5306.
(32)Shabashov, D.; Daugulis, O. Auxiliary-Assisted Palladium-Catalyzed Arylation and Alkylation of sp2 and sp3 Carbon−Hydrogen Bonds. J. Am.
Chem. Soc. 2010, 132, 3965-3972.
(33)Takada, H.; Oda, M.; Oyamada, A.; Ohe, K.; Uemura, S. Catalytic diastereoselective sulfimidation of diaryl sulfides and application of chiral
sulfimides to asymmetric allylic alkylation. Chirality 2000, 12, 299-312.
(34) Felpin, F.-X.; Landais, Y. Practical Pd/C-Mediated Allylic Substitution in Water. J. Org. Chem. 2005, 70, 6441-6446.
(35) Liu, Z.; Du, H. Development of Chiral Terminal-Alkene−Phosphine Hybrid Ligands for Palladium-Catalyzed Asymmetric Allylic Substitutions. Org.
Lett. 2010, 12, 3054-3057.
(36)Gan, K.-H.; Jhong, C.-J.; Yang, S.-C. Direct palladium/carboxylic acid-catalyzed C-allylation of cyclic 1,3-diones with allylic alcohols in water.
Tetrahedron 2008, 64, 1204-1212.
(37) Yang, H.; Fang, L.; Zhang, M.; Zhu, C. An Efficient Molybdenum(VI)-Catalyzed Direct Substitution of Allylic Alcohols with Nitrogen, Oxygen, and
Carbon Nucleophiles. Eur. J. Org. Chem. 2009, 666-672.
(38)HUANG, W.; SHEN, Q.-S.; WANG, J.-L.; ZHOU, X.-G. Direct Substitution of the Hydroxy Group at the Allylic/propargylic Position with Carbon-
and Heteroatom- centered Nucleophiles Catalyzed by Yb(OTf)3. Chin. J. Chem. 2008, 26, 729-735.
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