Two-Step Synthesis of Unsymmetrical Diaryl Sulfides by Electrophilic Thiolation of Non-functionalized (Hetero)arenes

Article abstract of DOI:10.1002/chem.201802806

This article reports the efficient preparation of a series of unsymmetrically substituted thioethers through a two-step procedure consisting of an initial metal-free C?H sulfenylation of electron-rich (hetero)arenes with newly prepared succinylthioimidazolium salts. Subsequent reaction of the arylthioimidazolium intermediates with Grignard reagents afford the desired thioethers. The synthetic protocol described is modular, scalable, and high yielding, and provides access to sulfides that are not easy to obtain through the existing methodologies. Importantly, no prefunctionalization of the initial (hetero)arene is required.

Full text of DOI:10.1002/chem.201802806

A Journal of
Accepted Article
Title: Two-Step Synthesis of Unsymmetrical Diaryl Sulfides via
Electrophilic Thiolation of Non-Functionalized Hetero(arenes)
Authors: Manuel Alcarazo, Marvin J. Böhm, Christopher Golz, and
Isabelle Rüter
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To be cited as: Chem. Eur. J. 10.1002/chem.201802806
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10.1002/chem.201802806
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Two-Step Synthesis of Unsymmetrical Diaryl Sulfides via
Electrophilic Thiolation of Non-Functionalized (Hetero)arenes
Marvin J. Böhm, Christopher Golz, Isabelle Rüter and Manuel Alcarazo*[a]
Abstract: This article reports the efficient preparation of a series of
unsymmetrically substituted thioethers through a two-step procedure
consisting of an initial metal-free C-H sulfenylation of electron-rich
(hetero)arenes with newly prepared succinylthioimidazolium salts.
Subsequent reaction of the arylthioimidazolium intermediates with
Grignards affords the desired thioethers. The synthetic protocol
described is modular, scalable and highly yielding, and provides
access to sulfides that are not easy to obtain through the existing
methodologies. Importantly, no prefunctionalization of the initial
(hetero)arene is required.
sulfenylation protocols very often require the preparation of a
new reagent for each [R-S+] moiety to be transferred to an
organic group (Scheme 1c).
Having recognized the advantages, but also the limitations of
metal-free approaches, we hypothesised about the possible
development of a generally applicable an easy to handle [S+2]
synthon, which might be used for the preparation of a broad
family of unsymmetrically substituted thioethers by consecutive
reaction with two different nucleophiles. Herein, we bring into
practice that idea by the synthesis and use of succinyl-
thioimidazolium salts 1. As it is described below, compound 1 is
able to react with
a
broad range of unfunctionalized
(hetero)aromatic rings via C-H sulfenylation to afford arylthio-
imidazolium salts. Reaction of these intermediates with
Grignards of different structures delivers the desired thioethers
in moderate to excellent yields (Scheme 1d).
Introduction
The abundance of natural products in which sulfur-containing
moieties are present,[1] together with the number of applications
that organosulfur compounds have found in seemly unrelated
fields such as drug development,[2] organic materials,[3] ligand
design[ 4 ] or polymer science,[ 5 ] makes versatile methods to
introduce sulfur containing moieties in organic molecules of
enormous synthetic interest (Scheme 1a). Among these, the
metal-catalysed cross-coupling reaction between thiols and
organic halides has attracted considerable attention since it
allows the synthesis of unsymmetrically substituted aryl sulfides
from easy available thiols and aryl halides or pseudohalides.[6]
Many advances have been achieved in this reaction, being
probably the replacement of the originally used Pd- and Ir-based
catalysts[7] by more abundant first row transition metals the most
prominent one (Scheme 1b).[ 8 ] Despite of this success the
employment of metal catalysts is not always exempt of
problems; they often suffer from the necessity of pre-
functionalised substrates and, if they are used at late stages of a
synthesis, the possibility of contamination of the final product
with toxic metal impurities is a serious issue.[9]
Selected molecules containing diarylsulfide moieties
a)
HO
S
O
O
N
S
N
Me
Me
.HCl
Me
AZD4407
Me
S
5-lipoxygenase
inhibitor
S
O
N
tBu
N
S
S
S
Fe
Ph
chiral ligands
thioridazine
anti-psychotic
BTBT
semiconductor
Cross-coupling approach
b)
Transition metal
X
S
Base
R'
R'-SH
R
R
R
Ligand, high T
X = halide
Electrophilc sulfenylation approach
c)
d)
H
S
Metal-free
R'
S
R
R'
LG
Metal-free alternatives for the synthesis of diaryl sulfides
have also been described. Very often these reactions consist of
the attack of sulfur electrophiles to (hetero)arenes through a
typical electrophilic aromatic substitution mechanism affording
the products of C-H sulfenylation.[10] This approach avoids any
pre-functionalization on the ring which suffers the electrophilic
attack; however, because most of the electrophilic sulfur
LG = SO2Na, succinimide, Cl, SPh...
This work:
Double electrophilic attack at sulfur
O
X
H
LG1
R'
LG2
N
S
S
X
S
1
R
O
R'-MgBr
iPr
iPr
N
N
Metal-free
reagents available, namely, N-thiosuccinimides,[
sulfonyl
11
]
R
R
Me
Me
chlorides,[12] sodium sulfinates[13] or sulfonium triflates[14] lack of
enough reactivity, the scope of the transformation is limited to
electron rich aromatic substrates. It is also of note that these
LG2
Scheme 1. The importance of unsymmetrical diaryl sulfides and different
approaches towards their synthesis.
[a]
M. Sc. Marvin Böhm, Dr. C. Golz, B. Sc. I. Rüter, and Prof. Dr. M.
Alcarazo
Results and Discussion
Institut für Organische und Biomolekulare Chemie
Georg-August-Universität Göttingen
Tammannstr. 2, 37077-Göttingen
Synthesis of succinylthioimidazolium salts. Inspired by the
oxidation of imidazole derived thione 2 by halogens to afford
E-mail: malcara@gwdg.de
[
15 ]
dihalosulfuranes 3,
and recognizing the ability of the
Supporting information for this article is given via a link at the end of
the document.
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10.1002/chem.201802806
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succinimide group to carry out the umpolung of the moieties
bonded to its nitrogen atom, we initially tested the oxidation of
thiourea 2 with N-chlorosuccinimide as a source for the desired
[S+2] synthon. To our satisfaction this reaction afforded
succinylthioimidazolium salt 1·Cl in excellent yield as a slightly
hygroscopic yellow solid, whose solid state structure was
determined by X-ray diffraction (Scheme 2).[16] Anion exchange
to hexafluoroantimonate with an excess of NaSbF6 allows the
isolation of 1·SbF6, a crystalline material which is easier to
handle. This synthetic route towards 1·SbF6 has been scaled up
to multigram quantities without compromising the yield of the
product.
the substrate. The sulfenylation protocol does not seems to be
affected by ethers, esters, amides or even acidic or basic
functionalities already present in the substrates such as free
alcohols, carboxylic acids or unprotected amino groups.
Unfortunately, under the optimized conditions only traces of the
desired products were obtained when furans, benzofurans or
anisole were employed as nucleophiles. This still remains as the
main limitation of the method.
CH3CN, 70°C
R-H + 1
R-SIm
SIm
SIm
OH
SIm
SIm
S
Br
S
Br
R
N
N
Ph
N
N
Me
H
Br2
iPr
iPr
iPr
iPr
N
N
H
N
N
a
a
a
b
8
; 81%
4
5
ref. 15
; 85%
; 60%
6
7
; R = H, 98%
Me
Me
a
Me
Me
; R = Ph, 72%
2
3
SIm
SIm
MeO
O
O
N
O
SIm
S
S
Cl
iPr
N
N
Me
OR
MeO
H
a)
iPr
12
;
61%b
N
N
a
a
9
; R = H, 80%
11
; 60%
a
10
; R = Et, 91%
Me
Me
H2N
Me2N
1.Cl
1.
SIm
b)
SbF6
OMe
Scheme 2. Synthesis and
S
MeO
molecular structure of succinylthioimidazolium chloride 1.Cl. Reagents and
conditions: a) NCS (1.0 equiv.), CH2Cl2, r.t., 98%; b) NaSbF6 (1.5 equiv.),
CH2Cl2, r.t., 92%.
b
SIm
; 52%
SIm
14
; 91%
b
b
13
; 90%
15
MeHN
OMe
=
S
ImS
SIm
iPr
iPr
N
N
MeO
17
In the solid state compound 1·Cl adopts a slightly distorted
T-shape. The N3-S1-Cl1 distribution is nearly linear (178.0°),
being the chloride anion slightly bent onto the top of the
positively charged imidazolium moiety (Cl1-S1-C1 angle 78.6°).
It is also worth noting that while the N3-S1 bond distance
(1.724(9) Å) corresponds to the typical one between these two
elements,[17] the S1-Cl1 interatomic distance (3.024(4) Å) is 15%
shorter than the sum of the van der Waals radii Cl-S (3.55 Å).
SIm
Me
Me
or Cl
b
a
; 58%
16
; 43%
SbF6
Scheme 3. Substrate scope of the electrophilic C-H sulfenylation; a1.Cl was
employed as sulfenylation reagent followed by anion exchange with NaSbF6; b
1.SbF6 was employed as sulfenylation reagent.
Figure 1 depicts the X-ray structures of compounds 8 and
13 (See the Supplementary Information for the analysis of 4, 6, 7,
9, 10, 11, 14 and 16).[16] All these salts feature similar attributes;
namely, an angular geometry with C4-S1-C1 bond angles in
between 100.0 and 105.0°, and C1-S1 bond distances in the
range of 1.740-1.770 Å as expected for single C-S bonds.
The hypercoordination of the S-atom in
consequence of its very strong electrophilic character in that
particular environment.
1 is a direct
Synthesis of arylthioimidazolium salts. Once an efficient
synthesis was available for 1, the following studies were focused
on establishing its reactivity towards aromatic structures. Initially,
1-methylindole was used as model substrate. To our delight, the
product of direct sulfenylation 4 was isolated in 98% yield when
the reaction was performed in acetonitrile at 70 °C (See the
Supporting Information for the optimization details). At lower
temperatures and employing other solvents the reaction was
sluggish, probably due to the lower solubility of salt 1·SbF6 under
these conditions. The scope and generality of the reaction was
subsequently investigated (Scheme 3). We were glad to see that
the electrophilic sulfenylation proceeds with a variety of other
electron rich aromatics, including substituted pyrroles 4-5,
indoles 6-11, (benzo)thiophenes 12-13, anilines 14-16, and even
anisole derivatives 17. Only one product was detected in all
cases, being the regioselectivity determined by the electronics of
Figure 1. Molecular structures of compounds
8 (left) and 13 (right).
Anisotropic displacement parameter shown at 50% probability level. Hydrogen
atoms and hexafluoroantimonate anions omitted for clarity.[16]
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10.1002/chem.201802806
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Scheme 4. Substrate scope of the reaction of imidazolium sulfides with
Grignards. All yields are of isolated products. Reaction conditions: a 1.5 equiv.
Grignard; b2.9 equiv. Grignard; c2.9 equiv. Grignard, LiCl, d5.0 equiv. Grignard;
e1.5 equiv. R-Li.
Synthesis of unsymmetrical diaryl sulfides. With this
selection of arylthioimidazolium salts in hand, we started a
preliminary exploration to identify possible nucleophiles that
could attack at the sulfur atom of these molecules and promote
THF
R-SIm + R'-MgBr
R-S-R'
-78 °C
r.t.
the release of the N-heterocyclic carbene, with the concomitant
formation of the desired diaryl-, alkenyl(aryl)-, or akyl(aryl)sulfide.
After some screening (see the Supporting Information for the
optimization details), it was gratifying to find that a variety of
Grignard reagents were suitable for that transformation, and
afforded in satisfactory yields a complete set of structurally
differentiated thioethers containing aryl-, heteroaryl-, alkenyl-
and/or alkyl-substituents directly attached to the sulfur atom 18-
49 (Scheme 4).[18] As standard conditions 1.5 equivalents of the
desired organo-magnesium reagent in THF were used; note
however that if acidic protons were present in the initial
imidazolium thioether, such as in the case of unprotected pyrrole
29 or indole ring 32, then additional equivalents of the
organometallic nucleophile were employed.
a) with (hetero)aryl Grignards
R
O
iPr
O
S
S
S
N
N
N
Me
Ph
Ph
Ph
a
a
e
18
19
20
21
22
23
; R = OMe, 94%
; 89%
; 72%
a
O
Me
Me
H
; R = F, 67%
O
a
; R = CN, 56%
O
tBu, 26%b
O
O
; R = CO2
S
N
Me
Me
O
Ph
Br
b
OMe
24
; 53%
N
S
N
c
25
; 54%
The functional group tolerance of this two-step synthesis is
inevitably limited by the high reactivity of the Grignard reagents
used. These are necessary to displace the carbene moiety from
arylthioimidazolium salts 4-17. All our attempts to use softer
organozinc reagents for this step were unsuccessful. On the
other hand it is noteworthy that the employment of Grignards
prepared following Knochel conditions partially alleviates this
inconvenient and allows the accommodation of additional
functionalities on the final thioether.[19] Hence, nitriles 20, esters
21 or even pyridine derivatives 25 and 28, which may be easily
modified in subsequent steps, could be installed as substituents.
Liberation of the carbene, either free or more probably as a Mg
complex could be confirmed by the detection of the
corresponding selenourea when the reaction mixtures are
quenched with excess of Se powder. Figure 2 shows the
molecular diagrams of compounds 27 and 32 obtained by X-ray
diffraction experiments; they confirm the expected connectivity
(For the solid state structures of sulfides 19, 20, 26 and 31 see
the Supplementary Information).
Ph
N
Ph
S
N
a
26
; 74%
S
Br
S
N
N
S
c
N
28
; 31%
Ph
c
S
27
Ph
; 79%
OMe
Ph
S
OMe
COOH
R
N
Me
N
MeO
S
a
H
N
30
; R = H; 87%
c
b
b
H
31
; R = Ph; 33%
32
; 61%
29
MeO
; 65%
S
OMe
OMe
Me
S
N
S
b
a
OMe
33
, 76%
NMe2
34
; 85%
NMe2
MeO
S
S
S
S
a
35
; 41%
R
MeO
d
36
; R = H, 65%
37
; R = Me, 75%
38
; R = OMe, 90%
Me
MeO
d
b
O
OMe
iPr
a S
OMe
40
; 50%
b
39
; 51%
Me
b) with alkyl/alkenyl Grignards
Me
R
Me
S
S
S
S
N
N
N
N
Ph
Ph
Ph
Ph
b
b
b
41
42
b
43
; 83%
; R = iPr, 64%
44
; 91%
45
; 88%
Figure 2. Molecular structures of compounds 27 (left) and 32 (right).
Anisotropic displacement parameter shown at 50% probability level. Hydrogen
atoms and solvent molecules omitted for clarity. [16]
e
e
; R = sBu, 67%
Me2N
Me2N
nBu
S
R
S
b
S
Me
47
48
; R = iPr, 94%
N
46
; 67%
d
b
49
; 89%
; R = cyclopentyl, 62%
Me
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Keen to underscore the utility of the synthetic method
described, we turned our attention to studying its possible
extension to the preparation of diaryl substituted selenides. With
this idea in mind selenourea 50 was subjected to oxidation with
N-chlorosuccinimide to afford succinylselenoimidazolium salt
51·Cl as an orange solid in excellent yield.[20] Interestingly, when
this compound was made react with electron rich arenes (N,N-
dimethylamino benzene) or heteroarenes (N-methylindole, N-
phenylpyrrol), the corresponding products of electrophilic
selenylation 52-54 were isolated in moderate yields as pale
yellow solids, which could be handled in air for short times
without evident decomposition (Scheme 5). As in the
sulfenylation case the reaction is regioselective, being only the
most electron rich carbon atom of the substrate the one that
suffers the electrophilic substitution.
Finally, the reaction of 52-54 with Grignards proceeded in a
similar manner to that observed for the sulfide analogues
allowing the isolation of asymmetrically substituted diaryl
selenides. Following this procedure compounds 55-58 were
prepared as illustrative examples (Scheme 6).
+ R'MgBr
R-SeIm
R-Se-R'
Me
MeO
Me
N
Me
N
Ph
Me
N
Se
Se
Se
Se
N
Me
MeO
63%a
MeO
81%b
74%a
92%a
O
57;
55;
58;
56;
=
N
O
N
Se
ImSe
Se
Cl
iPr
Scheme 6. Substrate scope of the reaction of imidazolium selenides with
Grignards. All yields are of isolated products. Reaction conditions: a 1.5 equiv.
Grignard, THF, -78 °C→r.t.; b2.9 equiv. Grignard, THF, -78 °C→r.t.
SbF6
a)
Se
iPr
iPr
iPr
N
N
N
iPr
iPr
N
N
Me
Me
Me
Me
b)
50
51
Me
Me
Conclusions
This article describes a general and efficient protocol for the
electrophilic C-H sulfenylation or selenylation of a variety of
(hetero)arenes by using inexpensive succinylthio- or succinyl-
selenoimidazolium salts as sulfur or selenium sources.
Subsequent reaction of these salts with Grignards affords
asymmetrically substituted organic sulfides and selenides of
different structures. A total of 35 examples are provided. We
conclude from these experiments that succinylthio- or
succinylselenoimidazolium salts behave as efficient [S+2]- and
[Se+2]-synthons, respectively.
Me
ImSe
N
N
Ph
48%
Me
ImSe
N
ImSe
Me
56%
53;
60%
54;
52;
Scheme 5. Synthesis of 51 and substrate scope of the electrophilic C-H
selenylation. All yields are of isolated products. Reaction conditions: a NCS,
CH3CN, rt, quant.; bArene (1.0 equiv.), CH3CN, 70 °C, 19h, and then NaSbF6.
The unambiguous establishment of the connectivity of 54
was possible by X-ray analysis. Suitable single crystals were
grown by slow diffusion of diethyl ether into a saturated
dichloromethane solution of this salt (Figure 3). In the solid state
the Se centre of 54 features an acuter angle around (C4-Se1-C1,
99.82°) if compared with those of 8 and 13, which probably
derives from the decreased tendency towards hybridization of
the heavier atoms in a group. A short contact between F1 and
Se1 was additionally observed (3.209(1)Å); this is surely a
consequence of the high electrophilicity of the selenium atom in
this compound.[18]
Experimental Section
Synthesis of 1·Cl: N-Chlorosuccinimide (134mg, 1.00 mmol) was added
to a solution of 2 (212 mg, 1.00 mmol) in DCE (10 mL) and the yellow
solution obtained was stirred for two hours at rt. After this the solvent was
removed in vacuo and 1·Cl was isolated as a light yellow solid (346 mg,
1.00 mmol, 98%). 1H NMR (300 MHz, CD2Cl2, ppm) δ = 1.62 (d, J = 7.0
Hz, 12H), 2.39 (s, 6H), 2.78 (s, 4H), 6.20 (hept, J = 7.1 Hz, 2H); 13C NMR
(75 MHz, CD2Cl2, ppm) δ = 11.2, 21.5, 29.3, 44.5, 54.6, 130.4, 177.0; IR
(ATR, cm-1): 2971, 2941, 1773, 1714, 1610, 1470, 1445, 1422, 1391,
1372, 1346, 1287, 1250, 1216, 1179, 1161, 1132, 1113, 1092, 1010,
943, 906, 869, 820, 802, 752, 664, 644; HRMS (ESI-pos.) calcd. for
C
15H24N3O2S [M+]: 310.1584, found: 310.1584.
Synthesis of 1·SbF6: NaSbF6 (1.94 g, 7.50 mmol, 1.5 equiv.) was added
to a solution of 1·Cl (1.73 g, 5.00 mmol) in MeCN (50 mL) and the yellow
suspension obtained was stirred for five hours. After this, the solvent was
removed in vacuo and the remaining solid extracted with DCM (4 x 50
ml). The organic phases were combined and the solvent was removed to
afford the desired compound 1·SbF6 as a yellow solid (2.51 g, 4.57 mmol,
92%). 1H NMR (300 MHz, CD2Cl2, ppm) δ = 1.57 (d, J = 7.2 Hz, 12H),
2.41 (s, 6H), 2.85 (s, 4 H, 7H), 6.23 (sept, J = 7.2 Hz, 2H); 13C NMR (126
MHz, CD2Cl2, ppm) δ = 11.2, 21.6, 29.3, 55.1, 132.9, 133.5, 176.7; IR
(ATR, cm-1): 2993, 1736, 1597, 1458, 1421, 1397, 1376, 1291, 1270,
Figure 3. Molecular structures of compounds 54. Anisotropic displacement
parameter shown at 50% probability level. Hydrogen atoms and solvent
molecules omitted for clarity. [16]
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1236, 1215, 1131, 1092, 1004, 819, 749; HRMS (ESI-pos.) calcd. for
C
Compound 9: White powder, 80%. 1H NMR (400 MHz, CD2Cl2, ppm) δ =
1.35 (d, J = 7.1 Hz, 12H), 2.34 (s, 6H), 3.21 (s, 2H), 3.85 (d, J = 1.3 Hz,
3H), 3.91 (d, J = 1.0 Hz, 3H), 5.32 – 5.39 (m, 2H), 6.75 (s, 1H), 7.05 (d, J
= 1.8 Hz, 1H);13C NMR (126 MHz, CD2Cl2, ppm) δ = 11.1, 21.3, 56.6,
56.8, 95.9, 98.9, 102.5, 121.9, 127.7, 129.7, 131.5, 138.4, 148.4, 151.4,
161.3; IR (ATR, cm-1): 3255, 1667, 1632, 1621, 1514, 1447, 1425, 1404,
1394, 1375, 1273, 1252, 1206, 1178, 1153, 1112, 1005, 850, 719; HRMS
(ESI-pos.) calcd. for C22H30N3O4S [M+]: 432.1952, found: 432.1947.
15H24N3O2S [M+]: 310.1584, found: 310.1584 .
Representative synthesis of arylthioimidazolium salts. Synthesis of
4: Pyrrole (27 mg, 0.4 mmol) was added to a solution of 1•SbF6 (262 mg,
0.480 mmol, 1.2 equiv.) in MeCN (4 mL) and the yellow solution obtained
heated to 70 °C for 16 h. After this all volatiles were removed in vacuo,
the remaining orange oil was dissolved in DCM (4 mL) and washed with
sat. aq. NaSbF6 (4 mL) for 5 min. After separation of the two phases the
organic layer was dried over MgSO4 and concentrated. Crude 4 was
purified through column chromatography (DCM:MeOH; 100:0→95:5) to
afford 4 as a yellow foam (175 mg, 0.34 mmol, 85%). 1H NMR (300 MHz,
CD2Cl2, ppm) δ = 1.54 (d, J = 7.2 Hz, 12H), 2.34 (s, 6H), 5.50 (hept, J =
7.2 Hz, 2H), 6.20 – 6.26 (m, 1H), 6.46 – 6.52 (m, 1H), 6.95 – 7.03 (m,
1H), 9.37 (s, 1H); 13C NMR (126 MHz, CD2Cl2, ppm) δ = 10.9, 21.4,
109.3, 111.4, 118.9, 124.8, 130.3, 136.2; IR (ATR, cm-1): 3181, 2716,
1772, 1715, 1621, 1603, 1377, 1070, 1051, 714, 649, 608; HRMS (ESI-
pos.) calcd. for C15H24N3S [M+]: 278.1685, found: 278.1686; (ESI-neg.)
Compound 10: Brown foam, 94%. 1H NMR (400 MHz, CD2Cl2, ppm) δ =
1.36 – 1.41 (m, 15H), 2.37 (s, 6H), 3.83 (s, 3H), 3.89 (s, 3H), 4.35 (q, J =
7.2 Hz, 2H), 5.33 – 5.39 (m, 2H), 6.56 (s, 1H), 7.05 (s, 1H); 13C NMR
(101 MHz, CD2Cl2, ppm) δ = 11.0, 14.6, 21.3, 54.1, 56.6, 56.7, 62.2, 95.6,
98.8, 104.6, 121.4, 126.0, 130.1, 131.3, 137.4, 148.7, 152.0, 159.7; IR
(ATR, cm-1): 3415, 2358, 1696, 1515, 1454, 1341, 1263, 1241, 1209,
1180, 1157, 1113, 1033, 1019, 1004, 832, 653; HRMS (ESI-pos.) calcd.
for C24H34N3O4S [M+]: 460.2265, found: 460.2266; (ESI-neg.) calcd. for
SbF6- [M-]: 234.8948, found: 234.8950.
-
calcd. for SbF6 [M-]: 234.8948, found: 234.8951.
Compound 11: Yellow foam, 60%. 1H NMR (300 MHz, CD2Cl2, ppm) δ =
1.49 (d, J = 7.1 Hz, 12H), 2.15 – 2.27 (m, 2H), 2.33 (s, 6H), 2.99 (t, J =
6.1 Hz, 2H), 4.15 – 4.24 (m, 2H), 5.53 – 5.76 (m, 2H), 7.03 (dd, J = 7.2,
1.0 Hz, 1H), 7.18 (dd, J = 8.0, 7.1 Hz, 1H), 7.41 (dd, J = 8.1, 0.9 Hz, 1H),
7.43 (s, 1H); 13C NMR (126 MHz, CD2Cl2, ppm) δ = 10.8, 21.4, 23.3, 24.9,
45.4, 53.7, 95.1, 115.5, 120.7, 122.6, 124.1, 126.6, 129.9, 133.1, 134.8,
138.2; IR (ATR, cm-1): 2941, 1620, 1505, 1467, 1448, 1383, 1325, 1247,
1219, 1168, 1135, 1110, 1034, 906, 827, 786, 750, 653, 601; HRMS
(ESI-pos.) calcd. for C22H30N3S [M+]: 342.1998, found: 342.1999; (ESI-
Compound 5: Yellow solid, 60%. 1H NMR (300 MHz, CD2Cl2 ppm) δ =
1.34 (d, J = 7.1 Hz, 12H), 2.29 (s, 6H), 5.00 (hept, J = 7.1 Hz, 2H), 6.40
(dd, J = 3.9, 3.0 Hz, 1H), 6.68 (dd, J = 3.9, 1.7 Hz, 1H), 7.13 (dd, J = 3.0,
1.8 Hz, 1H), 7.33 – 7.39 (m, 2H), 7.49 – 7.62 (m, 3H); 13C NMR (101
MHz, CD2Cl2, ppm) δ = 10.8, 21.3, 53.8, 111.7, 112.6, 121.9, 126.5,
128.9, 129.4, 130.4, 130.5, 135.8, 138.7; IR (ATR, cm-1): 2994, 1496,
1455, 1437, 1414, 1377, 1319, 1207, 1137, 1110, 1087, 1039, 768, 725,
700, 656, 615, 603; HRMS (ESI-pos.) calcd. for
C
21H28N3S [M+]:
-
-
354.1998, found: 354.2000; (ESI-neg.) calcd. for SbF6 [M-]: 234.8948,
neg.) calcd. for SbF6 [M-]: 234.8948, found: 234.8951.
found: 234.8951.
Compound 12: Yellow foam, 61%. 1H NMR (300 MHz, CD2Cl2, ppm) δ =
1.58 (d, J = 7.1 Hz, 12H), 2.39 (s, 6H), 2.47 (d, J = 1.1 Hz, 3H), 5.48
(hept, J = 7.1 Hz, 2H), 6.76 – 6.79 (m, 1H), 7.23 (d, J = 3.7 Hz, 1H);
13C NMR (75 MHz, CD2Cl2, ppm) δ = 10.9, 16.1, 21.4, 54.1, 121.7, 127.4,
131.0, 137.2, 149.2; IR (ATR, cm-1): 1422, 1396, 1377, 1218, 1138, 1113,
1
Compound 6: Yellow foam, 75%. H NMR (300 MHz, CD2Cl2, ppm) δ =
1.48 (d, J = 7.1 Hz, 12H), 2.33 (s, 6H), 3.84 (s, 3H), 5.54 – 5.66 (m, 2H),
7.27 – 7.39 (m, 2H), 7.40 (s, 1H), 7.43 – 7.47 (m, 1H), 7.61 – 7.66 (m,
1H); 13C NMR (75 MHz, CD2Cl2, ppm) δ = 10.8, 21.3, 33.9, 53.6, 95.6,
111.4, 118.3, 122.2, 123.9, 128.8, 130.1, 135.8, 137.6, 138.0; IR (ATR,
cm-1): 2988, 2363, 1621, 1458, 1417, 1376, 1244, 1113, 738, 657, 631;
HRMS (ESI-pos.) calcd. for C20H28N3S [M+]: 342.1998, found: 342.1999;
(ESI-neg.) calcd. for SbF6- [M-]: 234.8948, found: 234.8952.
1093, 1070, 954, 803, 712, 653, 604; HRMS (ESI-pos.) calcd. for
-
C
16H25N2S2 [M+]: 309.1454, found: 309.1454; (ESI-neg.) calcd. for SbF6
[M-]: 234.8948, found: 234.8950.
Compound 13: Yellow foam, 90%. 1H NMR (300 MHz, CD2Cl2, ppm) δ =
1.28 (d, J = 7.1 Hz, 12H), 2.27 (s, 6H), 3.88 (s, 3H), 3.89 (s, 3H), 5.06
(hept, J = 7.1 Hz, 2H), 7.05 – 7.11 (m, 2H), 7.11 – 7.15 (m, 1H), 7.37 (d,
J = 2.3 Hz, 1H), 7.45 (d, J = 8.9 Hz, 1H), 7.49 – 7.54 (m, 2H); 13C NMR
(126 MHz, CD2Cl2, ppm) δ = 10.9, 21.0, 53.9, 56.1, 56.3, 106.2, 112.1,
115.2, 116.3, 122.4, 124.4, 130.7, 131.7, 133.2, 135.9, 140.1, 149.2,
159.0, 161.7; IR (ATR, cm-1): 2939, 1605, 1529, 1477, 1462, 1440, 1421,
1397, 1378, 1300, 1290, 1248, 1215, 1176, 1112, 1063, 1030, 958, 850,
838, 805, 767, 735, 711, 652, 607; HRMS (ESI-pos.) calcd. for
1
Compound 7: Yellow foam, 72%. H NMR (400 MHz, CD2Cl2, ppm) δ =
1.22 (d, J = 7.1 Hz, 12H), 2.26 (s, 6H), 3.68 (s, 3H), 5.12 (hept, J = 7.1
Hz, 2H), 7.34 (t, J = 7.6 Hz, 1H), 7.38 – 7.45 (m, 3H), 7.54 (dd, J = 18.7,
8.0 Hz, 2H), 7.60 – 7.66 (m, 3H); 13C NMR (126 MHz, CD2Cl2, ppm) δ =
11.0, 21.2, 32.5, 53.7, 94.8, 111.6, 118.1, 122.8, 124.4, 128.7, 129.6,
129.7, 129.9, 130.8, 131.1, 137.9, 138.2, 146.9; IR (ATR, cm-1): 2994,
2942, 1693, 1622, 1465, 1445, 1427, 1396, 1378, 1338, 1294, 1236,
1218, 1157, 1135, 1112, 1020, 803, 745, 710, 650; HRMS (ESI-pos.)
calcd. for C26H32N3S [M+]: 418.2311, found: 418.2310; (ESI-neg.) calcd.
for SbF6- [M-]: 234.8948, found: 234.8952.
C
27H33N2O2S2 [M+]: 481.1978, found: 481.1980; (ESI-neg.) calcd. for
-
SbF6 [M-]: 234.8948, found: 234.8950.
Compound 8: Black foam, 81%. 1H NMR (600 MHz, CD2Cl2, ppm) δ =
1.38 (d, J = 7.1 Hz, 12H), 2.31 (s, 6H), 4.91 (s, 2H), 5.39 – 5.46 (m, 2H),
7.23 – 7.31 (m, 2H), 7.46 – 7.48 (m, 1H), 7.50 (d, J = 8.1 Hz, 1H), 9.45 (s,
1H); 13C NMR (126 MHz, CD2Cl2, ppm) δ = 11.0, 21.2, 53.7, 56.8, 93.7,
113.2, 117.5, 122.4, 124.1, 128.9, 129.9, 135.7, 137.9, 144.0; IR (ATR,
cm-1): 3392, 2983, 1709, 1619, 1448, 1422, 1395, 1376, 1344, 1327,
1293, 1269, 1230, 1216, 1191, 1174, 1151, 1139, 1113, 1074, 1030,
1010, 749, 653; HRMS (ESI-pos.) calcd. for C20H28N3OS [M+]: 358.1948,
Compound 14: Blue foam, 90%. 1H NMR (300 MHz, CD2Cl2, ppm) δ =
1.51 (d, J = 7.1 Hz, 12H), 2.38 (s, 6H), 2.96 (s, 6H), 5.35 – 5.50 (m, 2H),
6.64 – 6.70 (m, 2H), 7.15 – 7.22 (m, 2H); 13C NMR (126 MHz, CD2Cl2,
ppm) δ = 10.9, 21.5, 40.5, 53.9, 112.4, 113.9, 130.4, 133.4, 137.6, 152.0;
IR (ATR, cm-1): 2940, 1596, 1505, 1470 1444, 1426, 1393, 1373, 1360,
1219, 1198, 1172, 1141, 1113, 947, 809, 654, 608; HRMS (ESI-pos.)
calcd. for C19H30N3S [M+]: 332.2155, found: 332.2155; (ESI-neg.) calcd.
-
for SbF6 [M-]: 234.8948, found: 234.8950.
-
found: 358.1953; (ESI-neg.) calcd. for SbF6 [M-]: 234.8948, found:
Compound 15: Yellow oil, 52%. 1H NMR (300 MHz, CD2Cl2, ppm) δ =
1.49 (d, J = 7.1 Hz, 12H), 2.37 (s, 6H), 4.12 (s, 2H), 5.35 (sept, J = 7.1 Hz,
2 H), 6.69 (m, 2H), 7.09 (m, 2H); 13C NMR (75 MHz, CD2Cl2, ppm) δ =
234.8951.
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10.1002/chem.201802806
Chemistry - A European Journal
FULL PAPER
10.8, 21.3, 53.8, 115.2, 116.8, 130.5, 133.4, 137.1, 149.6; IR (ATR, cm-1):
3506, 3407, 2984, 2945, 1620, 1595, 1500, 1415, 1305, 835, 655; HRMS
(ESI-pos.) calcd. for C17H26N3S [M+]: 304.1851, found: 304.1842; (ESI-
Compound 21: Colorless oil, 26%. 1H NMR (600 MHz, CDCl3, ppm) δ =
1.56 (s, 12H), 6.42 (dd, J = 3.7, 3.0 Hz, 1H), 6.76 (dd, J = 3.7, 1.8 Hz,
1H), 6.90 – 6.95 (m, 2H), 7.13 (dd, J = 3.0, 1.8 Hz, 1H), 7.20 – 7.22 (m,
2H), 7.28 – 7.34 (m, 3H), 7.75 – 7.79 (m, 2H); 13C NMR (126 MHz, CDCl3,
ppm) δ = 28.4, 81.0, 110.0, 117.0, 122.0, 124.8, 126.3, 127.1, 127.7,
128.8, 129.8, 139.3, 145.8, 165.5; IR (neat, cm-1): 2978, 2928, 1707,
1590, 1498, 1456, 1435, 1392, 1366, 1318, 1306, 1290, 1255, 1162,
1139, 1118, 1107, 1090, 1035, 1012, 960, 847, 759, 724, 690, 620;
-
neg.) calcd. for SbF6 [M-]: 234.8948, found: 234.8948.
Synthesis of 16: White foam, 43%. 1H NMR (300 MHz, CD2Cl2, ppm) δ
= 1.50 (d, J = 7.1 Hz, 12H), 2.37 (s, 6H), 2.80 (s, 3H), 4.29 (s, 1H), 5.33 –
5.46 (m, 2H), 6.57 – 6.64 (m, 2H), 7.10 – 7.17 (m, 2H); 13C NMR (101
MHz, CD2Cl2, ppm) δ = 10.7, 21.3, 30.5, 53.7, 114.1, 130.4, 133.7, 151.6;
IR (ATR, cm-1): 3438, 2988, 1597, 1509, 1448, 1421, 1397, 1377, 1327,
1216, 1186, 1112, 823, 752; HRMS (ESI-pos.) calcd. for C18H28N3S [M+]:
HRMS (ESI-pos.) calcd. for
C21H28NO2S [M+H]: 352.1366, found:
352.1364.
-
318.1998, found: 318.2003; (ESI-neg.) calcd. for SbF6 [M-]: 234.8948,
Compound 22: Colourless oil, 89%. 1H NMR (400 MHz, CDCl3, ppm) δ =
0.69 (d, J = 6.9 Hz, 3H), 0.82 – 1.01 (m, 9H), 1.22 – 1.40 (m, 2H), 1.56 –
1.70 (m, 2H), 2.12 – 2.19 (m, 1H), 2.20 – 2.31 (m, 1H), 3.13 (td, J = 10.5,
4.1 Hz, 1H), 4.30 (d, J = 11.4 Hz, 1H), 4.56 (d, J = 11.4 Hz, 1H), 6.39 (t, J
= 3.3 Hz, 1H), 6.71 – 6.76 (m, 1H), 6.90 – 6.95 (m, 2H), 7.06 – 7.12 (m,
1H), 7.16 (d, J = 8.2 Hz, 2H), 7.20 – 7.25 (m, 2H), 7.27 – 7.36 (m, 3H);
13C NMR (101 MHz, CDCl3, ppm) δ = 16.2, 21.1, 22.5, 23.4, 25.6, 31.7,
34.7, 40.4, 48.4, 70.1, 78.8, 109.7, 118.5, 121.6, 126.1, 126.4, 126.6,
127.5, 128.6, 128.8, 136.4, 138.6, 139.6; IR (neat, cm-1): 2952, 2918,
2866, 1598, 1498, 1455, 1434, 1319, 1105, 1086, 1073, 1053, 1036,
1015, 834, 804, 760, 721, 692; HRMS (EI-pos.) calcd. for C27H33NOS
[M+]: 419.2283, found: 419.2275.
found: 234.8948.
Synthesis of 17: White solid, 58%. 1H NMR (300 MHz, CD2Cl2, ppm) δ =
1.48 (d, J = 7.1 Hz, 12H), 2.38 (s, 6H), 3.82 (s, 3H), 3.83 (s, 3H), 5.39
(hept, J = 7.1 Hz, 2H), 6.52 – 6.61 (m, 2H), 7.24 (d, J = 8.6 Hz, 1H);
13C NMR (126 MHz, CD2Cl2, ppm) δ = 11.0, 21.5, 54.0, 56.4, 57.0, 100.5,
107.5, 130.6, 134.4, 136.6, 159.9, 163.8; IR (ATR, cm-1): 2945, 2358,
1603, 1590, 1488, 1454, 1437, 1416, 1314, 1286, 1210, 1159, 1116,
1074, 1034, 828, 798, 653; HRMS (ESI-pos.) calcd. for C19H29N2O2S
-
[M+]: 349.1944, found: 349.1947; (ESI-neg.) calcd. for SbF6 [M-]:
234.8948, found: 234.8948.
Compound 23: Light yellow oil, 69%. 1H NMR (500 MHz, CD2Cl2, ppm)
δ = 6.07 (dd, J = 3.3, 0.9 Hz, 1H), 6.23 – 6.28 (m, 2H), 6.63 (dd, J = 3.7,
1.8 Hz, 1H), 6.97 (dd, J = 3.0, 1.8 Hz, 1H), 7.33 – 7.37 (m, 3H), 7.39 –
7.49 (m, 3H); 13C NMR (126 MHz, CD2Cl2, ppm) δ = 109.7, 111.9, 115.5,
119.6, 119.7, 126.5, 127.4, 128.1, 129.3, 140.0, 145.4, 146.0; IR (neat,
cm-1): 1715, 1597, 1498, 1456, 1435, 1391, 1367, 1319, 1213, 1205,
1151, 1136, 1111, 1087, 1073, 1059, 1035, 1004, 958, 905, 880, 762,
720, 692, 656, 634, 615; HRMS (ESI-pos.) calcd. for
Representative synthesis of diaryl-, aryl(alkenyl)-, and aryl(alkyl)
sulfides. Synthesis of 18: Compound 5 (60.2 mg, 0.102 mmol) was
dissolved in THF (1.0 mL) and cooled to -78 °C. Then, a solution of p-
methoxyphenylmagnesium bromide (0.5 M in THF, 306 µL, 0.153 mmol,
1.5 equiv.) was added drop wise and the mixture allowed to warm up to
r.t. overnight. The reaction was then quenched with sat. NH4Cl (5 mL)
and extracted with DCM (3 x 20 mL). Evaporation of the combined
organic phases afforded crude 18, which was subsequently purified by
column chromatography (Hexane:ethylacetate; 80:20). White solid (26.9
mg, 0.10 mmol, 94%). 1H NMR (300 MHz, CDCl3, ppm) δ = 3.74 (s, 3H),
6.35 (dd, J = 3.6, 3.0 Hz, 1H), 6.69 – 6.72 (m, 1H), 6.71 (d, J = 8.9 Hz,
2H), 6.92 (d, J = 8.9 Hz, 2H), 7.03 (dd, J = 3.0, 1.8 Hz, 1H), 7.20 – 7.25
(m, 2H), 7.30 – 7.38 (m, 3H); 13C NMR (75 MHz, CDCl3, ppm) δ = 55.5,
109.5, 114.6, 120.5, 126.2, 126.7, 127.5, 128.7, 129.3, 129.4, 139.7,
158.3; IR (ATR, cm-1): 2958, 2828, 2360, 1597, 1488, 1455, 1449, 1434,
1393, 1322, 1291, 1240, 1204, 1180, 1176, 1162, 1138, 1105, 1088,
1074, 1030, 1003, 962, 821, 808, 796, 762, 724, 692, 651, 636, 619, 605;
HRMS (EI-pos.) calcd. for C17H15NOS [M+]: 281.0874, found: 281.0871.
C14H11NOS [M+Na]: 264.0454, found: 264.0462.
Compound 24: White solid, 76%.Analyticaly pure material could only be
obtained after purification by HPLC with an Agilent Zorbax SB-C18
column using solvent gradient (CH3CN:H2O; 65:35 → 100:0). 1H NMR
(300 MHz, CD2Cl2, ppm) δ = 1.28 (s, 3H), 1.32 (s, 3H), 1.38 (s, 3H), 1.45
(s, 3H), 3.87 – 3.95 (m, 2H), 4.00 – 4.06 (m, 1H), 4.07 – 4.15 (m, 1H),
4.22 – 4.31 (m, 1H), 4.45 – 4.63 (m, 3H), 5.83 (d, J = 3.7 Hz, 1H), 6.40
(dd, J = 3.6, 3.0 Hz, 1H), 6.72 (dd, J = 3.6, 1.8 Hz, 1H), 6.86 – 6.93 (m,
2H), 7.07 - 7.14(m, 3H), 7.20 – 7.39 (m, 5H); 13C NMR (126 MHz, CD2Cl2,
ppm) δ = 25.8, 26.6, 27.1, 27.2, 67.7, 72.3, 73.2, 81.7, 82.3, 83.1, 105.8,
109.3, 110.1, 112.1, 118.6, 121.9, 126.3, 126.8, 127.1, 127.9, 128.8,
129.1, 135.5, 139.5, 139.9; IR (ATR, cm-1): 2917, 2360, 2341, 1595,
1559, 1498, 1456, 1432, 1380, 1372, 1320, 1252, 1214, 1164, 1121,
1075, 1017, 849, 761, 720, 693, 672, 653; HRMS calcd. (EI-pos.) for
Compound 19: White solid, 67% yield. 1H NMR (300 MHz, CDCl3, ppm)
δ = 6.39 (dd, J = 3.6, 3.0 Hz, 1H), 6.74 (dd, J = 3.6, 1.8 Hz, 1H), 6.82 –
6.95 (m, 4H), 7.07 (dd, J = 3.0, 1.8 Hz, 1H), 7.19 – 7.24 (m, 2H), 7.31 –
7.35 (m, 2H); 13C NMR (126 MHz, CDCl3, ppm) δ = 109.6, 115.9 (d, JC-F
= 22.0 Hz), 119.2, 121.1, 126.5, 126.6, 127.6, 128.6 (d, JC-F = 7.9 Hz),
128.7, 133.9, 133.9, 139.4, 161.2 (d, JC-F = 244.5 Hz); 19F NMR (282
MHz, CDCl3, ppm) δ = -117.3; IR (ATR, cm-1): 3048, 2360, 1586, 1487,
1434, 1394, 1317, 1216, 1156, 1134, 1088, 1034, 1010, 822, 806, 763,
749, 730, 722, 692, 649, 617, 604; HRMS (EI-pos.) calcd. for
C
29H33NO6S [M+]: 524.2101, found: 524.2085.
Compound 25: White solid, 54%. 1H NMR (600 MHz, CDCl3, ppm) δ =
6.48 (dd, J = 3.6, 3.0 Hz, 1H), 6.76 (dd, J = 3.7, 1.8 Hz, 1H), 7.16 – 7.26
(m, 3H), 7.39 – 7.44 (m, 3H), 7.56 – 7.61 (m, 2H), 7.71 – 7.74 (m, 1H),
8.06 (s, 1H); 13C NMR (126 MHz, CDCl3, ppm) δ = 109.8, 114.9, 116.5,
121.2, 126.1, 126.4, 126.5, 127.1, 127.2, 127.3, 128.4, 128.6, 129.7,
137.9, 139.9, 146.7, 159.2; IR (ATR, cm-1): 3054, 1541, 1495, 1485,
1365, 1321, 1144, 1133, 1111, 1091, 1036, 954, 906, 878, 863, 769, 748,
719, 693, 686, 676, 649, 601; HRMS (EI-pos.) calcd. for
C
16H12FNS [M+]: 269.0674, found: 269.0671.
Compound 20: Colorless oil, 65%. 1H NMR (300 MHz, CD3CN, ppm) δ =
6.46 (dd, J = 3.7, 3.0 Hz, 1H), 6.77 (dd, J = 3.7, 1.8 Hz, 1H), 6.91 – 6.98
(m, 2H), 7.24 – 7.41 (m, 6H), 7.45 – 7.52 (m, 2H); 13C NMR (126 MHz,
CDCl3, ppm) δ = 108.4, 110.2, 115.8, 118.9, 122.3, 125.5, 126.3, 127.5,
127.9, 128.9, 132.3, 139.0, 147.1; IR (neat, cm-1): 3048, 2225, 1590,
1498, 1482, 1455, 1434, 1394, 1319, 1139, 1077, 1036, 1014, 961, 912,
820, 763, 728, 692, 645, 620, 607; HRMS (EI-pos.) calcd. for
C
19H13BrN2S [M+]: 379.9983, found: 379.9983.
Compound 26: White solid, 74%. 1H NMR (600 MHz, CDCl3, ppm) δ =
3.82 (s, 3H), 6.43 (dd, J = 3.7, 2.9 Hz, 1H), 6.78 (dd, J = 3.7, 1.8 Hz, 1H),
6.86 – 6.92 (m, 4H), 7.12 (dd, J = 3.0, 1.8 Hz, 1H), 7.21 – 7.24 (m, 2H),
7.30 – 7.35 (m, 5H), 7.42 – 7.48 (m, 2H); 13C NMR (126 MHz, CDCl3,
ppm) δ = 55.5, 87.9, 89.6, 109.8, 114.1, 115.4, 117.7, 120.4, 121.7,
C
17H12N2S [M+]: 276.0721, found: 276.0716.
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10.1002/chem.201802806
Chemistry - A European Journal
FULL PAPER
125.7, 126.4, 126.8, 127.6, 128.7, 131.8, 133.0, 139.4, 139.8, 159.6; IR
(ATR, cm-1): 1604, 1509, 1498, 1456, 1436, 1396, 1319, 1286, 1244,
1179, 1172, 1138, 1106, 1031, 1011, 820, 763, 728, 694, 621; HRMS
(EI-pos.) calcd. for C25H19NOS [M+]: 381.1187, found: 381.1186.
4.27 (m, 2H), 6.72 – 6.75 (m, 2H), 6.93 – 7.04 (m, 2H), 7.11 – 7.15 (m,
2H), 7.30 – 7.36 (m, 2H); 13C NMR (126 MHz, CD2Cl2, ppm) δ = 23.5,
25.1, 45.0, 55.8, 102.5, 114.8, 117.1, 119.8, 121.1, 123.0, 127.7, 129.1,
130.6, 132.3, 135.4, 158.3; IR (ATR, cm-1): 2932, 1591, 1490, 1460,
1439, 1379, 1363, 1323, 1284, 1240, 1174, 1163, 1153, 1103, 1030, 958,
822, 777, 748, 608; HRMS (ESI-pos.) calcd. for C18H17NOS [M+H]:
296.1104, found: 296.1094.
Compound 27: White solid, 79%. 1H NMR (300 MHz, CD3CN, ppm) δ =
6.50 (dd, J = 3.8, 3.0 Hz, 1H), 6.93 (dd, J = 3.8, 1.8 Hz, 1H), 7.24 – 7.34
(m, 2H), 7.35 – 7.44 (m, 7H), 7.70 – 7.75 (m, 1H), 7.76 – 7.80 (m, 1H);
13C NMR (126 MHz, CD3CN, ppm) δ 111.3, 116.0, 122.3, 122.5, 123.8,
125.3, 127.2, 127.5, 129.1, 129.6, 129.9, 136.3, 139.7, 155.1, 173.2; IR
(ATR, cm-1): 3054, 2925, 1591, 1495, 1464, 1454, 1428, 1390, 1319,
1237, 1141, 1078, 1068, 1001, 958, 916, 765, 754, 726, 720, 691, 672,
617; HRMS (EI-pos.) calcd. for C17H12N2S2 [M+]: 308.0442, found:
308.0449.
Compound 34: Colorless oil, 85%. 1H NMR (400 MHz, CDCl3, ppm) δ =
2.46 (d, J = 1.1 Hz, 3H), 3.77 (s, 3H), 6.67 (dt, J = 3.5, 1.1 Hz, 1H), 6.79
– 6.85 (m, 2H), 7.05 (d, J = 3.5 Hz, 1H), 7.24 – 7.28 (m, 2H); 13C NMR
(126 MHz, CDCl3, ppm) δ = 15.9, 55.5, 114.7, 125.9, 129.1, 130.6, 130.7,
134.9, 145.3, 158.8; IR (neat, cm-1): 2917, 2831, 1592, 1573, 1490, 1459,
1439, 1285, 1241, 1212, 1172, 1160, 1104, 1065, 1030, 1006, 953, 822,
794, 637, 625; HRMS (EI-pos.) calcd. for C12H12OS2 [M+]: 236.0330,
found: 236.0324.
Compound 28: Colourless oil, 64%. 1H NMR (300 MHz, CDCl3, ppm) δ =
6.39 – 6.43 (m, 1H), 6.77 (ddd, J = 3.7, 1.8, 0.3 Hz, 1H), 7.12 (ddd, J =
3.0, 1.8, 0.3 Hz, 1H), 7.19 – 7.23 (m, 2H), 7.29 (td, J = 2.0, 0.3 Hz, 1H),
7.32 – 7.40 (m, 3H), 8.02 (s, 1H), 8.32 (s, 1H); 13C NMR (126 MHz,
CDCl3, ppm) δ = 110.2, 115.6, 122.0, 126.5, 127.5, 128.0, 128.9, 136.2,
139.0, 144.9, 147.1; IR (neat, cm-1): 3007, 2951, 2844, 1541, 1409, 1369,
1311, 1106, 1085, 1061, 1005, 983, 951, 875, 752, 686, 645; HRMS (EI-
pos.) calcd. for C15H11BrN2S [M+]: 329.9826, found: 329.9821.
Compound 35: White solid, 41%. 1H NMR (300 MHz, CDCl3, ppm) δ =
3.72 (s, 3H), 3.84 (s, 3H), 3.87 (s, 3H), 6.71 – 6.76 (m, 2H), 6.93 – 7.05
(m, 4H), 7.29 – 7.32 (m, 1H), 7.61 – 7.70 (m, 3H); 13C NMR (126 MHz,
CDCl3, ppm) δ = 55.5, 55.5, 55.8, 105.0, 114.0, 114.8, 114.8, 118.4,
124.5, 126.2, 128.2, 128.5, 131.0, 135.2, 137.4, 139.4, 146.1, 157.9,
160.0; IR (ATR, cm-1): 2934, 2832, 1603, 15712, 1557, 1524, 1490, 1471,
1436, 1402, 1299, 1285, 1113, 1062, 985, 905, 820, 803, 766, 731, 647,
636, 621; HRMS (EI-pos.) calcd. for C23H20O2S2 [M+]: 408.0854, found:
408.0854.
Compound 29: White solid, 65%. 1H NMR (300 MHz, CDCl3, ppm) δ =
3.76 (s, 3H), 6.28 (ddd, J = 3.4, 2.5 Hz, 1H), 6.54 (ddd, J = 3.4, 2.5, 1.5
Hz, 1H), 6.76 – 6.85 (m, 2H), 6.86 – 6.93 (m, 1H), 7.05 – 7.12 (m, 2H),
8.26 (s, 1H); 13C NMR (126 MHz, CDCl3, ppm) δ = 55.5, 110.4, 114.8,
117.7, 117.8, 121.5, 128.9, 129.3, 158.4; IR (ATR, cm-1): 3366, 2939,
2836, 1590, 1574, 1490, 1461, 1440, 1405, 1284, 1236, 1174, 1108,
1088, 1074, 1024, 1007, 928, 820, 795, 724, 656, 636, 622; HRMS (ESI-
pos.) calcd. for C11H11NOS [M+H]: 206.0634, found: 206.0630.
Compound 36: Colorless oil, 65%. 1H NMR (300 MHz, CDCl3, ppm) δ =
3.00 (s, 6H), 6.69 – 6.75 (m, 2H), 7.05 – 7.13 (m, 3H), 7.14 – 7.25 (m,
2H), 7.38 – 7.42 (m, 2H); 13C NMR (75 MHz, CDCl3, ppm) δ = 40.5,
113.1, 117.6, 125.1, 127.0, 128.9, 136.3, 140.4, 150.8; IR (neat, cm-1):
2880, 1678, 1592, 1551, 1504, 1475, 1439, 1355, 1314, 1260, 1224,
1193, 1167, 1129, 1100, 1085, 1063, 1023, 998, 944, 906, 811, 765, 736,
689, 644, 621, 610; HRMS (ESI-pos.) calcd. for C14H15NS [M+H]:
230.0998, found: 230.0999.
Compound 30: White solid, 87%. 1H NMR (500 MHz, CDCl3, ppm) δ =
3.73 (s, 3H), 3.83 (s, 3H), 6.69 – 6.78 (m, 2H), 7.09 – 7.17 (m, 2H), 7.13
– 7.20 (m, 1H), 7.25 – 7.33 (m, 1H), 7.32 (s, 1H), 7.36 (d, J = 8.1 Hz, 1H),
7.63 (d, J = 8.0 Hz, 1H); 13C NMR (126 MHz, CDCl3, ppm) δ = 33.3, 55.5,
102.6, 109.7, 114.5, 119.8, 120.4, 122.5, 128.5, 129.8, 130.1, 134.5,
137.5, 157.8; IR (ATR, cm-1): 2934, 2831, 1592, 1572, 1509, 1489, 1458,
1440, 1420, 1354, 1334, 1315, 1284, 1237, 1172, 1154, 1125, 1111,
1089, 1028, 1008, 820, 796, 766, 739, 637, 624, 610; HRMS (EI-pos.)
calcd. for C16H15NOS [M+]: 269.0869; found: 269.0873.
Compound 37: Colorless oil, 75%. 1H NMR (300 MHz, CDCl3, ppm) δ =
2.29 (s, 3H), 2.98 (s, 6H), 6.66 – 6.74 (m, 2H), 7.00 – 7.09 (m, 4H), 7.34
– 7.40 (m, 2H).[21]
Compound 38: White solid, 90%. 1H NMR (300 MHz, CDCl3, ppm) δ =
2.86 (s, 6H), 3.67 (s, 3H), 6.53 – 6.61 (m, 2H), 6.67 – 6.73 (m, 2H), 7.06
– 7.13 (m, 2H), 7.18 – 7.27 (m, 2H);13C NMR (75 MHz, CDCl3, ppm) δ =
40.5, 55.4, 113.1, 114.7, 120.6, 129.7, 131.0, 134.4, 137.4, 150.2, 158.4;
IR (ATR, cm-1): 2855, 1590, 1488, 1453, 1357, 1281, 1230, 1194, 1029,
808, 629; HRMS (EI-pos.) calcd. for C15H17NOS [M+]: 259.1031, found:
259.1024.
Compound 31: White solid, 33%. 1H NMR (300 MHz, CD3CN, ppm) δ =
3.68 (s, 3H), 3.70 (s, 3H), 6.70 – 6.76 (m, 2H), 6.92 – 6.98 (m, 2H), 7.11
– 7.19 (m, 1H), 7.30 (ddd, J = 8.3, 7.0, 1.2 Hz, 1H), 7.48 – 7.57 (m, 7H);
13C NMR (126 MHz, CDCl3, ppm) δ = 31.9, 55.5, 101.5, 109.8, 114.3,
114.5, 119.9, 120.9, 122.8, 127.8, 128.1, 128.3, 128.7, 129.9, 130.8,
137.6, 145.5, 157.5; IR (ATR, cm-1): 2922, 2852, 1490, 1460, 1436, 1379,
1285, 1277, 1238, 1176, 1034, 1024, 1011, 824, 815, 797, 737, 697, 620;
HRMS (EI-pos.) calcd. for C22H19NOS [M+]: 345.1178, found: 345.1187.
Compound 39: White solid, 51%. 1H NMR (300 MHz, CDCl3, ppm) δ =
0.71 (d, J = 6.9 Hz, 3H), 0.86 – 1.01 (m, 9H), 1.22 – 1.44 (m, 2H), 1.64
(ddt, J = 12.6, 9.7, 3.2 Hz, 2H), 2.17 (dtd, J = 12.2, 3.8, 1.9 Hz, 1H), 2.27
(hd, J = 7.0, 2.8 Hz, 1H), 2.99 (s, 6H), 3.14 (td, J = 10.6, 4.2 Hz, 1H),
4.32 (d, J = 11.4 Hz, 1H), 4.58 (d, J = 11.4 Hz, 1H), 6.67 – 6.73 (m, 2H),
7.08 – 7.13 (m, 2H), 7.17 – 7.22 (m, 2H), 7.34 – 7.40 (m, 2H); 13C NMR
(126 MHz, CDCl3, ppm) δ = 16.3, 21.2, 22.6, 23.5, 25.7, 31.8, 34.8, 40.5,
40.5, 48.5, 77.2, 78.8, 113.1, 118.1, 127.3, 128.4, 135.8, 136.2, 139.1,
150.6; IR (ATR, cm-1): 2950, 2917, 2865, 1593, 1505, 1491, 1444, 1356,
1224, 1193, 1169, 1103, 1082, 1066, 1014, 945, 806, 656; HRMS (EI-
pos.) calcd. for C25H35NOS [M+]: 397.2439, found: 397.2436.
Synthesis of 32: White solid, 61%. 1H NMR (400 MHz, CD2Cl2, ppm) δ =
3.77 (s, 3H), 3.89 (s, 3H), 6.92 (d, J = 2.6 Hz, 2H), 7.16 – 7.29 (m, 5H),
9.53 (s, 1H); 13C NMR (126 MHz, CDCl3, ppm) δ = 56.3, 56.4, 94.5,
100.9, 108.0, 123.0, 126.7, 127.5, 128.5, 129.4, 131.7, 135.4, 147.8,
151.6, 161.5; IR (ATR, cm-1): 2921, 1671, 1632, 1579, 1508, 1476, 1462,
1437, 1258, 1228, 1205, 1173, 1149, 1086, 1049, 1021, 1004, 913, 836,
797, 735, 689, 663; HRMS (ESI-pos.) calcd. for C17H15NO4S [M+Na]:
352.0614, found: 352.0610.
Compound 40: White solid, 65%. 1H NMR (400 MHz, CDCl3, ppm) δ =
3.79 (s, 3H), 3.80 (s, 3H), 3.84 (s, 3H), 6.40 – 6.46 (m, 1H), 6.49 (d, J =
2.6 Hz, 1H), 6.82 – 6.86 (m, 2H), 7.08 (dd, J = 8.5, 1.0 Hz, 1H), 7.25 –
Compound 33: White solid, 76%. 1H NMR (300 MHz, CD2Cl2, ppm) δ
2.20 – 2.31 (m, 2H), 3.00 (dd, J = 6.7, 5.5 Hz, 2H), 3.72 (s, 3H), 4.13 –
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10.1002/chem.201802806
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7.30 (m, 2H); 13C NMR (126 MHz, CDCl3, ppm) δ = 55.5, 55.6, 56.1, 99.2,
105.3, 114.8, 115.9, 126.4, 132.7, 133.4, 158.8, 158.9, 160.7; IR (ATR,
cm-1): 2937, 2833, 1589, 1573, 1490, 1459, 1436, 1410, 1300, 1280,
1240, 1206, 1161, 1159, 1102, 1008, 933, 917, 821, 794, 635, 622;
HRMS (EI-pos.) calcd. for C15H16O3S [M+]: 276.0820, found: 276.0825.
1133, 1100, 1077, 1012, 883, 762, 735, 710; HRMS (ESI-pos.) calcd. for
C13H17NS [M+H]: 220.1154, found: 220.1151.
Compound 47: Colourless oil, 94%. 1H NMR (400 MHz, CDCl3, ppm) δ =
1.23 (d, J = 6.7 Hz, 6H), 2.96 (s, 6H), 3.11 (hept, J = 6.7 Hz, 1H), 6.60 –
6.72 (m, 2H), 7.30 – 7.42 (m, 2H); 13C NMR (126 MHz, CDCl3, ppm) δ =
23.4, 40.0, 40.6, 112.6, 119.8, 136.1, 150.2; IR (neat, cm-1): 2956, 2922,
2860, 1592, 1502, 1443, 1350, 1224, 1193, 1167, 1153, 1130, 1100,
1060, 1049, 945, 811; HRMS (EI-pos.) calcd. for C11H17NS [M+]:
195.1082, found: 195.1089.
Compound 41: Colorless oil, 64%. 1H NMR (300 MHz, CDCl3, ppm) δ =
1.02 (d, J = 6.7 Hz, 6H), 2.72 (hept, J = 6.7 Hz, 1H), 6.29 (dd, J = 3.5, 2.9
Hz, 1H), 6.54 (dd, J = 3.6, 1.8 Hz, 1H), 7.00 (dd, J = 2.9, 1.8 Hz, 1H),
7.32 – 7.49 (m, 5H); 13C NMR (126 MHz, CDCl3, ppm) δ = 23.1, 40.5,
108.9, 120.1, 121.6, 125.6, 126.8, 127.2, 128.7, 140.1; IR (neat, cm-1):
2958, 2921, 2858, 1597, 1498, 1455, 1432, 1363, 1319, 1237, 1153,
1133, 1089, 1073, 1050, 1034, 959, 761, 718, 616, 607; HRMS (EI-pos.)
calcd. for C13H15NS [M+]: 217.0925, found: 217.0923.
Compound 48: Colourless oil, 62%. 1H NMR (300 MHz, CDCl3, ppm) δ =
1.50 – 1.64 (m, 4H), 1.69 – 1.81 (m, 2H), 1.84 – 2.01 (m, 2H), 2.95 (s,
6H), 3.29 – 3.41 (m, 1H), 6.60 – 6.70 (m, 2H), 7.32 – 7.39 (m, 2H);
13C NMR (75 MHz, CDCl3, ppm) δ = 24.7, 33.5, 40.6, 48.8, 112.8, 121.3,
135.1, 150.1; IR (neat, cm-1): 2952, 2799, 1593, 1502, 1443, 1350, 1223,
1192, 1167, 945, 810; HRMS (ESI-pos.) calcd. for C13H19NS [M+H]:
222.1311, found: 222.1317.
Compound 42: Yellow oil, 67%. 1H NMR (600 MHz, CDCl3, ppm) δ =
0.75 (t, J = 7.4 Hz, 3H), 0.99 (d, J = 6.8 Hz, 3H), 1.22 – 1.29 (m, 1H),
1.30 – 1.40 (m, 1H), 2.46 (h, J = 6.8 Hz, 1H), 6.28 (dd, J = 3.6, 2.9 Hz,
1H), 6.54 (dd, J = 3.6, 1.8 Hz, 1H), 7.00 (dd, J = 3.0, 1.8 Hz, 1H), 7.34 –
7.41 (m, 4H), 7.42 – 7.46 (m, 2H); 13C NMR (126 MHz, CDCl3, ppm) δ =
11.5, 20.6, 29.4, 47.3, 108.9, 120.2, 121.3, 125.5, 126.9, 127.2, 128.6,
140.1; IR (neat, cm-1): 2961, 2920, 1597, 1515, 1498, 1455, 1432, 1374,
1319, 1133, 1089, 1072, 1035, 958, 797, 761, 717, 692, 621, 607; HRMS
(EI-pos.) calcd. for C14H17NOS [M+]: 231.1082, found: 231.1088.
Compound 49: White solid, 89%. 1H NMR (300 MHz, CDCl3, ppm) δ =
1.96 (dd, J = 1.4, 0.8 Hz, 3H), 2.98 (s, 6H), 4.57 (s, 1H), 4.93 (q, J = 1.4
Hz, 1H), 6.63 – 6.73 (m, 2H), 7.31 – 7.39 (m, 2H); 13C NMR (75 MHz,
CDCl3, ppm) δ = 22.8, 40.4, 108.4, 112.8, 117.3, 136.4, 144.0, 150.8; IR
(ATR, cm-1): 2914, 1594, 1551, 1505, 1481, 1444, 1356, 1315, 1288,
1225, 1189, 1169, 1129, 1101, 1063, 1001, 846, 922, 853, 813, 766, 716,
Compound 43: Colorless oil, 83%. 1H NMR (300 MHz, CD2Cl2, ppm) δ =
1.44 (p, J = 7.3 Hz, 3H), 1.92 – 2.02 (m, 2H), 2.38 (d, J = 7.1 Hz, 2H),
4.87 – 4.89 (m, 1H), 4.91 – 4.95 (m, 1H), 5.67 (ddt, J = 15.9, 10.7, 6.7 Hz,
1H), 6.26 (dd, J = 3.6, 3.0 Hz, 1H), 6.49 (dd, J = 3.6, 1.8 Hz, 1H), 6.98
(dd, J = 3.0, 1.8 Hz, 1H), 7.34 – 7.51 (m, 5H); 13C NMR (126 MHz,
CD2Cl2, ppm) δ = 28.9, 32.8, 37.2, 109.4, 115.2, 119.2, 122.5, 125.7,
127.0, 127.7, 129.1, 138.3, 140.4; IR (neat, cm-1): 2926, 1718, 1639,
1597, 1516, 1498, 1455, 1433, 1393, 1319, 1295, 1273, 1257, 1205,
1174, 1133, 1089, 1073, 1034, 1000, 990, 958, 910, 879, 824,797, 761,
717, 692, 661, 641, 619, 606; HRMS (ESI-pos.) calcd. for
616; HRMS (EI-pos.) calcd. for C
11H15NS [M+]: 193.0925, found:
193.0920.
Synthesis of 51: 2-Selenoimidazoline (75.0 mg, 0.289 mmol) and N-
chlorosuccinimide (38.6 mg, 0.289 mmol) were dissolved in MeCN (2 mL)
and the mixture was stirred for 5 min at r.t. Removal of the solvents in
vacuo afforded 51 as
a light yellow solid (114 mg, 0.289 µmol,
quantitative). 1H NMR (400 MHz, CD2Cl2, ppm) δ = 1.48 – 1.70 (m, 12H),
2.36 (s, 6H), 2.61 (s, 4H), 6.03 (hept, J = 7.0 Hz, 2H); 13C NMR (101
MHz, CD2Cl2, ppm) δ 10.9, 21.3, 30.1, 56.1, 129.0, 142.8, 180.6; IR (ATR,
cm-1): 2176, 2037, 2029, 1983, 1969, 1707, 1594, 1511, 1360, 1178, 670,
658, 634, 624; HRMS (ESI-pos.) calcd. for C15H24N3O2S [M+]: 358.1029,
found: 358.1031.
C15H17NS [M+H]: 244.1154, found: 244.1157.
Compound 44: Colorless oil, 91%. 1H NMR (300 MHz, CDCl3, ppm) δ =
1.77 – 1.81 (m, 3H), 4.47 – 4.49 (m, 1H), 4.87 – 4.90 (m, 1H), 6.34 (dd, J
= 3.6, 2.9 Hz, 1H), 6.63 (dd, J = 3.6, 1.8 Hz, 1H), 7.06 (dd, J = 3.0, 1.8
Hz, 1H), 7.32 – 7.45 (m, 5H); 13C NMR (126 MHz, CDCl3, ppm) δ = 22.2,
108.7, 109.5, 118.7, 121.1, 126.1, 127.4, 128.7, 139.7, 143.3; IR (neat,
cm-1): 2955, 1596, 1489, 1456, 1448, 1433, 1393, 1320, 1290, 1240,
1204, 1180, 1172, 1161, 1137, 1105, 1087, 1029, 1003, 821, 808, 795,
761, 725, 691, 650, 635, 619; HRMS (EI-pos.) calcd. for C13H13NS [M+]:
215.0769, found: 215.0767.
Representative synthesis of arylselenoimidazolium salts. Synthesis
of 52: N-Methylindole (87 µL, 91 mg, 0.694 mmol) was added to a
solution of 51 (273 mg, 0.694 mmol.) in MeCN (5 mL) and the mixture
stirred at 70 °C for 17 h. Removal of the volatiles afforded a red solid,
which was dissolved in DCM (5 mL) and washed with sat. aq. NaSbF6
(3.0 mL). After separation of the two phases, the organic layer was dried
over MgSO4 and concentrated in vacuo. Crude 52 was purified by
column chromatography (DCM:MeOH; 100:0→95:5). Yellow foam
(244 mg, 0.390 mmol, 56%). 1H NMR (300 MHz, CD2Cl2, ppm) δ = 1.47
(d, J = 7.1 Hz, 12H), 2.32 (s, 6H), 3.85 (s, 3H), 5.63 (s, 2H), 7.26 – 7.38
(m, 2H), 7.41 – 7.46 (m, 2H), 7.59 – 7.64 (m, 1H); 13C NMR (75 MHz,
CD2Cl2, ppm) δ = 10.9, 21.4, 33.9, 55.2, 92.2, 111.2, 119.1, 122.1, 123.8,
129.7, 130.5, 136.9, 137.7; IR (ATR, cm-1): 2964, 2924, 2901, 1433,
1398, 1385, 1359, 1344, 1324, 1229, 1198, 1162, 1145, 1121, 1091, 945,
760, 602; HRMS (ESI-pos.) calcd. for C20H28N3Se [M+]: 390.1444, found:
Compound 45: Colourless oil, 88%. 1H NMR (400 MHz, CDCl3, ppm) δ =
1.64 (dd, J = 1.2, 0.5 Hz, 3H), 1.66 – 1.69 (m, 3H), 5.55 – 5.58 (m, 1H),
6.30 (dd, J = 3.6, 3.0 Hz, 1H), 6.53 (dd, J = 3.6, 1.8 Hz; 1H), 6.98 (dd, J =
2.9, 1.8 Hz, 1H), 7.33 – 7.48 (m, 5H); 13C NMR (126 MHz, CDCl3, ppm) δ
= 19.3, 25.1, 109.2, 117.4, 119.4, 122.3, 125.1, 126.6, 127.2, 128.7,
134.9, 139.8; IR (neat, cm-1): 2909, 1597, 1498, 1454, 1434, 1371, 1319,
1299, 1133, 1088, 1072, 1060, 1034, 959, 798, 760, 716, 692, 664, 619,
606; HRMS (ESI-pos.) calcd. for C14H15NS [M+H]: 230.0998, found:
230.0995.
-
390.1461; (ESI-neg.) calcd. for SbF6 [M-]: 234.8948, found: 234.8957.
Compound 53: Yellow solid, 48%. 1H NMR (300 MHz, CD2Cl2, ppm) δ
1.32 (d, J = 7.1 Hz, 12H), 2.29 (s, 6H), 5.02 (hept, J = 7.1 Hz, 2H), 6.41
(dd, J = 3.8, 3.0 Hz, 1H), 6.74 (dd, J = 3.8, 1.8 Hz, 1H), 7.13 (dd, J = 3.0,
1.7 Hz, 1H), 7.30 – 7.35 (m, 2H), 7.48 – 7.60 (m, 3H); 13C NMR (75 MHz,
CD2Cl2, ppm) δ = 10.8, 21.3, 55.2, 109.6, 111.9, 123.6, 126.6, 129.0,
129.2, 130.2, 130.8, 139.5; IR (ATR, cm-1): 3089, 3033, 2961, 2903,
1767, 1747, 1605, 1509, 1439, 1405, 1384, 1334, 1305, 1234, 1195,
Compound 46: Colorless oil, 64%. 1H NMR (300 MHz, CD2Cl2, ppm) δ =
0.79 (t, 3H), 1.25 – 1.34 (m, 4H), 1.45 – 1.57 (m, 2H), 2.59 – 2.69 (m,
2H), 3.34 (s, 3H), 7.13 – 7.37 (m, 4H), 7.71 (ddd, J = 7.6, 1.5, 0.8 Hz, 1H);
13C NMR (126 MHz, CD2Cl2, ppm) δ = 14.1, 22.3, 32.6, 33.4, 37.0, 104.4,
110.1, 119.7, 120.2, 122.5, 130.6, 134.4, 137.8; IR (neat, cm-1): 3057,
2917, 1512, 1488, 1476, 1462, 1419, 1329, 1315, 1241, 1204, 1152,
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10.1002/chem.201802806
Chemistry - A European Journal
FULL PAPER
1147, 1133, 1121, 1098, 1082, 914, 756, 716, 710, 618; HRMS (ESI-pos.)
Acknowledgements
calcd. for C21H28N3Se [M+]: 402.1444, found: 402.1456; (ESI-neg.) calcd.
-
for SbF6 [M-]: 234.8948, found: 234.8954.
Financial support from the Deutsche Forschungsgemeinschaft
(Al 1348/7-1) and (INST 186/1237-1) and the Stiftung der
Deutschen Wirtschaft (doctoral fellowship to M. J. B.) is
gratefully acknowledged.
Compound 54: Orange solid, 60%. 1H NMR (300 MHz, CD2Cl2, ppm) δ
= 2.36 (s, 6H), 2.96 (s, 6H), 5.47 (s, 2H), 6.65 (d, J = 8.9 Hz, 2H), 7.34 (d,
J = 8.9 Hz, 2H); 13C NMR (101 MHz, CD2Cl2, ppm) δ = 10.9, 21.5, 40.4,
55.2, 109.4, 114.0, 130.7, 136.0, 152.1; IR (ATR, cm-1): 2984, 2943,
2887, 2816, 1715, 1619, 1590, 1508, 1464, 1445, 1417, 1363, 1332,
1318, 1264, 1217, 1198, 1174, 1138, 1112, 1076, 1067, 991, 953, 945,
906, 815, 750, 738, 711, 653; HRMS (ESI-pos.) calcd. for C19H30N3Se
Keywords: thoiureas • thioether • cationic sulfides • electrophilic
thioetherification
-
[M+]: 380.1600, found: 380.1595; (ESI-neg.) calcd. for SbF6 [M-]:
234.8948, found: 234.8957.
[1]
(a) M. Kvasnika, M. Urban, N. J. Dickinson, J. Sarek, Nat. Prod. Rep.
2015, 32, 1303-1330; (b) D. Meng, W. Chen, W. Zhao, J. Nat. Prod.
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Representative synthesis of diarylselenides. Synthesis of 55: p-
Methoxyphenylmagnesium bromide (0.5 M in THF, 1.08 mL, 0.540 mmol,
1.5 equiv.) was added dropwise to a suspension of 52 (225 mg, 0.360
mmol) in THF (2.0 mL) at -78 °C. and the mixture allowed to warm up to
r.t. overnight. The orange solution thus obtained was quenched with sat.
NH4Cl (5 mL) and extracted with DCM (3 x 20 mL). The combined
organic phases were dried over MgSO4, concentrated in vacuo and the
residue was purified by column chromatography (Hexane:DCM;
80:20→0:100) to obtain 55 as a white solid (104.6 mg, 0.331 mmol, 92%).
1H NMR (300 MHz, CD2Cl2, ppm) δ = 3.71 (s, 3H), 3.83 (s, 3H), 6.71 (d, J
= 8.8 Hz, 2H), 7.14 (ddd, J = 8.0, 7.0, 1.1 Hz, 1H), 7.23 – 7.29 (m, 3H),
7.35 (s, 1H), 7.36 – 7.41 (m, 1H), 7.59 (d, J = 8.0 Hz, 1H); 13C NMR (101
MHz, CD2Cl2, ppm) δ = 33.5, 55.8, 97.8, 110.2, 115.2, 120.6, 120.7,
122.8, 124.2, 131.0, 131.9, 135.8, 138.1, 159.1; 77Se NMR (76 MHz,
CD2Cl2, ppm) δ = 196.9; IR (ATR, cm-1): 2939, 1598, 1578, 1497, 1281,
1157, 1118, 1016, 831, 817, 810, 796; HRMS (ESI-pos.) calcd. for
[2]
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M. Feng, B. Tang, S. H. Liang, X. Jiang, Curr. Top. Med. Chem. 2016,
16, 1200-1216.
(a) D. A. Boyd, Angew. Chem. Int. Ed. 2016, 55, 15486-15502; (b) D.
Wu, W. Pisula, M. C. Haberecht, X. Feng, K. Müllen, Org. Lett. 2009,
11, 5686-5689; (c) S. M. Yang, J. J. Shie, J. M. Fang, S. K. Nandy, Y. Y.
Chang, J. Org. Chem. 2002, 67, 5208-5215.
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(a) J. C. Carretero, Chem. Commun. 2011, 47, 2207-2211; (b) Chiral
Sulfur Ligands in Asymmetric Catalysis, H. Pellisier, RSC Catalysis
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(a) A. Kausar, S. Zulfiqar, M. I. Sarwar, Pol. Rev. 2014, 54, 185-267; (b)
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29, 471-489; (c) N. Spassky, Phosphorus Sulfur Silicon Relat. Elem.
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C. C. Eichman, J. P. Stambuli, Molecules, 2011, 16, 590-608.
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2013, 78, 9303-9308; (b) M. Sayah, M. G. Organ, Chem. Eur. J. 2011,
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7397-7403.
C
16H15NOSe [M+H]: 318.0392, found: 318.0388.
Synthesis of 56: Colourless oil, 63%. 1H NMR (300 MHz, CD2Cl2, ppm)
δ = 3.74 (s, 3H), 6.33 (dd, J = 3.6, 2.9 Hz, 1H), 6.66 (dd, J = 3.6, 1.8 Hz,
1H), 6.72 (d, J = 8.8 Hz, 2H), 7.02 – 7.09 (m, 3H), 7.18 – 7.23 (m, 2H),
7.31 – 7.39 (m, 3H); 13C NMR (101 MHz, CD2Cl2, ppm) δ 55.8, 110.3,
115.3, 116.4, 120.9, 121.9, 124.0, 126.7, 127.3, 128.0, 129.1, 130.2,
132.4, 141.0, 159.4; 77Se NMR (76 MHz, CD2Cl2, ppm) δ = 262.4; IR
(ATR, cm-1): 3050, 2979, 2944, 2915, 1578, 1471, 1444, 1396, 1306,
1207, 1094, 1079, 1011, 795, 776, 745, 704, 610; HRMS (ESI-pos.)
calcd. for C17H15NOSe [M+H]: 330.0392, found: 330.0387.
[8]
For selected references: (a) Z. Qiao, N. Gea, X. Jiang, Chem. Commun.
2015, 51, 10295-10298; (b) X. B. Xu, J. Liu, J. J. Zhang, Y. W. Wang, Y.
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Ying, Org. Lett. 2007, 9, 3495-3498; (d) O. Baldovino-Pantaleón, S.
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236-242; (e) Y. C. Wong, T. T. Jayanth, C. H. Cheng, Org. Lett. 2006, 8,
5613-5616.
Synthesis of 57: White solid, 81%. 1H NMR (300 MHz, CDCl3, ppm) δ =
2.95 (s, 6H), 3.77 (s, 3H), 6.64 (d, J = 8.8 Hz, 2H), 6.78 (d, J = 8.8 Hz,
2H), 7.33 (d, J = 8.8 Hz, 2H), 7.41 (d, J = 8.8 Hz, 2H); 13C NMR (75 MHz,
CDCl3, ppm) δ = δ 40.5, 55.4, 113.4, 115.0, 116.0, 123.7, 133.3, 135.7,
150.3, 158.9; 77Se NMR (MHz, CDCl3, ppm) δ = 380.0; IR (ATR, cm-1):
2951, 2918, 2865, 1593, 1505, 1491, 1444, 1357, 1194, 1102, 1083,
1065, 1015, 807; HRMS (ESI-pos.) calcd. for C15H17NOSe [M+H]:
308.0549, found: 308.0541.
[9]
See the “Q3D Elemental Impurities Guidance for Industry.” U. S.
Department of Health and Human Service, 2015.
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Gomez-Pardo, J. Cossy, Org. Lett. 2015, 17, 3898−3901; (c) M. Tudge,
M. Tamiya, C. Savarin, G. R. Humphrey, Org. Lett. 2006, 8, 565-568.
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9188-9190.
Synthesis of 58: White solid, 74%. 1H NMR (300 MHz, CD2Cl2, ppm) δ =
2.27 – 2.36 (m, 2H), 2.78 (t, J = 8.0 Hz, 2H), 2.93 (s, 6H), 6.20 (t, J = 4.7
Hz, 1H), 6.61 – 6.68 (m, 2H), 7.09 – 7.20 (m, 3H), 7.35 – 7.43 (m, 2H),
7.50 – 7.59 (m, 1H); 13C NMR (126 MHz, CDCl3, ppm) δ = δ 25.7, 28.5,
40.7, 113.6, 114.3, 126.3, 126.9, 127.8, 127.9, 130.8, 133.0, 134.8,
135.8, 136.9, 150.7; 77Se NMR (MHz, CDCl3, ppm) δ = 345.8; IR (ATR,
cm-1): 1587, 1503, 1480, 1446, 1424, 1358, 1315, 1277, 1260, 1228,
1195, 1170, 1083, 1066, 1043, 1029, 1015, 953, 935, 809, 779, 758, 729,
690; HRMS (ESI-pos.) calcd. for C18H19N1Se [M+H]: 330.0756; found:
330.0750.
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1586; d) A. J. Arduengo, E. M. Burgess, J. Am. Chem. Soc. 1977, 99,
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CCDC 1842202 (1•Cl), 1842214 (4), 1842208 (6), 1842198 (7),
1842205 (8), 1842207 (9), 1742205 (10), 1842213 (11), 1842199 (13),
1842200 (14), 1842204 (16), 1842211(19), 1842209 (20), 1842201
(26), 1842212 (27), 1842203 (32), 1844013 (54) and 1843380 (SI-1)
contain the supplementary crystallographic data for this article. This
data can be obtained free of charge from the Cambridge
Chrystallographic Data Centre via www.ccdc.cam.uk/data_request/cif.
[19] a) A. Krasovskiy, V. Krasovskaya, P. Knochel. Angew. Chem. Int. Ed.
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Naturforsch. B. 1993, 48, 973-977.
[21] Analytical data were in agreement with those reported: S. K. R.
Parumala, R. K. Peddinti Green Chem. 2015, 17, 4068-4073.
[17] „Structure Correlation“ H. B. Bürgi, J. D. Dunitz, Ed. Wiley 1994.
Apendix A: pages 752-858.
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M. J. Böhm, C. Golz, I. Rüter and M.
Alcarazo*
Page No. – Page No.
Two-Step Synthesis of
Unsymmetrical Diaryl Sulfides via
Electrophilic Thiolation of Non-
Functionalized Hetero(arenes)
Give me two: Succinylthioimidazolium and succinylselenoimidazolium salts are
able to react with two different nucleophiles, first with an unfunctionalized
(hetero)arene and subsequently with a Grignard, to afford a complete palette of
unsymmetrically substituted thio- or selenoethers.
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