N-Imidazolylation of Sulfoximines from N-Cyano Sulfoximines, 1-Alkynes, and N-Sulfonyl Azides

Article abstract of DOI:10.1002/adsc.201500636

The rhodium-catalyzed N-imidazolylation of N-sulfonyl-1,2,3-triazoles with a variety of N-cyano sulfoximines has been developed for the synthesis of N-imidazolyl sulfoximines via elimination of molecular nitrogen. Copper-catalyzed [3+2] cycloaddition followed by rhodium-catalyzed N-imidazolylation from 1-alkynes, N-sulfonyl azides, and N-cyano sulfoximines is also demonstrated for the synthesis of N-imidazolyl sulfoximines in a one-pot procedure.

Full text of DOI:10.1002/adsc.201500636

UPDATES
DOI: 10.1002/adsc.201500636
N-Imidazolylation of Sulfoximines from N-Cyano Sulfoximines,
1-Alkynes, and N-Sulfonyl Azides
Sanghyuck Kim,a Ji Eun Kim,a Jinsub Lee,a and Phil Ho Leea,*
a
National Creative Research Initiative Center for Catalytic Organic Reactions, Department of Chemistry, Kangwon
National University, Chuncheon 200-701, Republic of Korea
Fax: (+82)-33-259-5667; e-mail: phlee@kangwon.ac.kr
Received: July 1, 2015; Revised: August 8, 2015; Published online: October 28, 2015
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500636.
Abstract: The rhodium-catalyzed N-imidazolylation
of N-sulfonyl-1,2,3-triazoles with a variety of N-
cyano sulfoximines has been developed for the syn-
thesis of N-imidazolyl sulfoximines via elimination
of molecular nitrogen. Copper-catalyzed [3+2] cy-
cloaddition followed by rhodium-catalyzed N-imi-
dazolylation from 1-alkynes, N-sulfonyl azides, and
N-cyano sulfoximines is also demonstrated for the
synthesis of N-imidazolyl sulfoximines in a one-pot
procedure.
(hetero)aryl sulfoximines has been described. Al-
though Bolm and Miura recently reported a Cu-cata-
lyzed direct sulfoximination of azoles and polyfluoro-
arenes,[13] we are not aware of any reported examples
of the N-imidazolylation of sulfoximines. Accordingly,
the establishment of synthetic method for N-imidazol-
yl sulfoximines from easily available starting materials
provides a formidable challenge.
Recently, a synthetic method using N-sulfonyl-
1,2,3-triazoles as precursors of an a-imino Rh carbe-
noid has been widely studied.[14] Especially, Fokin and
Lee described that the Rh-catalyzed reaction of 1,2,3-
triazoles with nitriles and bromo cyanides afforded
imidazoles[15] and 2-bromoimidazoles,[16] respectively.
In our continuing studies related to the synthesis of
nitrogen heterocyclic compounds using N-sulfonyl-
1,2,3-triazoles,[17] we envisioned that if N-cyano sul-
foximines could be used as a nucleophile in reacting
with N-sulfonyl-1,2,3-triazoles, N-imidazolyl sulfoxi-
Keywords: cyano sulfoximines; cyclization; imida-
zoles; imidazolylation; multicomponent reaction
Introduction
Sulfoximines are significant privileged scaffolds which mines would be obtained via denitrogenative [3+2]
are extensively found in bioactive compounds,[1] chiral cycloaddition. Herein, we demonstrate the Rh-cata-
auxiliaries,[2] and ligands used in asymmetric synthe- lyzed N-imidazolylation of N-sulfonyl-1,2,3-triazoles
sis.[3] In consequence, the development of efficient with a variety of N-cyano sulfoximines for the synthe-
synthetic approaches for sulfoximines and their func- sis of N-imidazolyl sulfoximines via elimination of
tionalizations has been continuously required.[4] In molecular nitrogen. Moreover, the Cu-catalyzed [3+
particular, N-(hetero)aryl sulfoximines are attractive 2] cycloaddition followed by Rh-catalyzed N-imidazo-
due to the fact that a multitude of their derivatives lylation from 1-alkynes, N-sulfonyl azides, and N-
exhibit anticancer activity[5] or have proved useful as cyano sulfoximines has been developed for the syn-
agrochemicals.[6]
Functionalization of sulfoximines is typically classi- cedure.
thesis of N-imidazolyl sulfoximines as a one-pot pro-
À
À
fied to two categories: N H and a-C H bond func-
tionalization. Among them, functionalization of the
À
N H bond in sulfoximines is more general from a syn- Results and Discussion
thetic viewpoint due to the intrinsic nucleophilicity of
the nitrogen atom. To date, a variety of functionaliza- We initially tried to optimize the N-imidazolylation
À
tions of the N H bond in sulfoximines such as N-cy- conditions for the reaction of S-phenyl-N-cyano sul-
anation,[7] N-alkynylation,[8] N-acylation,[9] N-alkyla- foximine (1a) with N-tosyl-4-phenyl-1,2,3-triazole (2a)
tion,[9a,10] N-alkenylation,[11] and N-arylation[12] have generated from [3+2] cycloaddition of phenylacety-
been reported (Scheme 1). However, in contrast, only lene with N-tosyl azide in the presence of copper(I)
a limited number of synthetic methods for N- thiophene-2-carboxylate (CuTC) (Table 1).[18] A varie-
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Scheme 1. Synthetic approach for N-substitued sulfoximines.
ty of Rh catalysts such as Rh2(OAc)4, Rh2(Oct)4, Rh2(OPiv)4 (1.0 mol%) was the catalyst of choice (en-
Rh2(S-DOSP)4, Rh2(S-PTAD)4, Rh2(esp)2, and tries 1–6). Further examination of solvents disclosed
Rh2(OPiv)4 in toluene was screened to reveal that that toluene is the optimal solvent, while other sol-
vents such as CHCl3, cyclohexane, chlorobenzene, and
benzene showed inferior reactivity (see the Support-
Table 1. Optimization of the reaction conditions.[a]
ing Information). Increasing the amount of 2a and
catalyst led to the formation of the N-imidazolyl sul-
foximine 3a in good to excellent yields. The best
result was achieved from treatment of 1a (0.2 mmol,
1.0 equiv.) with 2a (3.0 equiv.) using Rh2(OPiv)4
(2.0 mol%) in toluene at 808C for 30 min, providing
the S-phenyl-N-imidazolyl sulfoximine (3a) in 87%
isolated yield (entry 10). N-Sulfonyltriazoles tend to
decompose when treated with an Rh catalyst, there-
fore, 3 equiv. of 2a were needed for improving the
yield.
At the outset, triazoles 2 bearing a number of dif-
ferent sulfonyl groups at the N-1 were screened in the
N-imidazolylation with S-phenyl-N-cyano sulfoximine
(1a) under the optimal conditions (Scheme 2). A
modification of the sulfonyl groups at N-1 of triazoles
2 did not largely influence the reaction efficiency.
Gratifyingly, 4-methyl-, 4-methoxy-, and 4-trifluoro-
methylbenzenesulfonyl triazoles 2 produced the N-
imidazolyl sulfoximines (3a, 3b, and 3c) in good yields
ranging from 82% to 87%. Sulfonyltriazoles having
alkyl groups such as methyl, n-butyl, and isopropyl
also underwent N-imidazolylation, affording the de-
sired sulfoximines. The optimal reaction conditions
were obtained with the reaction of N-(methanesulfon-
yl)-4-phenyl-1,2,3-triazole 2d with sulfoximine 1a in
the presence of Rh2(OPiv)4 (2.0 mol%) in toluene at
Entry Cat. (mol%)
2a [equiv.] t [h] Yield [%][b]
1
2
3
4
5
6
7
8
9
10
Rh2(OAc)4 (1.0)
Rh2(Oct)4 (1.0)
1
1
1
1
1
1
1.5
2
2
16
12
16
16
2
0.5 39
0.5 44
0.5 58
0
30
11
18
38
Rh2(S-DOSP)4 (1.0)[c]
Rh2(S-PTAD)4 (1.0)[d]
Rh2(esp)2 (1.0)[e]
Rh2(OPiv)4 (1.0)
Rh2(OPiv)4 (1.0)
Rh2(OPiv)4 (1.0)
Rh2(OPiv)4 (2.0)
Rh2(OPiv)4 (2.0)
0.5 66
3
0.5 91 (87)[f]
[a]
Reactions were carried out with 1a (0.2 mmol), 2a (1–
3 equiv.) and Rh catalyst (1.0–2.0 mol%) in toluene
(2.0 mL) at 808C under a nitrogen atmosphere.
NMR yield using CH2Br2 as an internal standard.
Rh2(S-DOSP)4 =tetrakis[(S)-(À)-N-(p-dodecylphenylsul-
fonyl)prolinato]dirhodium(II).
Rh2(S-PTAD)4 =tetrakis[(S)-(+)-(1-adamantyl)-(N-
phthalimido)acetato]dirhodium.
Rh2(esp)2 =bis[rhodium(a,a,a’,a’-tetramethyl-1,3-ben-
zenedipropionic acid)].
[b]
[c]
[d]
[e]
[f]
Isolated yield of 3a.
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Scheme 2. Scope of the sulfonyl group at N-1 of the triazoles. Reactions were carried out with 1a (0.2 mmol), 2 (0.6 mmol),
and Rh2(OPiv)4 (2.0 mol%) in toluene (2.0 mL).
Scheme 3. Scope of triazoles. Reactions were carried out with 1a (0.2 mmol), 2 (0.6 mmol), and Rh2(OPiv)4 (2.0 mol%) in
toluene (2.0 mL) under a nitrogen atmosphere.
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Scheme 4. Scope of N-cyano sulfoximines. Reactions were carried out with 1a (0.2 mmol), 2 (0.6 mmol), and Rh2(OPiv)4
(2.0 mol%) in toluene (2.0 mL) under a nitrogen atmosphere.
808C for 30 min, producing the N-imidazolyl sulfox- the corresponding N-imidazolyl sulfoximines in good
imine 3d in 92% yield.
to excellent yields ranging from 80% to 99%. Howev-
We next investigated the scope and limitations of er, the 2-methoxyphenyl-substituted triazole (2i) was
this transformation by examining a variety of substitu- less reactive and the N-imidazolyl sulfoximine 3i was
ents on the aryl group of the N-(methanesulfonyl)-4- produced in 61% yield. 4-Trifluoromethylphenyl-sub-
aryl-1,2,3-triazoles 2 under the optimal conditions stituted triazole 2l was smoothly converted to the de-
(Scheme 3). Electronic modification of substituents sired product 3l. Electron-withdrawing chloro and
on the aryl group of 2 influenced the reaction efficien- bromo groups are useful for the N-imidazolylation, af-
cy. For example, 4-aryl-1,2,3-triazoles bearing elec- fording the desired products (3m–3p) in good yields.
tron-donating 3- and 4-methyl and 3- and 4-methoxy In contrast to 2i, 2-bromophenyl-substituted triazole
groups underwent the N-imidazolylation, producing (2o) was subjected to the N-imidazolylation to give
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N-Imidazolylation of Sulfoximines from N-Cyano Sulfoximines
Scheme 5. N-Imidazolylation of sulfoximines from 1-alkynes, N-mesyl azide, and N-cyano sulfoximines in one-pot. Reactions
were carried out with 1 (0.2 mmol), 5 (0.66 mmol), MsN3 (0.6 mmol), CuTC (10.0 mol%), and Rh2(OPiv)4 (2.0 mol%) in tol-
uene (2.0 mL) under a nitrogen atmosphere.
3o in 90% yield. When the triazole (2q) having a 2- yield. S,S-Dimethyl-N-cyano sulfoximine also took
naphthyl group was treated with sulfoximine 1a, the part in the N-imidazolylation to afford the desired
N-imidazolylation took place to provide 3q in 85% product 4m in 73% yield. S,S-Diphenyl-N-cyano sulf-
yield. To our satisfication, the catalytic imidazolyla- oximine also worked, leading to the corresponding
tion using 4,5-disubstituted triazole 2r smoothly oc- S,S-diphenyl-N-imidazolyl sulfoximine (4p) in 81%
curred to furnish 3r in 82% yield.[19] The Rh-catalyzed yield.
cyclization was amenable with respect to thiophen-3-
To show the synthetic efficiency of the N-imidazoly-
yl-substituted triazole 2s to produce 3s in 65% yield. lation, we next attempted synthesis of the N-imdazol-
4-Cyclohexenyltriazole 2t was compatible with the op- yl sulfoximines from N-cyano sulfoximines, 1-alkynes,
timal conditions, furnishing the desired sulfoximine 3t and N-mesyl azide in one-pot (Scheme 5).[19a,21] Phe-
in 62% yield. Treatment of N-mesyl-1,2,3-triazole pos- nylacetylene, N-mesyl azide, and S-phenyl-N-cyano
sessing a 4-n-hexyl group with sulfoximine (1a) pro- sulfoximine in the presence of CuTC (10.0 mol%)
vided the desired product 3u in acceptable yield.
and Rh2(OPiv)4 (2.0 mol%) in toluene were stirred at
Encouraged by these results, we next investigated room temperature for 1 h and then, the reaction mix-
the scope and functional group tolerance of the Rh- ture was continuously stirred at 808C for 30 min, af-
catalyzed N-imidazolylation of N-mesyl-4-phenyl- fording S-phenyl-N-imidazolyl sulfoximine 3d in 69%
1,2,3-triazole 2a by modification of the N-cyano sul- yield. When 4-methylphenylacetylene 5b was em-
foximines 1 (Scheme 4). Electronic modification of ployed, the desired N-imidazolyl sulfoximine 3h was
a large number of substituents on the aryl ring of S- obtained in 92% yield. However, 4-methoxyphenyla-
aryl-N-cyano sulfoximines 1 did not much affect the cetylene is less reactive and then 3k was produced in
reaction efficiency. N-Cyano sulfoximines bearing 58% yield. 4-Chlorophenylacetylene was compatible
electron-donating methyl substituents on the phenyl with the present reaction conditions. Electronic modi-
ring are useful in the present transformation, afford- fication of substituents on the aryl group in S-aryl-N-
ing the desired S-tolyl-N-imidazolyl sulfoximines (4a– cyano sulfoximines did not largely effect the reaction
4c) in good yields ranging from 82% to 87%. S-3,5- efficiency. For example, S-aryl-N-cyano sulfoximines
Dimethylphenyl-N-cyano sulfoximine also worked, having not only electron-donating methyl and me-
leading to the desired N-imidazolyl sulfoximine 4d in thoxy groups but also electron-withdrawing chloro
91% yield. Despite the presence of a strong electron- and trifluoromethyl groups on the aryl ring were sub-
donating methoxy group, N-imidazolyl sulfoximines jected to [3+2] cycloaddition followed by N-imidazo-
(4e, 4f, and 4n) were produced in good yields. N-Imi- lylation in one-pot, furnishing the desired N-imidazol-
dazolylation was compatible with halide functional yl sulfoximines in good yields from 63% to 77%. The
groups such as chloro and bromo groups. The struc- present method worked equally well with S,S-dimeth-
ture of 4j was confirmed by X-ray crystallography.[20] yl-N-sulfoximine, producing the N-imidazolyl-S,S-di-
When S-4-trifluoromethylphenyl-substituted N-cyano methyl sulfoximine 4m in 56% yield.
sulfoximine underwent the N-imidazolylation under
A plausible mechanism for the synthesis of N-imi-
the optimal conditions, the corresponding N-imidazol- dazolyl sulfoximines (3 and 4) from N-cyano sulfox-
yl sulfoximines 4k and 4o were obtained in 90% and imines 1, 1-alkynes 5, and N-sulfonyl azides 6 in one-
82% yields, respectively. N-Imidazolylation also took pot is shown in Scheme 6. Foremost, a reversible ring-
place in S-2-naphthyl-N-cyano sulfoximine, producing chain tautomerization of N-sulfonyltriazole 2 generat-
S-2-naphthyl-N-imidazolyl sulfoximine (4l) in 82% ed from Cu-catalyzed [3+2] cycloaddition of 1-alkyne
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anisaldehyde. Flash column chromatography was carried out
using silica gel (230–400 mesh). 1H NMR (400 MHz),
13C NMR (100 MHz) spectra were recorded on an NMR
spectrometer. Deuterated chloroform was used as the sol-
vent and chemical shift values (d) are reported in parts per
million relative to the residual signals of this solvent [d=
1
1
7.26 for H (chloroform-d), d=2.05 for H (acetone-d6), d=
1
2.50 for H (DMSO-d6), d=77.2 for 13C (chloroform-d), d=
29.9, 206.7 for 13C (acetone-d6) and for d=39.51 for 13C
(DMSO-d6)]. Infrared spectra were recorded on an FT-IR
spectrometer as either a thin film pressed between two
sodium chloride plates or as a solid suspended in a potassium
bromide disk. High resolution mass spectra (HR-MS) were
obtained by fast atom bombardment (FAB) using a double
focusing magnetic sector mass spectrometer and electron
impact (EI) ionization technique (magnetic sector – electric
sector double focusing mass analyzer). Melting points were
determined in open capillary tubes.
Scheme 6. A plausible mechanism.
General Procedure for the Preparation of S-Methyl-S-
phenyl-N-imidazolyl Sulfoximines
To a test tube were added N-cyano sulfoximine deriva-
tives[7,23] (1, 0.2 mmol), triazole[17,24] (2, 0.6 mmol), and
Rh2(OPiv)4 (2.0 mol%) in toluene (0.1M). The resulting
mixture was stirred at 808C for 0.5 h. After celite filtration
5 with N-sulfonyl azide 6 affords a-diazo imine A.
The subsequent irreversible treatment of A with Rh
catalyst yields a-imino Rh-carbenoid B along with ni-
trogen gas. Nucleophilic attack of N-cyano sulfox-
imine 1 to the electrophilic Rh-carbenoid B provides and evaporation of the solvents undert vacuum, the crude
product was purified by column chromatography on silica
gel to afford 3 and 4; yields: 72–99%.
Rh-bound zwitterionic intermediate C, which is a nitri-
lium ion.[22] At that moment, the anionic rhodium of
C pushes an electron pair, which moves the imine
moiety to allow the nitrogen atom to become nucleo-
philic enough to react with nitrilium ion C to furnish
N-imidazolyl sulfoximines 3 and 4 with regeneration
of the Rh catalyst.
S-Methyl-S-phenyl-N-(4-phenyl-1-tosyl)imidazolyl sulfox-
imine (3a): yield: 79.0 mg (87%); Rf =0.3 (Et2O:CH2Cl2:
hexane=1:2:3); brown solid; mp 79–818C; 1H NMR
(400 MHz, CDCl3): d=8.07 (d, J=7.8 Hz, 2H), 7.89 (d, J=
8.4 Hz, 2H), 7.70–7.65 (m, 3H), 7.60 (d, J=7.6 Hz, 2H),
7.48 (s, 1H), 7.30 (t, J=7.6 Hz, 2H), 7.24 (d, J=8.1 Hz,
2H), 7.20 (d, J=7.3 Hz, 1H), 3.49 (s, 3H), 2.38 (s, 3H);
13C NMR (100 MHz, CDCl3): d=146.5, 145.3, 138.8, 138.2,
135.0, 133.9, 133.0, 129.6, 129.5, 128.3, 128.3, 128.1, 127.2,
125.0, 109.7, 43.7, 21.7; IR (film): n=3154, 3062, 3028, 2981,
2927, 1732, 1529, 1447, 1372, 1342, 1234, 1169, 1111, 1091,
1011, 673, 588 cmÀ1; HR-MS (EI): m/z=451.1023, calcd. for
C23H21N3O3S2 [M]+: 451.1024.
S-Methyl-S-phenyl-N-[1-(4-methoxyphenyl)sulfonyl]-4-
phenylimidazolyl sulfoximine (3b): yield: 77.0 mg (82%);
Rf =0.3 (Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 65–
678C; 1H NMR (400 MHz, CDCl3): d=8.11 (d, J=7.6 Hz,
2H), 7.94 (d, J=9.1 Hz, 2H), 7.70–7.65 (m, 3H), 7.61 (t, J=
7.6 Hz, 2H), 7.48 (s, 1H), 7.30 (t, J=7.5 Hz, 2H), 7.20 (t,
J=7.3 Hz, 1H), 6.89 (d, J=9.0 Hz, 2H), 3.81 (s, 3H), 3.51
(s, 3H); 13C NMR (100 MHz, CDCl3): d=164.1, 146.9, 138.9,
138.0, 133.9, 133.0, 130.7, 129.6, 129.4, 128.4, 128.1, 127.2,
124.9, 114.2, 109.7, 55.7, 43.7; IR (film): n=3154, 3063, 3029,
2929, 2841, 1594, 1528, 1497, 1447, 1367, 1344, 1263, 1234,
1164, 1112, 1091, 1015, 730, 587 cmÀ1; HR-MS (EI): m/z=
467.0971, calcd. for C23H21N3O4S2 [M]+: 467.0973.
Conclusions
In summary, we have developed a robust Rh-cata-
lyzed N-imidazolylation of N-sulfonyl-1,2,3-triazoles
with a variety of N-cyano sulfoximines for the synthe-
sis of N-imidazolyl sulfoximines via elimination of
molecular nitrogen. Cu-catalyzed [3 + 2] cycloaddi-
tion followed by Rh-catalyzed N-imidazolylation from
1-alkynes, N-sulfonyl azides, and N-cyano sulfox-
imines is also demonstrated for the synthesis of N-
imidazolyl sulfoximines in one-pot.
Experimental Section
General Methods
S-Methyl-S-phenyl-N-[4-phenyl-1-(4-trifluoromethylphe-
nyl)sulfonyl]imidazolyl sulfoximine (3c): yield: 83.0 mg
(82%); Rf =0.3 (Et2O:CH2Cl2:hexane=1:2:3); brown solid;
Reactions were carried out in oven-dried glassware under
an air atmosphere unless otherwise stated. Rh2(OAc)4,
Rh2(Oct)4, Rh2(S-DOSP)4, Rh2(S-PTAD)4, Rh2(esp)2, and
Rh2(OPiv)4 were purchased and were used as received.
Commercially available reagents were used without purifica-
tion. All reaction mixtures were stirred magnetically and
were monitored by thin-layer chromatography using silica
gel pre-coated glass plates, which were visualized with UV
light and then developed using either iodine or a solution of
1
mp 69–718C; H NMR (400 MHz, CDCl3): d=8.14 (d, J=
8.2 Hz, 2H), 8.09 (d, J=7.2 Hz, 2H), 7.74–7.61 (m, 7H),
7.48 (s, 1H), 7.32 (t, J=7.5 Hz, 2H), 7.23 (t, J=7.3 Hz, 1H),
3.54 (s, 3H); 13C NMR (100 MHz, CDCl3): d=146.7, 141.3,
128.8, 138.6, 135.6 (q, JC,F =33.3 Hz), 134.1, 132.6, 129.7,
128.9, 128.4, 127.9, 127.5, 123.0 (q, JC,F =272.0 Hz), 126.2 (q,
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J
C,F =3.7 Hz), 125.0, 109.3, 43.7; IR (film): n=3157, 3065,
CDCl3): d=146.2, 138.7, 138.2, 137.1, 134.1, 130.1, 129.7,
129.1, 128.1, 124.9, 108.7, 43.6, 41.6, 21.3; IR (film): n=3157,
3064, 3022, 2927, 2865, 1609, 1563, 1529, 1359, 1234, 1195,
1163, 1107, 1016, 965, 910, 731, 553 cmÀ1; HR-MS (EI):
m/z=389.0865, calcd. for C18H19N3O3S2 [M]+: 389.0868.
S-Methyl-S-phenyl-N-[1-mesyl-4-(2-methoxyphenyl)]imi-
dazolyl sulfoximine (3i): yield: 50.0 mg (61%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 195–1968C;
1H NMR (400 MHz, CDCl3): d=8.19 (d, J=7.3 Hz, 2H),
8.07 (dd, J=7.7 Hz, 1.7 Hz, 1H), 7.70 (t, J=7.3 Hz, 1H),
7.66 (s, 1H), 7.63 (t, J=7.5 Hz, 2H), 7.21 (ddd, J=8.2 Hz,
7.4 Hz, 1.7 Hz, 1H), 6.98 (td, J=7.5 Hz, 1.0 Hz, 1H), 6.91
(d, J=8.2 Hz, 1H), 3.93 (s, 3H), 3.60 (s, 3H), 3.44 (s, 3H);
13C NMR (100 MHz, CDCl3): d=156.4, 145.3, 138.8, 134.0,
133.6, 129.7, 128.2, 128.1, 127.8, 121.4, 120.5, 113.7, 110.3,
55.2, 43.6, 41.6; IR (film): n=3188, 3063, 3014, 2928, 2837,
1533, 1490, 1358, 1235, 1164, 1106, 1086, 1016, 964, 752,
3032, 2929, 1776, 1608, 1566, 1532, 1447, 1322, 1233, 1174,
1062, 1012, 910, 732, 716, 622, 602 cmÀ1; HR-MS (EI): m/z=
505.0743, calcd. for C23H18F3N3O3S2 [M]+: 505.0742.
S-Methyl-S-phenyl-N-(1-mesyl-4-phenyl)imidazolyl sulfox-
imine (3d): yield: 69.0 mg (92%); Rf =0.3 (Et2O:CH2Cl2:
hexane=1:2:3); brown solid; mp 135–1378C; 1H NMR
(400 MHz, CDCl3): d=8.18 (d, J=7.5 Hz, 2H), 7.73–7.67
(m, 3H), 7.64 (t, J=7.5 Hz, 2H), 7.36 (s, 1H), 7.33 (t, J=
7.5 Hz, 2H), 7.24 (t, J=7.4 Hz, 1H), 3.60 (s, 3H), 3.45 (s,
3H); 13C NMR (100 MHz, CDCl3): d=146.3, 138.6, 138.1,
134.1, 132.9, 129.7, 128.4, 128.1, 127.3, 125.0, 109.2, 43.7,
41.6; IR (film): n=3423, 3347, 3144, 3061, 3025, 2928, 1530,
1447, 1349, 1232, 1165, 1111, 1015, 965, 733, 555 cmÀ1; HR-
MS (EI): m/z=375.0708, calcd. for C17H17N3O3S2 [M]+:
375.0711.
S-Methyl-S-phenyl-N-[1-(butylsulfonyl)-4-phenyl]imida-
zolyl sulfoximine (3e): yield: 71.0 mg (85%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 65–678C;
1H NMR (400 MHz, CDCl3): d=8.19 (d, J=7.6 Hz, 2H),
7.73–7.69 (m, 3H), 7.63 (t, J=7.5 Hz, 2H), 7.36 (s, 1H), 7.33
(t, J=7.5 Hz, 2H), 7.23 (t, J=7.3 Hz, 1H), 3.71–3.54 (m,
2H), 3.58 (s, 3H), 1.83–1.67 (m, 2H), 1.41 (q, J=7.5 Hz,
2H), 0.88 (t, J=7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d=146.3, 138.7, 137.9, 134.0, 132.9, 129.7, 128.4, 128.2, 127.3,
125.0, 110.0, 53.4, 43.6, 25.0, 21.2, 13.5; IR (film): 3154, 3061,
3029, 2961, 2932, 2874, 1608, 1564, 1529, 1447, 1345, 1234,
1158, 1112, 1015, 996, 731, 714, 558 cmÀ1; HR-MS (EI):
m/z=417.1182, calcd. for C20H23N3O3S2 [M]+: 417.1181.
S-Methyl-S-phenyl-N-[1-(isopropylsulfonyl)-4-phenyl]imi-
dazolyl sulfoximine (3f): yield: 70.0 mg (87%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 67–698C;
1H NMR (400 MHz, CDCl3): d=8.20 (d, J=7.6 Hz, 2H),
7.71–7.68 (m, 3H), 7.63 (t, J=7.5 Hz, 2H), 7.36 (s, 1H), 7.33
(t, J=7.5 Hz, 2H), 7.23 (t, J=7.4 Hz, 1H), 4.09 (p, J=
6.9 Hz, 1H), 3.57 (s, 3H), 1.45 (d, J=6.9 Hz, 3H), 1.35 (d,
J=6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=146.5,
138.8, 137.9, 134.0, 133.0, 129.6, 128.4, 128.2, 127.3, 125.0,
110.7, 54.8, 43.6, 16.3, 15.5; IR (film): n=3155, 3063, 3031,
2985, 2935, 2876, 1608, 1530, 1447, 1352, 1235, 1150, 1015,
912, 732, 603 cmÀ1; HR-MS (EI): m/z=403.1022, calcd. for
C19H21N3O3S2 [M]+: 403.1024.
S-Methyl-S-phenyl-N-[1-mesyl-4-(3-methylphenyl)]imida-
zolyl sulfoximine (3g): yield: 71.0 mg (91%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 68–708C;
1H NMR (400 MHz, CDCl3): d=8.19 (d, J=7.5 Hz, 2H),
7.71 (t, J=7.3 Hz, 1H), 7.64 (t, J=7.6 Hz, 2H), 7.52 (s, 1H),
7.49 (d, J=7.8 Hz, 1H), 7.35 (s, 1H), 7.22 (t, J=7.6 Hz,
1H), 7.05 (d, J=7.5 Hz, 1H), 3.61 (s, 3H), 3.44 (s, 3H), 2.36
(s, 3H); 13C NMR (100 MHz, CDCl3): d=146.2, 138.7, 138.2,
138.0, 134.1, 132.8, 129.7, 128.3, 128.2, 128.1, 125.7, 122.1,
109.2, 43.6, 41.6, 21.5; IR (film): n=3156, 3060, 3019, 2927,
2863, 1611, 1530, 1359, 1235, 1189, 1164, 1113, 1016, 965,
910, 731, 557 cmÀ1; HR-MS (EI): m/z=389.0869, calcd. for
C18H19N3O3S2 [M]+: 389.0868.
S-Methyl-S-phenyl-N-[1-mesyl-4-(4-methylphenyl)]imida-
zolyl sulfoximine (3h): yield: 77.0 mg (99%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 88–898C;
1H NMR (400 MHz, CDCl3): d=8.19 (d, J=7.5 Hz, 2H),
7.71 (t, J=7.4 Hz, 1H), 7.63 (t, J=7.5 Hz, 2H), 7.59 (d, J=
8.1 Hz, 2H), 7.32 (s, 1H), 7.14 (d, J=7.9 Hz, 2H), 3.40 (s,
3H), 3.44 (s, 3H), 2.34 (s, 3H); 13C NMR (100 MHz,
555 cmÀ1
;
HR-MS (EI): m/z=405.0820, calcd. for
C18H19N3O4S2 [M]+: 405.0817.
S-Methyl-S-phenyl-N-[1-mesyl-4-(3-methoxyphenyl)]imid-
azolyl sulfoximine (3j): yield: 67.0 mg (83%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 63–658C;
1H NMR (400 MHz, CDCl3): d=8.18 (d, J=7.5 Hz, 2H),
7.71 (t, J=7.4 Hz, 1H), 7.64 (t, J=7.5 Hz, 2H), 7.36 (s, 1H),
7.29–7.22 (m, 3H), 6.79 (ddd, J=7.8 Hz, 2.5 Hz, 1.6 Hz,
1H), 3.82 (s, 3H), 3.60 (s, 3H), 3.45 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=159.7, 146.2, 138.7, 137.9, 134.3,
134.1, 129.7, 129.5, 128.1, 117.5, 113.1, 110.4, 109.5, 55.3,
43.7, 41.6; IR (film): n=3156, 3064, 3014, 2930, 2835, 1606,
1530, 1359, 1321, 1231, 1164, 1112, 1016, 908, 731, 555 cmÀ1
;
HR-MS (EI): m/z=405.0813, calcd. for C18H19N3O4S2 [M]+:
405.0817.
S-Methyl-S-phenyl-N-[1-mesyl-4-(4-methoxyphenyl)]imid-
azolyl sulfoximine (3k): yield: 65.0 mg (80%); Rf =0.3
(Et2O: CH2Cl2:hexane=1:2:3); brown solid; mp 79–818C;
1H NMR (400 MHz, CDCl3): d=8.19 (d, J=7.6 Hz, 2H),
7.71 (t, J=7.4 Hz, 1H), 7.65–7.60 (m, 4H), 6.87 (d, J=
8.9 Hz, 2H), 3.81 (s, 3H), 3.59 (s, 3H), 3.43 (s, 3H);
13C NMR (100 MHz, CDCl3): d=159.0, 146.2, 138.7, 137.9,
134.1, 129.7, 128.1, 126.3, 125.7, 113.8, 108.0, 55.3, 43.7, 41.6;
IR (film): n=3157, 3065, 3014, 2930, 2837, 1614, 1568, 1529,
1357, 1244, 1163, 1016, 965, 911, 836, 730, 555 cmÀ1; HR-MS
(EI): m/z=405.0814, calcd. for C18H19N3O4S2 [M]+: 405.0817.
S-Methyl-S-phenyl-N-[1-mesyl-4-(4-trifluoromethylphen-
yl)]imidazolyl sulfoximine (3l): yield: 75.0 mg (84%); Rf =
0.3 (Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 168–
1
1698C; H NMR (400 MHz, CDCl3): d=8.17 (d, J=8.1 Hz,
2H), 7.78 (d, J=8.3 Hz, 2H), 7.72 (t, J=7.4 Hz, 1H), 7.64
(t, J=7.6 Hz, 2H), 7.57 (d, J=8.2 Hz, 2H), 7.45 (s, 1H),
3.59 (s, 3H), 3.47 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
146.6, 138.4, 136.7, 136.4, 134.2, 129.8, 129.0 (JC,F =32.3 Hz),
128.1, 125.4 (JC,F =3.8 Hz), 125.1, 124.3 (JC,F =271.7 Hz),
110.6, 43.8, 41.6; IR (film): n=3158, 3068, 3019, 2931, 1617,
1530, 1415, 1361, 1324, 1235, 1165, 1116, 1015, 966, 849, 732,
556 cmÀ1
;
HR-MS (EI): m/z=443.0584, calcd. for
C18H16F3N3O3S2 [M]+: 443.0585.
S-Methyl-S-phenyl-N-[1-mesyl-4-(3-chlorophenyl)]imida-
zolyl sulfoximine (3m): yield: 73.0 mg (89%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 159–1608C;
1H NMR (400 MHz, CDCl3): d=8.18 (d, J=7.7 Hz, 2H),
7.72 (t, J=7.4 Hz, 1H), 7.69 (t, J=1.7 Hz, 1H), 7.65 (t, J=
7.6 Hz, 2H), 7.53 (dt, J=7.6 Hz, 1.3 Hz, 1H), 7.38 (s, 1H),
Adv. Synth. Catal. 2015, 357, 3707 – 3717
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
3713

UPDATES
Sanghyuck Kim et al.
7.25 (t, J=7.8 Hz, 1H), 7.21–7.18 (m, 1H), 3.60 (s, 3H), 3.45
(s, 3H); 13C NMR (100 MHz, CDCl3): d=146.5, 138.5, 136.8,
134.8, 134.4, 134.2, 129.7, 129.6, 128.1, 127.3, 125.1, 123.0,
109.9, 43.7, 41.6; IR (film): n=3154, 3066, 3019, 2929, 1772,
1710, 1603, 1530, 1416, 1361, 1235, 1166, 1115, 1016, 966,
910, 735, 555 cmÀ1; HR-MS (EI): m/z=409.0323, calcd. for
C17H16ClN3O3S2 [M]+: 409.0322.
(td, J=7.4 Hz, 1.8 Hz, 1H), 7.13–7.07 (m, 2H), 3.59 (s, 3H),
3.46 (s, 3H), 3.13–3.08 (m, 2H), 3.04–3.00 (m, 2H);
13C NMR (100 MHz, CDCl3): d=147.2, 139.0, 134.0, 133.5,
130.6, 129.6, 128.2, 127,4, 126.5, 126.2, 124.2, 121.6, 43.6,
42.3, 28.7, 21.6; IR (film): n=3061, 3019, 2928, 2844, 1585,
1535, 1362, 1310, 1231, 1166, 1105, 965, 735, 546 cmÀ1; HR-
MS (EI): m/z=401.0865, calcd. for C19H19N3O3S2 [M]+:
401.0868.
S-Methyl-S-phenyl-N-[1-mesyl-4-(thiophen-3-yl)]imidazol-
yl sulfoximine (3s): yield: 50.0 mg (65%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 81–838C;
1H NMR (400 MHz, CDCl3): d=8.18 (d, J=7.1 Hz, 2H),
7.71 (t, J=7.4 Hz, 1H), 7.64 (t, J=7.5 Hz, 2H), 7.52 (dd, J=
2.9 Hz, 1.3 Hz, 1H), 7.29–7.25 (m, 2H), 7.22 (s, 1H), 3.58 (s,
3H), 3.43 (s, 3H); 13C NMR (100 MHz, CDCl3): d=146.3,
138.6, 134.7, 134.6, 134.1, 129.7, 128.1, 125.9, 125.1, 120.5,
109.0, 43.7, 41.6; IR (film): n=3149, 3108, 3067, 3018, 2928,
1773, 1717, 1616, 1530, 1360, 1233, 1163, 1109, 1016, 961,
911, 731, 556 cmÀ1; HR-MS (EI): m/z=381.0273, calcd. for
C15H15N3O3S3 [M]+: 381.0276.
S-Methyl-S-phenyl-N-[4-(4-chlorophenyl)-1-mesyl]imida-
zolyl sulfoximine (3n): yield: 73.0 mg (89%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 165–1668C;
1H NMR (400 MHz, CDCl3): d=8.17 (d, J=7.4 Hz, 2H),
7.72 (t, J=7.4 Hz, 1H), 7.65 (d, J=8.0 Hz, 2H), 7.61 (d, J=
8.5 Hz, 2H), 7.35 (s, 1H), 7.29 (t, J=8.6 Hz, 2H), 3.59 (s,
3H), 3.45 (s, 3H); 13C NMR (100 MHz, CDCl3): d=146.4,
138.5, 137.1, 134.2, 132.9, 131.4, 129.7, 128.6, 128.1, 126.3,
109.5, 43.8, 41.6; IR (film): n=3151, 3066, 3019, 2929, 1605,
1560, 1530, 1359, 1235, 1165, 1114, 1091, 1015, 910, 734, 630,
558 cmÀ1
;
HR-MS (EI): m/z=409.0323, calcd. for
C17H16ClN3O3S2 [M]+: 409.0322.
S-Methyl-S-phenyl-N-[4-(2-bromophenyl)-1-mesyl]imida-
zolyl sulfoximine (3o): yield: 82.5 mg (90%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 187–1888C;
1H NMR (400 MHz, CDCl3): d=8.18 (d, J=7.6 Hz, 2H),
7.86 (dd, J=7.9 Hz, 1.7 Hz, 1H), 7.81 (s, 1H), 7.71 (t, J=
7.4 Hz, 1H), 7.64 (t, J=7.5 Hz, 2H), 7.57 (dd, J=8.0 Hz,
1.1 Hz, 1H), 7.29 (td, J=7.3 Hz, 1.2 Hz, 1H), 7.08 (td, J=
7.9 Hz, 1.7 Hz, 1H), 3.58 (s, 3H), 3.48 (s, 3H); 13C NMR
(100 MHz, CDCl3); d=145.5, 138.6, 135.7, 134.1, 133.6,
133.3, 130.7, 129.7, 128.3, 128.1, 127.2, 120.7, 113.3, 43.8,
41.7; IR (film): n=3180, 3064, 3016, 2928, 1557, 1531, 1359,
1233, 1165, 1108, 1015, 772, 741, 555 cmÀ1; HR-MS (EI):
m/z=452.9819, calcd. for C17H16BrN3O3S2 [M]+: 452.9816.
S-Methyl-S-phenyl-N-[4-(4-bromophenyl)-1-mesyl]imida-
zolyl sulfoximine (3p): yield: 79.0 mg (87%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 156–1578C;
1H NMR (400 MHz, CDCl3): d=8.17 (d, J=8.2 Hz, 2H),
7.72 (t, J=7.8 Hz, 1H), 7.64 (t, J=7.8 Hz, 2H), 7.55 (d, J=
8.4 Hz, 2H), 7.44 (d, J=8.5 Hz, 2H), 7.36 (s, 1H), 3.59 (s,
3H), 3.45 (s, 3H); 13C NMR (100 MHz, CDCl3): d=146.5,
138.6, 137.1, 134.1, 131.9, 131.5, 129.7, 128.1, 126.6, 121.0,
109.5, 43.8, 41.6; IR (film): n=3147, 3062, 3019, 2928, 2852,
1600, 1558, 1529, 1401, 1359, 1235, 1165, 1115, 1013, 965,
895, 734, 556 cmÀ1; HR-MS (EI): m/z=452.9814, calcd. for
C17H16BrN3O3S2 [M]+: 452.9816.
S-Methyl-S-phenyl-N-(4-naphthyl-1-mesyl)imidazolyl sul-
foximine (3q): yield: 72.0 mg (85%); Rf =0.3 (Et2O:
CH2Cl2:hexane=1:2:3); brown solid; mp 145–1478C;
1H NMR (400 MHz, CDCl3): d=8.22–8.20 (m, 3H), 7.84 (d,
J=7.7 Hz, 1H), 7.80 (d, J=8.3 Hz, 2H), 7.74 (dd, J=8.6 Hz,
1.6 Hz, 1H), 7.72–7.69 (m, 1H), 7.65 (t, J=7.4 Hz, 2H), 7.49
(s, 1H), 7.44 (pd, J=7.9 Hz, 1.4 Hz, 2H), 3.64 (s, 3H), 3.47
(s, 3H); 13C NMR (100 MHz, CDCl3): d=146.5, 138.6, 138.1,
134.1, 133.6, 132.9, 130.2, 129.7, 128.2, 128.1, 128.0, 127.7,
126.2, 125.7, 123.7, 123.3, 109.8, 43.7, 41.6; IR (film): n=
3153, 3057, 3020, 2928, 1773, 1714, 1606, 1530, 1364, 1320,
1233, 1165, 1110, 1016, 962, 909, 730, 552 cmÀ1; HR-MS
(EI): m/z=425.0864, calcd. for C21H19N3O3S2 [M]+: 425.0868.
S-Methyl-S-phenyl-N-(3-mesyl-4,5-dihydro-3H-naph-
S-Methyl-S-phenyl-N-(4-cyclohexenyl-1-mesyl)imidazolyl
sulfoximine
(3t):
yield:
47.2 mg
(62%);
Rf =0.4
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 63–658C;
1H NMR (400 MHz, CDCl3): d=8.17 (d, J=7.5 Hz, 2H),
7.70 (t, J=7.4 Hz, 1H), 7.63 (t, J=7.6 Hz, 2H), 6.90 (s, 1H),
6.46 (t, J=3.7 Hz, 1H), 3.57 (s, 3H), 3.38 (s, 3H), 2.18–2.15
(m, 4H), 1.72–1.68 (m, 2H), 1.65–1.60 (m, 2H); 13C NMR
(100 MHz, CDCl3): d=146.0, 139.7, 138.9, 134.0, 129.6,
128.6, 128.1, 124.2, 108.1, 43.6, 41.4, 25.2, 25.0, 22.5, 22.4; IR
(film): n=3057, 3019, 2928, 2844, 1585, 1535, 1512, 1362,
1310, 1231, 1208, 1166, 1122, 1105, 965, 735, 546 cmÀ1; HR-
MS (EI): m/z=379.1024, calcd. for C17H21N3O3S2 [M]+:
379.1024.
S-Methyl-S-phenyl-N-(4-hexyl-1-mesyl)imidazolyl sulfox-
imine
(3u):
yield:
26.5 mg
(44%);
Rf =0.4
(Et2O:CH2Cl2:hexane=1:2:3); yellow liquid; 1H NMR
(400 MHz, CDCl3): d=8.15 (d, J=8.0 Hz, 2H), 7.69 (t, J=
7.4 Hz, 1H), 7.61 (t, J=7.6 Hz, 2H), 6.76 (s, 1H), 3.49 (s,
3H), 3.39 (s, 3H), 2.39 (t, J=7.5 Hz, 2H), 1.52–1.47 (m,
2H), 1.30–1.24 (m, 6H), 0.87 (t, J=6.8 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=145.6, 140.1, 138.7, 133.9, 129.6,
128.2, 109.5, 43.6, 41.5, 31.7, 28.9, 28.3, 28.2, 22.6, 14.1; IR
(film): n=3167, 3132, 3064, 3017, 2928, 2857, 1617, 1583,
1525, 1447, 1359, 1234, 1160, 1112, 1016, 964, 772, 746,
553 cmÀ1
;
HR-MS (EI): m/z=383.1337, calcd. for
C17H25N3O3S2 [M]+: 383.1337.
S-Methyl-S-(2-methylphenyl)-N-(1-mesyl-4-phenyl)imida-
zolyl sulfoximine (4a): yield: 64.6 mg (83%), Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 76–778C;
1H NMR (400 MHz, CDCl3): d=8.31 (dd, J=8.0 Hz, 1.2 Hz,
1H), 7.63 (d, J=7.1 Hz, 2H), 7.55 (td, J=11.2 Hz, 1.3 Hz,
1H), 7.46 (t, J=7.7 Hz, 1H), 7.37 (d, J=7.5 Hz, 1H), 7.33
(s, 1H), 7.31 (t, J=7.5 Hz, 2H), 7.21 (t, J=7.3 Hz, 1H), 3.64
(s, 3H), 3.42 (s, 3H), 2.76 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=146.2, 138.1, 138.0, 136.4, 133.9, 133.3, 133.0,
130.1, 128.4, 127.3, 126.9, 125.0, 109.1, 42.8, 41.6, 20.5; IR
(film): n=3154, 3059, 3028, 2930, 1608, 1565, 1527, 1447,
1347, 1230, 1164, 1104, 1064, 1011, 963, 927, 759, 713,
tho[1,2-d])imidazolyl sulfoximine (3r): yield: 65.8 mg
559 cmÀ1
;
HR-MS (EI): m/z=389.0869, calcd. for
(82%); Rf =0.3 (Et2O:CH2Cl2:hexane=1:2:3); yellow solid;
C18H19N3O3S2 [M]+: 389.0868.
1
mp 77–798C; H NMR (400 MHz, CDCl3): d=8.21 (d, J=
S-Methyl-S-(3-methylphenyl)-N-(1-mesyl-4-phenyl)imida-
zolyl sulfoximine (4b): yield: 64.1 mg (82%); Rf =0.3
7.3 Hz, 2H), 7.70 (t, J=7.3 Hz, 1H), 7.65–7.60 (m, 3H), 7.18
3714
asc.wiley-vch.de
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2015, 357, 3707 – 3717

UPDATES
N-Imidazolylation of Sulfoximines from N-Cyano Sulfoximines
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 69–718C;
1H NMR (400 MHz, CDCl3): d=7.99–7.97 (m, 2H), 7.70 (d,
J=7.1 Hz, 2H), 7.51–7.50 (m, 2H), 7.36 (s, 1H), 7.33 (t, J=
7.5 Hz, 2H), 7.23 (t, J=7.6 Hz, 1H), 3.59 (s, 3H), 3.44 (s,
3H), 2.49 (s, 3H); 13C NMR (100 MHz, CDCl3): d=146.4,
140.0, 138.6, 138.1, 134.9, 132.9, 129.5, 128.4, 128.3, 127.3,
125.2, 125.0, 109.2, 43.7, 41.6, 21.4; IR (film): n=3649, 3154,
3058, 3027, 2928, 1607, 1529, 1447, 1348, 1235, 1164, 1110,
1023, 964, 770, 714, 558 cmÀ1; HR-MS (EI): m/z=389.0869,
calcd. for C18H19N3O3S2 [M]+: 389.0868.
8.06 (dq, J=7.9 Hz, 0.9 Hz, 1H), 7.69–7.66 (m, 3H), 7.57 (t,
J=8.0 Hz, 1H), 7.36 (s, 1H), 7.33 (t, J=7.7 Hz, 2H), 7.24 (t,
J=7.4 Hz, 1H), 3.59 (s, 3H), 3.44 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=145.8, 140.5, 138.1, 135.9, 134.3,
132.8, 131.0, 128.5, 128.4, 127.4, 126.3, 125.0, 109.4, 43.7,
41.7; IR (film): n=3155, 3057, 3019, 2926, 1608, 1564, 1528,
1447, 1410, 1349, 1236, 1164, 1105, 1023, 965, 784, 712,
674 cmÀ1
;
HR-MS (EI): m/z=409.0320, calcd. for
C17H16ClN3O3S2 [M]+: 409.0322.
S-(4-Chlorophenyl)-S-methyl-N-(1-mesyl-4-phenyl)imida-
zolyl sulfoximine (4h): yield: 61.5 mg (75%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 75–778C;
1H NMR (400 MHz, CDCl3): d=8.12 (d, J=8.8 Hz, 2H),
7.68 (d, J=7.1 Hz, 2H), 7.60 (d, J=8.8 Hz, 2H), 7.36 (s,
1H), 7.34 (t, J=7.5 Hz, 2H), 7.23 (t, J=7.4 Hz, 1H), 3.59 (s,
3H), 3.43 (s, 3H); 13C NMR (100 MHz, CDCl3): d=145.9,
141.0, 138.1, 137.1, 132.8, 130.0, 129.7, 128.4, 127.4, 125.0,
109.4, 43.8, 41.6; IR (film): n=3155, 3057, 3019, 2926, 1608,
1564, 1528, 1447, 1410, 1349, 1236, 1164, 1105, 1023, 965,
784, 712, 674 cmÀ1; HR-MS (EI): m/z=409.0320. calcd. for
C17H16ClN3O3S2 [M]+: 409.0322.
S-(2-Bromophenyl)-S-methyl-N-(1-mesyl-4-phenyl)imida-
zolyl sulfoximine (4i): yield: 63.0 mg (69%); Rf =0.4
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 72–748C;
1H NMR (400 MHz, CDCl3): d=8.52 (dd, J=8.0 Hz, 1.6 Hz,
1H), 7.76 (dd, J=7.9 Hz, 1.1 Hz, 1H), 7.64 (td, J=7.4 Hz,
1.1 Hz, 1H), 7.53–7.49 (m, 3H), 7.31 (s, 1H), 7.27 (t, J=
7.5 Hz, 2H), 7.19 (t, J=7.3 Hz, 1H), 3.76 (s, 3H), 3.45 (s,
3H); 13C NMR (100 MHz, CDCl3): d=145.5, 137.8, 137.4,
135.8, 134.8, 133.1, 132.9, 128.3, 128.2, 127.2, 124.8, 120.1,
109.2, 42.2, 41.8; IR (film): n=3154, 3061, 3028, 2929, 1694,
1607, 1566, 1528, 1447, 1359, 1232, 1165, 1106, 1037, 1008,
964, 713, 555 cmÀ1; HR-MS (EI): m/z=452.9819, calcd. for
C17H16BrN3O3S2 [M]+: 452.9816.
S-Methyl-S-(4-methylphenyl)-N-(1-mesyl-4-phenyl)imida-
zolyl sulfoximine (4c): yield: 68.0 mg (87%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 65–668C;
1H NMR (400 MHz, CDCl3): d=8.05 (d, J=8.4 Hz, 2H),
7.70 (d, J=7.1 Hz, 2H), 7.42 (d, J=8.0 Hz, 2H), 7.36 (s,
1H), 7.33 (t, J=7.5 Hz, 2H), 7.23 (t, J=7.3 Hz, 1H), 3.58 (s,
3H), 3.44 (s, 3H), 2.47 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=146.4, 145.2, 138.1, 135.6, 132.9, 130.3, 128.4,
128.1, 127.3, 125.0, 109.2, 43.8, 41.5, 21.7; IR (film): n=3154,
3061, 3026, 2927, 1691, 1608, 1564, 1529, 1447, 1348, 1231,
1164, 1112, 1009, 964, 771, 714, 554 cmÀ1; HR-MS (EI):
m/z=389.0869, calcd. for C18H19N3O3S2 [M]+: 389.0868.
S-(3,5-Dimethylphenyl)-S-methyl-N-(1-mesyl-4-phenyl)-
imidazolyl sulfoximine (4d): yield: 74.0 mg (91%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 72–738C;
1H NMR (400 MHz, CDCl3): d=7.79 (s, 2H), 7.71 (d, J=
7.1 Hz, 2H), 7.36 (s, 1H), 7.35–7.30 (m, 3H), 7.23 (t, J=
7.4 Hz, 1H), 3.57 (s, 3H), 3.44 (s, 3H), 2.44 (s, 6H);
13C NMR (100 MHz, CDCl3): d=146.5, 139.8, 138.4, 138.1,
135.8, 133.0, 128.4, 127.3, 125.5, 125.0, 109.2, 43.7, 41.5, 21.3;
IR (film): n=3152, 3057, 3013, 2926, 2865, 1607, 1565, 1529,
1447, 1348, 1231, 1164, 1101, 1024, 965, 770, 713, 561 cmÀ1
;
HR-MS (EI): m/z=403.1207, calcd. for C19H21N3O3S2 [M]+:
403.1024.
S-(3-Methoxyphenyl)-S-methyl-N-(1-Mesyl-4-phenyl)imid-
azolyl sulfoximine (4e): yield: 82.0 mg (87%); Rf =0.2
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 59–608C;
1H NMR (400 MHz, CDCl3): d=7.75–7.73 (m, 2H), 7.71 (d,
J=7.1 Hz, 2H), 7.52 (t, J=8.2 Hz, 1H), 7.37 (s, 1H), 7.34 (t,
J=7.5 Hz, 2H), 7.25–7.20 (m, 2H), 3.89 (s, 3H), 3.60 (s,
3H), 3.45 (s, 3H); 13C NMR (100 MHz, CDCl3): d=160.4,
146.3, 139.9, 138.2, 132.9, 130.7, 128.4, 127.4, 125.0, 121.2,
120.2, 112.2, 109.2, 55.9, 43.5, 41.6; IR (film): n=3154, 3064,
3014, 2928, 2837, 1597, 1530, 1483, 1348, 1251, 1164, 1109,
1018, 965, 770, 713, 596, 553 cmÀ1; HR-MS (EI): m/z=
405.0817, calcd. for C18H19N3O4S2 [M]+: 405.0817.
S-(4-Bromophenyl)-S-methyl-N-(1-mesyl-4-phenyl)imida-
zolyl sulfoximine (4j): yielçd: 80.0 mg (88%); Rf =0.4
(Et2O:CH2Cl2:hexane=1:2:3); brown solid; mp 84–858C;
1H NMR (400 MHz, CDCl3): d=8.04 (d, J=8.7 Hz, 2H),
7.77 (d, J=8.7 Hz, 2H), 7.68 (d, J=7.1 Hz, 2H), 7.36 (s,
1H), 7.33 (t, J=7.5 Hz, 2H), 7.24 (t, J=7.4 Hz, 1H), 3.58 (s,
3H), 3.43 (s, 3H); 13C NMR (100 MHz, CDCl3): d=145.9,
138.1, 137.7, 133.0, 132.8, 129.8, 129.6, 128.5, 127.4, 125.0,
109.4, 43.8, 41.6; IR (film): n=3152, 3085, 3061, 3019, 2927,
1608, 1528, 1350, 1235, 1164, 1111, 1024, 1003, 964, 771, 713,
556 cmÀ1
;
HR-MS (EI): m/z=452.9818, calcd. for
C17H16BrN3O3S2 [M]+: 452.9816.
S-(4-Methoxyphenyl)-S-methyl-N-(1-mesyl-4-phenyl)imid-
azolyl sulfoximine (4f): yield: 68.0 mg (84%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 69–708C;
1H NMR (400 MHz, CDCl3): d=8.10 (d, J=9.0 Hz, 2H),
7.71 (d, J=7.1 Hz, 2H), 7.36 (s, 1H), 7.33 (t, J=7.5 Hz,
2H), 7.23 (t, J=7.4 Hz, 1H), 7.08 (d, J=9.0 Hz, 2H), 3.90
(s, 3H), 3.58 (s, 3H), 3.45 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=164.1, 146.5, 138.1, 133.0, 130.3, 129.8, 128.4,
127.3, 125.0, 114.9, 109.1, 55.8, 44.0, 41.5; IR (film): n=3155,
3061, 3015, 2928, 2841, 1592, 1529, 1497, 1348, 1313, 1262,
1163, 1112, 1020, 965, 772, 714, 555 cmÀ1; HR-MS (EI): m/
z=405.0814, calcd. for C18H19N3O4S2 [M]+: 405.0817.
S-Methyl-S-(4-trifluoromethylphenyl)-N-(1-mesyl-4-phe-
nyl)imidazolyl sulfoximine (4k): yield: 80.6 mg (90%); Rf =
0.3 (Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 72–
748C; 1H NMR (400 MHz, CDCl3): d=8.33 (d, J=8.2 Hz,
2H), 7.91 (d, J=8.3 Hz, 2H), 7.67 (d, J=7.1 Hz, 2H), 7.37
(s, 1H), 7.33 (t, J=7.5 Hz, 2H), 7.24 (t, J=7.3 Hz, 1H), 3.62
(s, 3H), 3.43 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
145.7, 142.4, 138.2, 135.8 (JC,F =33.3 Hz), 132.7, 128.9, 128.5,
127.5, 126.9 (JC,F =3.7 Hz), 125.0, 123.1 (JC,F =273.5 Hz),
109.5, 43.7, 41.7; IR (film): n=3156, 3057, 3028, 2929, 1692,
1608, 1530, 1448, 1403, 1322, 1240, 1166, 1062, 1027, 1010,
965, 714, 556 cmÀ1; HR-MS (EI): m/z=443.0584, calcd. for
C18H16F3N3O3S2 [M]+: 443.0585.
S-(3-Chlorophenyl)-S-methyl-N-(1-mesyl-4-phenyl)imida-
zolyl sulfoximine (4g): yield: 59.2 mg (72%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 70–728C;
1H NMR (400 MHz, CDCl3): d=8.19 (t, J=1.8 Hz, 1H),
S-Naphthyl-S-methyl-N-(1-mesyl-4-phenyl)imidazolyl sulf-
oximine
(4l):
yield:
69.7 mg
(82%);
Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 79–808C;
Adv. Synth. Catal. 2015, 357, 3707 – 3717
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
3715

UPDATES
Sanghyuck Kim et al.
1H NMR (400 MHz, CDCl3): d=8.79 (s, 1H), 8.11 (dd, J=
Synthesis of S-Aryl-S-methyl- or S,S-Dimethyl-N-
8.7 Hz, 1.9 Hz, 1H), 8.06 (d, J=8.7 Hz, 2H), 7.95 (d, J=
7.9 Hz, 1H), 7.72–7.64 (m, 4H), 7.38 (s, 1H), 7.31 (t, J=
7.5 Hz, 2H), 7.22 (t, J=7.3 Hz, 1H), 3.66 (s, 3H), 3.46 (s,
3H); 13C NMR (100 MHz, CDCl3): d=146.4, 138.1, 135.5,
135.5, 132.9, 132.3, 130.4, 130.1, 129.6, 129.6, 128.4, 128.1,
127.9, 127.3, 125.0, 122.4, 109.3, 43.7, 41.6; IR (film): n=
3154, 3057, 3027, 2928, 1607, 1529, 1447, 1347, 1232, 1194,
1165, 1107, 1074, 1022, 965, 770, 713, 554 cmÀ1; HR-MS
(EI): m/z=425.0870, calcd. for C21H19N3O3S2 [M]+: 425.0868.
S,S-Dimethyl-N-(1-mesyl-4-phenyl)imidazolyl sulfoximine
(4m): yield: 45.7 mg (73%); Rf =0.3 (Et2O:CH2Cl2:
hexane=1:2:3); yellow solid; mp 186–1878C; 1H NMR
(400 MHz, CDCl3): d=7.71 (d, J=7.1 Hz, 2H), 7.35 (t, J=
7.5 Hz, 2H), 7.34 (s, 1H), 7.25 (t, J=7.4 Hz, 1H), 3.48 (s,
6H), 3.43 (s, 3H); 13C NMR (100 MHz, CDCl3): d=146.4,
137.8, 132.8, 128.5, 127.4, 125.0, 109.0, 42.1, 41.5; IR (film):
3155, 3023, 2930, 1607, 1528, 1448, 1348, 1227, 1164, 1107,
1037, 963, 772, 731, 715, 553 cmÀ1; HR-MS (EI): m/z=
313.0554, calcd. for C12H15N3O3S2 [M]+: 313.0555.
imidazolyl Sulfoximine in One-Pot
A reaction test tube was charged with copper(I) thiophene-
2-carboxylate (10.0 mol%), Rh2(OPiv)4 (2.0 mol%), alkyne
5 (3.3 equiv.), N-mesyl azide 6 (3.0 equiv.), then N-cyano S-
aryl-S-methyl- or S,S-dimethyl sulfoximine (1, 1.0 equiv.)
and toluene (0.1m) were added under a nitrogen atmos-
phere. The reaction mixture was stirred at 258C for 1 h, and
then heated at 808C for 30 min. After celite filtration and
evaporation of the solvents under vacuum, the crude prod-
uct was purified by column chromatography on silica gel
(Et2O:CH2Cl2:hexane=1:2:3) to afford 3; yield: 56–92%.
Acknowledgements
This work was supported by the National Research Founda-
tion of Korea (NRF) grant funded by the Korea government
(2011-0018355).
S-(4-Methoxyphenyl)-S-methyl-N-(1-mesyl-4-phenyl)imid-
azolyl sulfoximine (4n): yield: 80.9 mg (83%); Rf =0.3
(Et2O:CH2Cl2:hexane=1:2:3); yellow solid; mp 150–1528C;
1H NMR (400 MHz, CDCl3): d=8.09 (d, J=9.0 Hz, 2H),
7.90 (dd, J=7.9 Hz, 1.7 Hz, 1H), 7.81 (s, 1H), 7.58 (dd, J=
8.0 Hz, 0.8 Hz, 1H), 7.29 (td, J=7.3 Hz, 1.2 Hz, 1H), 7.10–
7.06 (m, 3H), 3.90 (s, 3H), 3.56 (s, 3H), 3.48 (s, 3H);
13C NMR (100 MHz, CDCl3): d=164.1, 145.7, 135.7, 133.6,
133.3, 130.7, 130.4, 129.7, 128.3, 127.2, 120.7, 114.9, 113.3,
55.8, 44.0, 41.6; IR (film): n=3180, 3064, 3016, 2929, 2837,
1592, 1532, 1497, 1359, 1263, 1164, 1109, 1020, 768, 728,
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