Thermally induced N-S bond insertion reaction of diazo compounds with: N -sulfenylsuccinimides: Synthesis of sulfides and mechanism studies

Article abstract of DOI:10.1039/c7ob02488f

A metal-free gem-functionalization reaction of diazo compounds with N-sulfenylsuccinimides via a formal N-S bond insertion process has been reported. The transformation features mild reaction conditions, broad substrate scope and functional group tolerance, offering an efficient approach to sulfide synthesis in moderate to high yields. In addition, the mechanism studies indicate the formation of free carbene under thermal conditions followed by ylide generation, then N-S bond cleavage and C-N bond formation occurred in sequence to give the sulfide products.

Full text of DOI:10.1039/c7ob02488f

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DOI: 10.1039/C7OB02488F
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ARTICLE
Thermally induced N-S bond insertion reaction of diazo
compounds with N-sulfenylsuccinimides: synthresis of sulfides
and mechanism studies
Received 00th January 20xx,
Accepted 00th January 20xx
Xiaolu Zhang,a Yang Zheng,a Lihua Qiu*a and Xinfang Xu*a,b
DOI: 10.1039/x0xx00000x
A metal-free gem-functionalization reaction of diazo compounds with N-sulfenylsuccinimides via a formal N–S bond insert
process has been reported. The transformation features mild reaction conditions, broad substrate scope and functional
group tolerance, offering an efficient approach to sulfides in moderate to high yields. In addition, the mechanism studies
indicate the formation of free carbene under thermal conditions followed by ylide generation, then N-S bond cleavage and
C-N bond formation occurred in sequence to give the sulfide products.
www.rsc.org/
Introduction
Diazo compounds, which are pervasively used as carbene
precursor,1 are versatile and powerful reagents, and have been
extensively applied in modern synthetic organic chemistry.2
Among these transformations, the direct introduction of two
substituents onto the carbon center of the diazo group,
namely gem-difunctionalization, has attracted much attention
recently.3 Three major approaches of the dinitrogen extrusion
processes are widely acknowledged through different reactive
intermediates: 1) metal carbene mediated reactions, which
includes multi-component reactions (MCRs),4 X-X (X = Si, Sn or
C) insertion,5 X-Y insertion reactions (Scheme 1a),6 and others;7
2) Lewis acid8 or substrate promoted9 transformations via
procarbenium ion intermediate (Scheme 1b); 3) thermolysis or
photolysis induce free carbene processes.10-14 However,
compared to the other two versions, selective transformation
via free carbene intermediate is more challenging, as the
reactivity and selectivity of free carbenes are more difficult to
tune. Recent advances include cross-coupling reaction,10
cyclopropenation and cyclopropanation,11 X-H and C-H
insertion,12 S-S σ-bond insertion (Scheme 1c),13 and others.14
Inspired by those works, together with our continuing interest
in reactions of free carbenes derived from diazo
coumpounds,15 we envisaged that N-sulfenylsuccinimide, a
good sulfur electrophile, could be easily attacked by the free
carbene generated in situ from the diazo compounds under
thermal conditions.6a,13a Herein, we describe a thermally
Scheme 1 Diazo compound gem-difunctionalization
.
induced formal S-N bond insertion reaction of free carbene
with N-sulfenylsuccinimides through radical intermediates,
and provide an efficient approach to sulfides in moderate to
high yields (Scheme 1d).
Results and discussion
We commenced the investigation by inducing the thermal
decomposition of phenyl diazoacetate 1a in the presence of N-
o
phenylsulfenylsuccinimide 2a in DCE (Table 1). At 80 C for 24
a.Key Laboratory of Organic Synthesis of Jiangsu Province; College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, Suzhou 215123
(P. R. China) E-mail: qiulihua@suda.edu.cn, xinfangxu@suda.edu.cn.
b.State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin
300071, China
h and the expected product 3aa was afforded in 27% yield
(entry 1). Encouraged by these results, other solvents,
including benzene, toluene, and trifluoromethylbenzene, were
investigated (entries 2-4), and the best results were obtained
†
Electronic Supplementary Information (ESI) available. Experimental section,
characterization of all compounds, copies of 1H and 13C NMR spectra for all target
compounds. See DOI: 10.1039/x0xx00000x
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Table 1 Optimization of the reaction conditionsa
Table 2 N–S Bond insertion reaction of diazoacetates 1 with 2aa
View Article Online
DOI: 10.1039/C7OB02488F
Entry
1
Solvent
DCE
Temp (oC)
Yield (%)b
27c
80
2
3
4
5
benzene
PhCH3
80
44c
48
110
PhCF3
PhCF3
PhCF3
105
90
85
26c
6
70
trace
a
All the reactions were carried out on a 0.2 mmol scale in 2.0 mL of
solvent in a sealed tube under argon atmosphere at the indicated
temperature, and the diazo compound was added via a syringe pump
over
5 h followed by stirring for additional 7 h under these
a
b
c
Reaction conditions: 1 (0.4 mmol) and 2a (0.2mmol) in PhCF3 (2.0
conditions. Isolated yields. In 24 h, all of the diazo compound 1a
was consumed and the rest of 2a was recovered. DCE =1,2-
dichloroethane.
mL) under argon atmosphere at 105oC for 12 h; and the yields are
b
o
c
given in isolated yields. At 110 C. Reaction was carried out in 4.0
mmol scale. d With 0.8 mmol of 1a. PMP = p-MeOC6H4.
o
with trifluoromethylbenzene at 105 C for 12 h (entry 4, 85%
o
isolated yield). Reducing the reaction temperature to 90 C
We further evaluated the generality of this reaction
regarding N-sulfenylsuccinimides
electric property and position of substituent groups on the
phenyl group of N-sulfenylsuccinimides had little influence
on the reactivity, generating the corresponding products in
high to excellent yields (3gb 3gi 3ab, and 3ae). Moreover, the
alkyl substituted substrates 2j 2l were quite compatible in this
transformation, which afforded the products in 3gj 3gl
2. As shown in Table 3, the
slow down the reactivity drastically (entry 5) and < 5%
conversion was found at 70 oC or below (entry 6).
2
With the optimal reaction conditions in hand, we
subsequently investigated the reactions between a series of
-
,
aryl diazo esters
being tested reacted with 2a smoothly to give high yields (>
71%, 3aa 3ea, and 3ga 3ia). In the case of 1f with a strong
1 with 2a (Table 2). Most diazo compounds
-
-
-
-
synthetically useful yields. Furthermore, this method was also
amenable to substrates derived from phthalimides, and the
EWG such as CF3, the substrate showed lower reactivity under
the optimized conditions and 3fa was obtained in 42% yield
when the reaction was carried out at 110 oC. The diazoacetates
with various ester groups (R) were reliably accommodated,
corresponding products were generated in >78% yields (3am
3an, and 3go). Notably, the diphenyl diazo compound, which is
precursor of donor/donor-free carbene, could also
,
a
producing the corresponding products in 57-72% yields (3ja
-
participate in the reactions and afforded the product 3oe in
61% yield.
3na). It is worth mentioning that these groups, especially
benzyl (3ka), alkenyl (3la), and alkynyl (3ma) groups which
were recognized as reactive functional groups towards metal
carbene for C-H insertion, cyclopropanation, and
cyclopropenation reactions, respectively, were all well-
To shed light on the reaction mechanism, control
experiments and crossover reaction were carried out (Scheme
2). Firstly, a competition experiment was performed: aryl diazo
ester 1l and sulfenylsuccinimide 2o was subjected to reaction
in the presence of Rh2(OAc)4,19 and only cyclopropanation
tolerated in this reaction. However, the
α α-
-styryl16 and
benzyl17 diazo compounds, due to the inherent instability of
these materials under thermal conditions, only intramolecular
product
8 was isolated in >90% yield instead of delivering the
corresponding N-S insertion product (Scheme 2a). Moveover,
according to the reported dirhodium-catalyzed version, the N-
S insertion product 3qo was isolated only in 44% yield due to
the steric effect,6a while this is not a problem at all under
current metal-free conditions and the same product was
obtained in 80% yield (Scheme 2b). These results clearly
illustrated the distinction between the metal carbene reaction
and current method, which shown preference to react with
the electrophilic sulfur. Then control experiment in the
cyclization product and
β-H shift product were detected,
respectivley under current conditions.18 Moreover, 1n derived
from (-)-Menthol reacted well with 2a, producing 3na in 66%
yield and 1.5:1 dr under briefly optimized conditions. In
addition, the reaction proceeded smoothly on a gram scale,
and 3ga was obtained in 89 % yield when the reaction was
carried out on a 4.0 mmol scale (note c).
2 | J. Name., 2012, 00, 1-3
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Table 3 Substrate scope of N-sulfenylsuccinimides 2a
View Article Online
DOI: 10.1039/C7OB02488F
O
N2
O
PhCF3
105 oC, 12 h
+
N
Ar
R1
SR2
N
SR2
R1
O
2
O
Ar
1
3
b
3gb, R = 4-Me, 73% 3gf
3gc, R = 2-Me, 82% 3gg
3gd, R = 3-Me, 80% 3gh
, R = 4-NO2, 66%
, R = 4-Br, 75%
, R = 4-Cl, 71%
, R = 4-F, 83%
O
N
R
S
O
O
CO2Me 3ge
3gi
, R = 4-MeO, 95%
PMP
O
O
O
N
N
N
SC5H11
SBn
CO2Me
b
SC7H15
CO2Me
c
O
O
CO2Me
PMP
3gk
PMP
3gj
, 55%
PMP
c
3gl
, 38%
, 47%
Me
OMe
O
O
O
S
N
SPh
N
S
N
O
CO2Me
O
Ph
CO2Me
O
Ph
CO2Me
3go, 78%
3am, 84%
3an, 82%
MeO
Me
OMe
OMe
O
O
O
N
S
N
N
Ph
S
S
O
O
O
Ph
3ab
CO2Me
, 70%
Ph
3ae
CO2Me
, 71%
Ph
, 61%
3oe
a Reaction conditions: 1 (0.4 mmol) and 2 (0.2 mmol) in PhCF3(2.0 mL)
o
under argon atmosphere at 105 C for 12 h; and the yields are given
in isolated yields. b At 110 oC. c At 100 oC. d Yield given in parentheses
is the results in the presence of Rh2(OAc)4 with hexane as solvent at
80 oC. PMP = p-MeOC6H4.
Scheme 2 Control reactions and crossover experiment.
presence of 5.0 equivalent of TEMPO was carried out under
standard conditions, and the reaction was inhibited to give the
insertion product only in 30% yield with 4 as the major product
via direct oxidation (Scheme 2c). Moreover, the free radical
intermediate was intercepted and the corresponding product
5
was detected by LC-MS (Scheme 2d, and see Figure S5 for
details). The crossover reaction was performed by subjecting
an equivalent amount of 2b and 2n with 1a and under the
Conclusions
optimal reaction conditions, and four products 3ab, 3ae, 3am,
In conclusion, we have developed a thermally induced gem-
functionalization reaction of diazo compounds with N-
sulfenylimides via a formal N–S bond insert process, which
provided an efficient approach to sulfides in moderate to high
yields under mild reaction conditions with broad substrate
scope and functional group tolerance. A reaction pathway
involving a sequential N-S bond cleavage and C-N bond
formation process was proposed and verified experimentally
via crossover reactions. Further exploration of free carbene
transformations and mechanism studies are ongoing in our
laboratory.
3an were generated in a 26 : 20 : 24 : 30 ratio (Scheme 2e, and
see Figure S6-S10 for details).18 These results suggested that
free radical intermediates are involved in this transformation.
Based on these and previous works,13 a plausible reaction
mechanism was proposed. Initially, the diazoacetate
1
decomposed to generate free carbene under thermal
condition and addition with electrophilic N-sulfenylsuccinimide
2
to form the ylide intermediate. Then N-S bond cleavage and
C-N bond formation occurred successively to generate the
formal N-S insertion product . However, further studies are
3
needed to unambiguously establish the reaction
transformation.
As shown in Eq (1), to demonstrate the utility of these
Experimental section
sulfide products. The imine derivative 6 could be obtained in
73% yield under slightly modified reported conditions.6a
General remarks
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All reactions are carried out in oven-dried (140
Journal Name
C) glassware 128.3, 75.8, 53.7, 28.0; HRMS (TOF MS ESI+) cVailecwuAlratitceledOnflioner
°
under an atmosphere of argon. Solvents are dried and C19H16ClNNaO4S[M+Na]+: 412.0386, founDdO4I1: 120..01033899/.C7OB02488F
degassed by the standard methods. Flash column Spectral data of compound 3ea. White solid, mp: 70.6-71.3
chromatography is performed using silica gel (300-400 mesh). oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.76 – 7.71 (m, 2H), 7.52
Analytical thin-layer chromatography is performed using glass – 7.43 (comp, 4H), 7.40 – 7.35 (m, 1H), 7.28 – 7.22 (m, 2H),
plates pre-coated with 300-400 mesh silica gel impregnated 3.63 (s, 3H), 2.57 – 2.39 (comp, 4H); 13C NMR (100 MHz, CDCl3)
1
with a fluorescent indicator (254 nm). H NMR and 13C NMR (δ, ppm) 174.7, 167.2, 137.8, 134.3, 131.3, 130.6, 129.9, 129.7,
spectra are recorded in CDCl3 on a 400 MHz spectrometer; 128.9, 123.6, 75.9, 53.8, 28.0; HRMS (TOF MS ESI+) calculated
chemical shifts are reported in ppm with the solvent signals as for C19H16BrNNaO4S [M+Na]+: 415.9881, found 455.9880.
reference, and coupling constants (J) are given in Hertz. The
Spectral data of compound 3fa. White solid, mp: 125.4-
peak information is described as: br = broad, s = singlet, d = 126.2 oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.98 (d, J = 8.3 Hz,
doublet, t = triplet, q = quartet, m= multiplet, comp = 2H), 7.62 (d, J = 8.4 Hz, 2H), 7.50 – 7.44 (m, 2H), 7.39 (t, J = 7.4
composite. High-resolution mass spectra (HRMS) are recorded Hz, 1H), 7.26 (t, J = 7.6 Hz, 2H), 3.65 (s, 3H), 2.58 – 2.41 (m, 4H);
on a commercial apparatus (ESI or CI Source).
13C NMR (100 MHz, CDCl3) (δ, ppm) 174.7, 167.1, 139.2, 137.8,
130.84 (d, J = 32.6 Hz), 130.75, 129.5, 129.0, 128.6, 125.2 (q, J
= 3.7 Hz), 124.0 (d, J = 272.4 Hz), 75.9, 53.9, 28.0; HRMS (TOF
MS ESI+) calculated for C20H16F3NNaO4S[M+Na]+: 446.0650,
found 446.0641.
General Procedure for N-S Bond Insertion Reaction
To a 10-mL oven-dried vial containing a magnetic stirring bar,
and
2
(0.2 mmol) in PhCF3 (0.5 mL), was added the solution of
(0.4 mmol) in PhCF3 (1.5 mL) via a syringe
Spectral data of compound 3ga. White solid, mp: 133.8-
diazo compound
1
o
1
134.5 C. H NMR (400 MHz, CDCl3) (δ, ppm) 7.79 – 7.73 (m,
2H), 7.51 – 7.45 (m, 2H), 7.39 – 7.33 (m, 1H), 7.23 (d, J = 7.5 Hz,
2H), 6.91 – 6.85 (m, 2H), 3.82 (s, 3H), 3.63 (s, 3H), 2.54 – 2.41
(comp, 4H); 13C NMR (100 MHz, CDCl3) (δ, ppm) 174.8, 167.7,
159.9, 137.7, 130.4, 130.2, 129.5, 128.8, 126.9, 113.5, 76.1,
55.4, 53.6, 28.1; HRMS (TOF MS ESI+) calculated for
C20H19NNaO5S[M+Na]+: 408.0882, found 408.0876.
o
pump in 5 hours at 105 C under argon atmosphere. The
reaction mixture was stirred for additional 7 h under these
conditions. After the reaction was completed, the reaction
mixture was directly purified by column chromatography on
silica gel without any additional treatment (eluent: Hexanes :
EtOAc = 20:1 to 3:1) to give the pure products
high yields.
3 in moderate to
Spectral data of compound 3ha. White solid, mp: 74.0-76.6
oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.88 – 7.50 (comp, 3H),
7.34 – 7.27 (m, 2H), 7.24 – 7.18 (m, 2H), 7.02 – 6.96 (m, 1H),
6.86 – 6.81 (m, 1H), 3.75 (s, 3H), 3.68 (s, 3H), 2.40 (s, 4H); 13C
NMR (100 MHz, CDCl3) (δ, ppm) 174.5, 167.5, 157.2, 137.5,
131.0, 130.2, 129.9, 129.5, 128.5, 123.5, 120.6, 112.1, 75.3,
56.0, 53.7, 27.9; HRMS (TOF MS ESI+) calculated for
C20H19NaNO5S[M+Na]+: 408.0882, found 408.0883.
Spectral data of compound 3aa. White solid, mp: 148.8-
o
1
149.2 C. H NMR (400 MHz, CDCl3) (δ, ppm) 7.91 – 7.72 (m,
2H), 7.50 (d, J = 7.2 Hz, 2H), 7.43 – 7.30 (comp, 4H), 7.29 – 7.20
(m, 2H), 3.63 (s, 3H), 2.55 – 2.38 (comp, 4H); 13C NMR (100
MHz, CDCl3) (δ, ppm) 174.7, 167.6, 137.8, 135.0, 130.4, 130.0,
128.8, 128.8, 128.2, 128.0, 76.4, 53.6, 28.0; HRMS (TOF MS
ESI+) calculated for C19H17NaNO4S[M+Na]+: 378.0776, found
378.0780.
Spectral data of compound 3ia. White solid, mp: 99.8-101.1
1
Spectral data of compound 3ba. White solid, mp: 78.7-80.8
1
oC. H NMR (400 MHz, CDCl3) (δ, ppm) 7.87 (d, J = 8.0 Hz, 1H),
oC. H NMR (400 MHz, CDCl3) (δ, ppm) 7.70 (d, J = 8.4 Hz, 2H),
7.49 (d, J = 7.3 Hz, 2H), 7.34 – 7.26 (m, 2H), 7.20 (t, J = 7.6 Hz,
2H), 6.98 (t, J = 7.6 Hz, 1H), 6.83 (d, J = 8.0 Hz, 1H), 3.74 (s, 3H),
3.67 (s, 3H), 2.39 (s, 4H); 13C NMR (100 MHz, CDCl3) (δ, ppm)
174.5, 167.5, 157.2, 137.5, 130.9, 130.2, 129.9, 129.4, 128.4,
123.4, 120.5, 112.1, 75.2, 55.9, 53.6, 27.8; HRMS (TOF MS ESI+)
calculated for C20H19NaNO5S[M+Na]+: 408.0882, found
408.0877.
7.50 (d, J = 7.0 Hz, 2H), 7.36 (t, J = 7.4 Hz, 1H), 7.27 – 7.21 (m,
2H), 7.17 (d, J = 8.2 Hz, 2H), 3.63 (s, 3H), 2.54 – 2.40 (comp, 4H),
2.35 (s, 3H); 13C NMR (100 MHz, CDCl3) (δ, ppm) 174.8, 167.7,
138.7, 137.8, 132.0, 130.4, 130.1, 128.9, 128.8, 127.9, 76.4,
53.6, 28.0, 21.2; HRMS (TOF MS ESI+) calculated for
C20H19NNaO4S[M+Na]+: 392.0932, found 392.0923.
Spectral data of compound 3ca. White solid, mp: 104.4-
Spectral data of compound 3ja. White solid, mp: 131.1-
o
1
105.0 C. H NMR (400 MHz, CDCl3) (δ, ppm) 7.87 – 7.81 (m,
2H), 7.49 – 7.44 (m, 2H), 7.37 (t, J = 7.4 Hz, 1H), 7.25 (t, J = 7.6
Hz, 2H), 7.09 – 7.01 (m, 2H), 3.64 (s, 3H), 2.73 – 2.34 (comp,
4H); 13C NMR (100 MHz, CDCl3) (δ, ppm) 174.8, 167.5, 162.9 (d,
J = 249.1 Hz), 137.7, 130.9 (d, J = 3.4 Hz), 130.6, 130.2, 130.1,
128.9, 115.1 (d, J = 21.8 Hz), 75.8, 53.7, 28.0; HRMS (TOF MS
ESI+) calculated for C19H16FNNaO4S[M+Na]+: 396.0682, found
396.0672.
o
1
131.9 C. H NMR (400 MHz, CDCl3) (δ, ppm) 7.88 – 7.79 (m,
2H), 7.50 (d, J = 7.1 Hz, 2H), 7.40 – 7.30 (comp, 4H), 7.24 (t, J =
7.7 Hz, 2H), 4.33 – 3.95 (m, 2H), 2.46 (comp, 4H), 1.12 (t, J =
7.1 Hz, 3H);13C NMR (101 MHz, CDCl3) (δ, ppm) 174.7, 167.0,
137.8, 135.0, 130.4, 130.1, 128.8, 128.7, 128.04, 128.03, 76.5,
63.0, 28.0, 13.8; HRMS (TOF MS ESI+) calculated for
C20H19NNaO4S[M+Na]+: 392.0932, found 392.0923.
Spectral data of compound 3ka. White solid, mp: 43.1-48.1
oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.82 – 7.76 (m, 2H), 7.54
– 7.49 (m, 2H), 7.35 (comp, 4H), 7.25 (comp, 5H), 7.09 – 7.04
(m, 2H), 5.15 (d, J = 12.3 Hz, 1H), 4.96 (d, J = 12.3 Hz, 1H), 2.44
(s, 4H); 13C NMR (101 MHz, CDCl3) (δ, ppm) 174.7, 166.9, 137.9,
135.0, 134.9, 130.4, 129.9, 128.8, 128.7, 128.5, 128.2, 128.1,
Spectral data of compound 3da. White solid, mp: 64.1-64.7
oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.83 – 7.76 (m, 2H), 7.48
– 7.43 (m, 2H), 7.39 – 7.31 (m, 3H), 7.28 – 7.22 (m, 2H), 3.63 (s,
3H), 2.58 – 2.36 (m, 4H); 13C NMR (100 MHz, CDCl3) (δ, ppm)
174.7, 167.3, 137.8, 134.9, 133.7, 130.6, 129.7, 129.6, 128.9,
4 | J. Name., 2012, 00, 1-3
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128.0, 127.9, 76.5, 68.4, 28.0; HRMS (TOF MS ESI+) calculated (100 MHz, CDCl3) (δ, ppm) 174.8, 167.8, 159.8, 138.6, 138.2,
View Article Online
for C25H22NO4S[M+H]+: 432.1270, found 432.1267.
134.7, 131.1, 129.8, 129.5, 128.6, 126.9, D1O13I:.150,.17063.91/,C57O5B.40,254838.5F,
Spectral data of compound 3la. White solid, mp: 43.1-48.1 28.0, 21.3; HRMS (TOF MS ESI+) calculated for
oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.88 – 7.82 (m, 2H), 7.54 C21H21NNaO5S[M+Na]+: 422.1038, found 422.1033.
– 7.49 (m, 2H), 7.40 – 7.33 (m, 4H), 7.30 (comp, 4H), 7.27 –
Spectral data of compound 3ge. White solid, mp: 109.4-
o
1
7.21 (m, 4H), 6.40 (d, J = 15.9 Hz, 1H), 6.10 – 6.00 (m, 1H), 4.79 109.8 C. H NMR (400 MHz, CDCl3) (δ, ppm) 7.77 – 7.69 (m,
– 4.59 (m, 1H), 2.53 – 2.42 (m, 4H); 13C NMR (100 MHz, CDCl3) 2H), 7.40 – 7.35 (m, 2H), 6.89 – 6.84 (m, 2H), 6.79 – 6.73 (m,
(δ, ppm) 174.7, 166.9, 137.9, 136.3, 135.0, 134.2, 130.4, 130.0, 2H), 3.80 (s, 3H), 3.75 (s, 3H), 3.63 (s, 3H), 2.48 (comp, 1H); 13C
128.8, 128.8, 128.7, 128.2, 128.1 126.7, 122.4, 76.6, 67.2, 28.1; NMR (100 MHz, CDCl3) (δ, ppm) 174.9, 167.8, 161.5, 159.7,
HRMS (TOF MS ESI+) calculated for C27H24NO4S[M+H]+: 139.3, 129.4, 126.9, 120.7, 114.3, 113.5, 76.0, 55.4, 55.3, 53.5,
458.1426, found 458.1417.
Spectral data of compound 3ma. White solid, mp: 52.2-54.8 438.0987, found 438.0988.
28.0; HRMS (TOF MS ESI+) calculated for C21H21NNaO6S[M+Na]+:
1
oC. H NMR (400 MHz, CDCl3) (δ, ppm) 7.85 (d, J = 6.9 Hz, 2H),
Spectral data of compound 3gf. White solid, mp: 77.6-78.2
7.56 – 7.51 (m, 2H), 7.40 – 7.34 (comp, 6H), 7.31 (t, J = 7.4 Hz, oC. H NMR (400 MHz, CDCl3) (δ, ppm) 8.04 (d, J = 8.8 Hz, 2H),
3H), 7.25 (m, 2H), 4.91 (d, J = 15.6 Hz, 1H), 4.80 (d, J = 15.6 Hz, 7.68 (d, J = 8.9 Hz, 2H), 7.57 (d, J = 8.8 Hz, 2H), 6.87 (d, J = 8.9
1H), 2.53 – 2.46 (comp, 4H); 13C NMR (100 MHz, CDCl3) (δ, ppm) Hz, 2H), 3.81 (s, 3H), 3.63 (s, 3H), 2.61 (comp, 4H); 13C NMR
174.7, 166.4, 137.9, 134.7, 131.9, 130.5, 129.8, 128.9, 128.8, (100 MHz, CDCl3) (δ, ppm) 174.9, 167.0, 160.1, 148.4, 139.3,
128.4, 128.2, 128.1, 126.8, 122.2, 87.2, 82.1, 76.2, 55.1, 28.0; 136.7, 129.7, 126.0, 123.4, 113.7, 75.9, 55.4, 53.7, 28.1; HRMS
HRMS (TOF MS ESI+) calculated for C27H21NNaO4S[M+Na]+: (TOF MS ESI+) calculated for C20H18N2NaO7S[M+Na]+: 453.0732,
1
478.1089, found 478.1089.
found 453.0725.
Spectral data of compound 3na (two isomers). White solid,
Spectral data of compound 3gg. White solid, mp: 96.9-97.6
mp: 61.7-62.2 C. H NMR (400 MHz, CDCl3) (δ, ppm) one oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.76 – 7.66 (m, 2H), 7.40
isomer: 7.71 – 7.69 (m, 2H), 7.56 – 7.54 (m, 2H), 7.38 – 7.19 – 7.29 (m, 4H), 6.91 – 6.84 (m, 2H), 3.81 (s, 3H), 3.63 (s, 3H),
(comp, 6H), 4.64 (td, J = 10.9, 4.2 Hz, 1H), 2.50 – 0.76 (comp, 2.55 (comp, 4H); 13C NMR (100 MHz, CDCl3) (δ, ppm) 174.8,
13H), 0.84 (d, J = 6.5 Hz, 3H), 0.60 (d, J = 7.0 Hz, 3H), 0.43 (d, J 167.4, 159.9, 138.9, 132.0, 129.5, 129.3, 126.7, 125.2, 113.6,
= 7.0 Hz, 3H); the other isomer: 7.91 – 7.89 (m, 2H), 7.49 – 75.8, 55.4, 53.6, 28.1; HRMS (TOF MS ESI+) calculated for
7.47 (m, 2H), 7.38 – 7.19 (comp, 6H), 4.55 (td, J = 10.9, 4.2 Hz, C20H18BrNNaO5S[M+Na]+: 485.9981, found 485.9972.
o
1
1H), 2.50 – 0.76 (comp, 13H), 0.87 (d, J = 6.4 Hz, 3H), 0.71 (d, J
Spectral data of compound 3gh. White solid, mp: 65.6-66.3
= 6.8 Hz, 3H), 0.39 (d, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.75 – 7.67 (m, 2H), 7.42
(δ, ppm) combination of the two isomers: 174.6, 174.4, 166.9, – 7.36 (m, 2H), 7.24 – 7.17 (m, 2H), 6.90 – 6.84 (m, 2H), 3.81 (s,
166.8, 138.1, 137.7, 135.0, 134.6, 130.4, 130.3, 130.25, 130.0, 3H), 3.63 (s, 3H), 2.54 (comp, 4H); 13C NMR (100 MHz, CDCl3) (δ,
128.8, 128.6, 128.4, 128.3, 127.9, 127.8, 127.5, 77.8, 77.4, 77.2, ppm) 174.9, 167.4, 159.9, 138.7, 136.9, 129.4, 129.0, 128.7,
76.6, 47.4, 47.2, 39.9, 34.2, 31.5, 28.0, 25.6, 24.9, 23.2, 22.7, 126.7, 113.6, 75.9, 55.4, 53.6, 28.1; HRMS (TOF MS ESI+)
22.1, 22.0, 21.0, 20.8, 15.7, 15.4; HRMS (TOF MS ESI+) calculated for C20H18ClNNaO5S[M+Na]+: 442.0492, found
calculated for C28H33NNaO4S [M+Na]+:502.2028, found 442.0481.
502.2013.
Spectral data of compound 3gi. White solid, mp: 45.3-46.6
Spectral data of compound 3gb. White solid, mp: 78.6-79.7 oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.76 – 7.67 (m, 2H), 7.50
oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.79 – 7.68 (m, 2H), 7.35 – 7.42 (m, 2H), 6.99 – 6.83 (comp, 4H), 3.81 (s, 3H), 3.63 (s, 1H),
(d, J = 8.0 Hz, 2H), 7.05 (d, J = 8.0 Hz, 2H), 6.87 (d, J = 9.0 Hz, 2.62 – 2.45 (comp, 4H); 13C NMR (100 MHz, CDCl3) (δ, ppm)
2H), 3.80 (s, 3H), 3.62 (s, 1H), 2.54 – 2.41 (m, 4H), 2.30 (s, 3H); 174.8, 167.6, 164.3 (d, J = 251.8 Hz), 159.9, 139.7 (d, J = 8.7 Hz),
13C NMR (100 MHz, CDCl3) (δ, ppm) 174.8, 167.7, 159.8, 140.8, 129.4, 126.7, 125.6 (d, J = 3.4 Hz), 116.0 (d, J = 21.7 Hz), 113.6,
137.6, 129.6, 129.4, 126.9, 126.6, 113.4, 75.9, 55.3, 53.5, 28.0, 75.9, 55.4, 53.6, 28.1; HRMS (TOF MS ESI+) calculated for
21.4; HRMS (TOF MS ESI+) calculated for C21H21NNaO5S C20H18FNNaO5S[M+Na]+: 426.0787, found 426.0773.
[M+Na]+:422.1038, found 422.1024.
Spectral data of compound 3gc. White solid, mp: 131.8- oC. H NMR (400 MHz, CDCl3) (δ, ppm) 7.61 (d, J = 9.0 Hz, 2H),
Spectral data of compound 3gj. White solid, mp: 45.3-46.6
1
o
1
132.4 C. H NMR (400 MHz, CDCl3) (δ, ppm) 7.81 – 7.75 (m, 7.29 (comp, 4H), 7.21 (t, J = 7.0 Hz, 1H), 6.89 (d, J = 9.0 Hz, 2H),
2H), 7.38 (dd, J = 7.7, 1.0 Hz, 1H), 7.25 – 7.20 (m, 1H), 7.16 (d, J 3.86 (q, J = 14.2 Hz, 2H), 3.81 (s, 3H), 3.71 (s, 3H), 2.34 (comp,
= 6.9 Hz, 1H), 7.06 – 6.99 (m, 1H), 6.90 – 6.83 (m, 2H), 3.81 (s, 4H); 13C NMR (100 MHz, CDCl3) (δ, ppm) 175.6, 167.8, 159.8,
3H), 3.55 (s, 3H), 2.46 (comp, 4H), 2.41 (s, 3H); 13C NMR (100 136.5, 131.5, 129.5, 129.1, 128.6, 127.3, 125.6, 114.0, 113.7,
MHz, CDCl3) (δ, ppm) 174.9, 167.7, 159.8, 145.3, 138.8, 130.6, 73.3, 55.4, 53.7, 35.4, 28.2. HRMS (TOF MS ESI+) calculated for
130.3, 130.2, 129.7, 127.6, 125.9, 113.3, 75.6, 55.4, 53.3, 28.1, C21H22NO5S [M+Na]+: 422.1038, found 422.1040.
21.6; HRMS (TOF MS ESI+) calculated for C21H21NNaO5S[M+Na]+:
422.1038, found 422.1024.
Spectral data of compound 3gk. Colorless oil
MHz, CDCl3) (δ, ppm) 7.59 – 7.55 (m, 2H), 6.89 – 6.83 (m, 2H),
.
1H NMR (400
Spectral data of compound 3gd. White solid, mp: 146.8- 3.80 (s, 3H), 3.74 (s, 3H), 2.77 (s, 4H), 2.54 – 2.41 (m, 2H), 1.54
o
1
147.1 C. H NMR (400 MHz, CDCl3) (δ, ppm) 7.79 – 7.70 (m, – 1.47 (m, 2H), 1.30 (comp, 4H), 0.86 (t, J = 7.1 Hz, 3H); 13C
2H), 7.29 (d, J = 8.9 Hz, 2H), 7.14 (m, 2H), 6.91 – 6.85 (m, 2H), NMR (100 MHz, CDCl3) (δ, ppm) 175.7 167.7, 159.8, 129.7,
3.82 (s, 3H), 3.63 (s, 3H), 2.46 (comp, 4H), 2.27 (s, 3H); 13C NMR 126.1, 113.6, 73.0, 55.4, 53.6, 31.5, 31.3, 28.4, 28.1, 22.4, 14.0;
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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Organic & Biomolecular Chemistry
Page 6 of 8
ARTICLE
Journal Name
HRMS (TOF MS ESI+) calculated for C20H19NaNO5S[M+Na]+: Procedure for the synthesis of 6
View Article Online
DOI: 10.1039/C7OB02488F
402.1351, found 402.1352.
To a 10-mL oven-dried vial containing a magnetic stirring bar,
3ga (77 mg, 0.2 mmol) in MeOH (2.0 mL), was added 85%
hydrazine hydrate (64 uL, 1.0 mmol) dropwise over 2 min at 0
Spectral data of compound 3gl. White solid, mp: 42.2-44.4
oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.60 – 7.54 (m, 2H), 6.90
– 6.83 (m, 2H), 3.80 (s, 3H), 3.74 (s, 3H), 2.77 (s, 4H), 2.54 –
2.38 (m, 2H), 1.56 – 1.44 (m, 2H), 1.35 – 1.22 (m, 14H), 0.87 (t,
J = 6.9 Hz, 3H);13C NMR (100 MHz, CDCl3) (δ, ppm) 175.7, 167.7,
159.8, 129.7, 126.1, 113.6, 73.0, 55.4, 53.6, 32.0, 31.6, 29.7,
29.6, 29.4, 29.4, 29.1, 28.4, 28.39, 22.8, 14.2; HRMS (TOF MS
ESI+) calculated for C24H35NNaO5S[M+Na]+: 472.2134, found
472.2132.
o
oC under stirring. The reaction mixture was stirred at 0 C for
additional 1 h, and then warmed up to room temperature and
reacted overnight. After the reaction completed, the solvents
were removed in vacuo and the residue was dissolved in water
(8.0 mL), the pH of solution was then adjusted to 1-2 by adding
o
1N HCl at 0 C. The mixture was stirred for 1h at room
temperature, and then filtered. The filtrate was treated with
solid Na2CO3 until the pH reached at 11-12. The mixture was
extracted with CH2Cl2 (5.0 mL x 3). The combined extracts
Spectral data of compound 3am 6a 1
H NMR (400 MHz, CDCl3)
.
(δ, ppm) 7.90 (d, J = 6.8 Hz, 2H), 7.69 (s, 4H), 7.41 – 7.33 (m,
3H), 7.30 (d, J = 8.0 Hz, 2H), 6.80 (d, J = 7.9 Hz, 2H), 3.69 (s, 3H),
2.16 (s, 3H); 13C NMR (100 MHz, CDCl3) (δ, ppm) 168.0, 166.4,
140.5, 137.7, 135.4, 134.3, 131.4, 129.5, 128.7, 128.1, 128.1,
126.2, 123.3, 76.5, 53.6, 21.3.
were dried over Na2SO4, concentrated and dried in vacuo after
1
in 73% yield (28.4 mg). H
filtration to provide a yellow oil
6
NMR (400 MHz, CDCl3) (δ ppm) 7.26 – 7.22 (m, 2H), 7.03 – 6.98
(m, 2H), 6.21 (s, 1H), 3.84 (s, 3H), 3.83 (s, 3H); 13C NMR (100
MHz, CDCl3) (δ ppm) 165.2, 160.4, 137.4, 130.4, 121.4, 114.8,
55.5, 52.5. HRMS (TOF MS CI+) calculated for C10H12NO3[M+H]+:
194.0817, found 194.0818.
Spectral data of compound 3an 6a 1
H NMR (400 MHz, CDCl3)
.
(δ, ppm) 7.89 (d, J = 7.0 Hz, 2H), 7.69 (s, 4H), 7.37 (comp, 5H),
6.51 (d, J = 8.6 Hz, 2H), 3.69 (s, 3H), 3.63 (s, 3H); 13C NMR (100
MHz, CDCl3) (δ, ppm) 168.0, 166.4, 161.3, 139.4, 135.4, 134.3,
131.3, 128.6, 128.1, 128.0, 123.3, 120.4, 114.2, 76.5, 55.3, 53.6.
Spectral data of compound 3go 6a 1
H NMR (400 MHz, CDCl3)
.
Conflicts of interest
(δ, ppm) 7.83 (d, J = 9.0 Hz, 2H), 7.68 (s, 4H), 7.42 (d, J = 7.1 Hz,
2H), 7.17 (t, J = 7.5 Hz, 1H), 7.00 (t, J = 7.7 Hz, 2H), 6.90 (d, J =
9.0 Hz, 2H), 3.82 (s, 3H), 3.69 (s, 3H).13C NMR (100 MHz, CDCl3)
(δ, ppm) 168.1, 166.4, 159.9, 137.7, 134.3, 131.3, 130.0, 129.9,
129.6, 128.7, 127.0, 123.3, 113.5, 76.3, 55.4, 53.6.
There are no conflicts to declare.
Acknowledgements
Spectral data of compound 3ab 6a 1
H NMR (400 MHz, CDCl3) Support for this research from the National Natural Science
.
(δ, ppm) 7.84 – 7.77 (m, 2H), 7.35 (comp, 5H), 7.05 (d, J = 7.9 Foundation of China and NSFC of Jiangsu (NSFC21602148, and
Hz, 2H), 3.63 (s, 3H), 2.48 (comp, 4H), 2.31 (s, 3H); 13C NMR BK20150315), the Priority Academic Program Development
(100 MHz, CDCl3) (δ, ppm) 174.8, 167.7, 140.9, 137.8, 135.1, (PAPD) of Jiangsu Higher Education Institutions and the project
129.6, 128.7, 128.1, 128.0, 126.4, 76.3, 53.6, 28.1, 21.5; HRMS of scientific and technologic infrastructure of Suzhou
(TOF MS ESI+) calculated for C20H19NNaO4S[M+Na]+: 392.0932, (SZS201708) are gratefully acknowledged.
found 392.0919.
Spectral data of compound 3ae. White solid, mp: 60.0-61.0
oC. 1H NMR (400 MHz, CDCl3) (δ, ppm) 7.83 – 7.76 (m, 2H), 7.43
– 7.39 (m, 2H), 7.38 – 7.32 (m, 3H), 6.79 – 6.74 (m, 2H), 3.76 (s,
3H), 3.64 (s, 3H), 2.52 – 2.48 (comp, 4H); 13C NMR (100 MHz,
CDCl3) (δ, ppm) 174.8, 167.7, 161.6, 139.4, 135.1, 128.7, 128.2,
127.9, 120.6, 114.3, 76.4, 55.5, 53.6, 28.1; HRMS (TOF MS ESI+)
calculated for C20H19NNaO5S[M+Na]+: 408.0882, found
408.0872.
Notes and references
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Spectral data of compound 3oe. White solid, mp: 66.1-66.8
1
oC. H NMR (400 MHz, CDCl3) (δ, ppm) 7.43 (d, J = 8.8 Hz, 2H),
7.30 (comp, 5H), 7.18 (d, J = 8.3 Hz, 2H), 7.08 (d, J = 8.4 Hz, 2H),
6.90 (d, J = 8.8 Hz, 2H), 6.49 (s, 1H), 3.82 (s, 3H), 2.72 (s, 4H);
13C NMR (100 MHz, CDCl3) (δ, ppm) 176.8 160.2, 138.8, 137.5,
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Spectral data of compound 3qo.6a 1H NMR (400 MHz, CDCl3)
(δ, ppm) 8.10 – 8.02 (m, 1H), 7.73 – 7.64 (m, 4H), 7.45 – 7.38
(m, 2H), 7.26 – 7.19 (m, 2H), 7.15 – 7.08 (m, 2H), 6.96 (t, J = 7.7
Hz, 2H), 3.78 (s, 3H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) (δ,
ppm) 167.9, 166.3, 137.7, 137.1, 134.4, 133.6, 132.9, 131.2,
130.2, 129.9, 129.0, 128.6, 128.4, 125.9, 123.4, 77.3, 53.8, 21.7.
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Organic & Biomolecular Chemistry
Journal Name
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Organic & Biomolecular Chemistry
Page 8 of 8
ARTICLE
Journal Name
TOC
View Article Online
DOI: 10.1039/C7OB02488F
A metal-free gem-functionalization reaction of diazo compounds
via a formal N–S bond insert process under mild conditions is
presented
8 | J. Name., 2012, 00, 1-3
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