Imino-λ3-iodane and Catalytic Amount of I2-Mediated Synthesis of N-Allylsulfenamides via [2,3]-Sigmatropic Rearrangement

Article abstract of DOI:10.1002/ejoc.202000961

A facile metal-free [2,3]-sigmatropic rearrangement reaction of allyl sulfides via N-sulfilimine intermediates has been developed. Treatment of allyl sulfides with imino-λ³-iodanes in the presence of a catalytic amount of elemental iodine allow

Full text of DOI:10.1002/ejoc.202000961

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Iodine-mediated Reactions
Imino-λ3-iodane and Catalytic Amount of I2-Mediated Synthesis
of N-Allylsulfenamides via [2,3]-Sigmatropic Rearrangement
Cody L. Makitalo,[a] Akira Yoshimura,*[a,b] Gregory T. Rohde,[c] Irina A. Mironova,[b]
Rosa Y. Yusubova,[b] Mekhman S. Yusubov,[b] Viktor V. Zhdankin,[a] and Akio Saito[d]
Abstract: A facile metal-free [2,3]-sigmatropic rearrangement good yields. Several N-allylsulfenamide structures have been
reaction of allyl sulfides via N-sulfilimine intermediates has been confirmed by single-crystal X-ray crystallography. The reaction
developed. Treatment of allyl sulfides with imino-λ3-iodanes in initially involves the sulfonylimino group transfer reaction be-
the presence of a catalytic amount of elemental iodine allowed tween imino-λ3-iodane and the sulfur atom, resulting in the
the reaction to proceed under mild conditions and gave the formation of N-sulfilimine species, followed by [2,3]-sigmatropic
corresponding N-allylsulfenamide compounds in moderate to rearrangement to form the N-allylsulfenamide.
Introduction
N-allylsulfenamides under suitable reaction conditions. This
transformation reaction is useful for the synthesis of sulfen-
amide compounds, which have found important applications in
bioactivity and material chemistry.[5] The sulfur protective
group can be readily removed under mild conditions to pro-
duce the unprotected N-allylamides.[4f,4g,6]
Sulfur ylide compounds are versatile reagents that are widely
useful in organic synthesis, and various types of sulfur ylides
have been prepared.[1] Many useful reactions and synthetic pro-
cedures have been developed using these ylides. Particularly,
[2,3]-sigmatropic rearrangement of sulfur ylides is an important
chemical transformation leading to various bond–bond-forming
reactions, which have been demonstrated as useful reaction
tools for making various sulfur compounds in organic synthe-
sis.[1a,1i–1k] Sulfur–nitrogen ylides, sulfilimines, are known as
mono-aza analog of sulfoxides, and these compounds can be
used as efficient nitrogen installing reagents in various reac-
tions.[2] Some sulfilimines can also be converted by appropriate
oxidants to sulfoximines, which can be used as active materials
in medicinal or synthetic chemistry.[3] Sulfilimines with an allyl
group are known to be active intermediates, which could be
generated from allyl sulfides and nitrogen-based oxidants un-
der appropriate reaction conditions.[4] Several research groups
reported that the generation of allylsulfilimines involves
[2,3]-sigmatropic rearrangement leading to the formation of
Organohypervalent iodine compounds are known as power-
ful oxidizing reagents that can be universally as well as effi-
ciently employed in a variety of important conversion reac-
tions.[7] Some hypervalent iodine(III) reagents allow for a facile
oxidative ligand transfer to form the new bond–bond-forming
products.[8] Recently, a number of nitrogen transfer reactions
such as azidation,[9] amination,[10] and sulfonylimidation[11] us-
ing hypervalent iodine(III) reagents with nitrogen ligands have
been developed. In particular, imino-λ3-iodanes are an impor-
tant class of nitrogen ligand transfer reagents, and a variety of
nitrogen bond forming reactions with various atoms, including
carbon atom or heteroatoms, have been reported using these
reagents.[12] Many of reactions using imino-λ3-iodanes require
the use of metal salts or metal complexes as a catalyst for gen-
erating highly active species. For example, the reaction of allyl
sulfides using imino-λ3-iodanes in the presence of a metal cata-
lyst provided the corresponding N-allylsulfenamide compounds
via [2,3]-sigmatropic rearrangement of the intermediate N-sulfil-
imine species (Scheme 1a).[13] However, some metallic reagents
are toxic, expensive, or not easy to prepare. From an environ-
mental issue and handling viewpoint, the development of
metal-free reaction conditions is significant for green chemistry.
Several groups have reported examples of reactions without
the use of metallic reagents.[14] For example, Lamar and Nicho-
las have developed the metal-free C–H amination reaction us-
ing imino-λ3-iodanes in the presence of a catalytic amount of
elemental iodine.[14a] Lamar group also reported the reaction
of an aldehyde with imino-λ3-iodanes under similar metal-free
reaction conditions yielding the imidation products in moder-
ate to good yields.[14b] Minakata and co-workers reported the
[a] C. L. Makitalo, Dr. A. Yoshimura, Prof. Dr. V. V. Zhdankin
Department of Chemistry and Biochemistry, University of Minnesota Duluth,
Minnesota 55812, USA
E-mail: ayoshimu@d.umn.edu
[b] Dr. A. Yoshimura, I. A. Mironova, Dr. R. Y. Yusubova, Prof. Dr. M. S. Yusubov
Research School of Chemistry and Applied Biomedical Sciences, The Tomsk
Polytechnic University,
634050 Tomsk, Russia
[c] Dr. G. T. Rohde
Marshall School,
Duluth, Minnesota 55811, USA
[d] Prof. Dr. A. Saito
Division of Applied Chemistry, Institute of Engineering, Tokyo University of
Agriculture and Technology,
2-23-16 Naka-cho, Koganei, Tokyo 184-8588, Japan
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.202000961.
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aziridination reactions of styrenes using (N-tosylimino)-phenyl-
λ3-iodane under metal-free conditions.[14c] Recently, our group
found the metal-free synthetic procedure of (N-sulfonyl)-sulfil-
imine compounds from various sulfides using imino-λ3-
iodanes.[14d]
Table 1. Optimization of preparation of N-allylsulfenamide 3a from allyl
methyl sulfide 1a using (N-tosylimino)-phenyl-λ3-iodane 2a.[a]
[b]
Solvent
I2 [mol-%]
Time [h]]
3a Yield[%]
[c]
1
2
3
4
5
6
7
8
MeCN
AcOEt
2
2
2
2
2
2
2
2
2
1
0.5
0
2
24
24
24
24
24
24
24
24
24
24
24
24
12
24
93
92
[c]
CH2Cl2
CHCl3
MeOH
Heptane
ClCH2CH2Cl
PhH
97 (97)
[c]
94
40
[c]
14[c]
96[c]
55
9
Ether
32[c]
92 (77)
88 (73)
(65)
10
11
12
13
14[d]
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
Scheme 1. Synthesis of N-allylsulfenamide from allylsufide using PhINTs.
(78)
(91)
To the best of our knowledge, however, the synthetic
approach to N-allylsulfenamide from allyl sulfides using imino-
λ3-iodanes under metal-free conditions has not been reported.
Herein, we report the straightforward metal-free synthesis of
N-allylsulfenamide compounds via [2,3]-sigmatropic rearrange-
ment of N-sulfilimine intermediates, which can be initially syn-
thesized from allyl sulfides and imino-λ3-iodanes in the pres-
ence of a catalytic amount of elemental iodine (Scheme 1b).
2
[a] Reaction conditions: allyl methyl sulfide 1a (0.20 mmol, 1 equiv.) and
imino-λ3-iodane 2a (0.24 mmol, 1.2 equiv.) with I2 (0–2 mol-%) stirred in a
solvent (2 mL) at room temperature for 12–24 h. [b] Yields of product 3a
determined from 1H NMR spectra of the reaction mixture (using as 1,1,2,2-
tetrachloroethane as an internal standard) are shown (numbers in parenthe-
ses show an isolated yield of 3a). [c] Allyl methyl sulfide 1a was detected
from the reaction mixture. [d] Reaction was performed under dark conditions.
sulfide 1d using imino-λ3-iodane with different substituents
2b–2d proceeded smoothly producing respective N-allylsulfen-
amides in moderate yields 3f–3k (entries 6–11). It is noteworthy
that this reaction method also worked on substituted allyl sulf-
ides to give desired sigmatropic rearrangement products 3l–3s
in moderate yields (entries 12–19). Meanwhile, the reaction of
2-vinylthiolane 1i using imino-λ3-iodane 2a afforded the eight-
membered ring product 3s albeit in 20 % yield due to giving
complex mixture along with a small amount of 1h (entry 19).
Compared to the previously reported preparation of N-allyl-
sulfenamide from allyl sulfide using imino-λ3-iodane under
metal catalyst conditions, our procedure gave the correspond-
ing [2,3]-sigmatropic rearrangement products in comparable or
higher yields.[13] In particular, the large scaled reaction of
phenyl allyl sulfide 1d (1 mmol) using optimized conditions
gave the desired product 3d in 70 % (entry 4). The structures
of products 3a and 3q were established by X-ray crystallogra-
phy (See Figure1, see the Supporting Information for details).
One potential utility of N-allylsulfenamides is that they have
Results and Discussion
Our approach to metal-free synthesis of N-allylsulfenamide is
based on our group's recently reported synthesis of N-sulfil-
imine from sulfide with imino-λ3-iodanes in the presence of a
catalytic amount of elemental iodine.[14d] In our initial experi-
ments, we investigated the reaction of allyl methyl sulfide 1a
(1 equiv.) with (N-tosylimino)-phenyl-λ3-iodane 2a (1.2 equiv.)
in the presence of a catalytic amount of I2 (2 mol-%) in various
solvents at room temperature (Table 1, entries 1–9). We have
found that the reaction in dichloromethane gave the desired
product 3a in 97 % isolated yield. Decreasing the amount of
I2 catalyst from 2 mol-% to 0.5 mol-% afforded the desired prod-
uct 3a in slightly lower yields (entries 10 and 11). When the
reaction was performed in the absence of I2, the product 3a
was produced in moderate yield (entry 12). This result indicated
that the presence of the I2 catalyst was effective for the conver-
sion of the desired product. Shortening of the reaction time
reduced the desired product 3a yield (entry 13). Finally, the been known to be easily converted to N-allyl sulfonamide.[4g]
reaction proceeded efficiently under dark conditions without The reaction of the prepared N-allylsulfenamides 3a, 3l under
significant changes (entry 14).[14c,14d]
basic conditions resulted in the S–N bond cleavage to produce
the respective N-allyl sulfonamides 4a,b in good yields
(Scheme 2).
In the next step, we investigated the preparation of various
N-allylsulfenamides 3 from the respective substituted allyl sulf-
ides 1 using imino-λ3-iodanes 2 with 2 mol-% I2 as catalyst
In order to clarify the reaction mechanism of allyl sulfide
under optimized reaction conditions (Table 2). In general, the with imino-λ3-idoane in the presence of I2, we have carried out
reaction of ethyl 1b, propyl 1c, or phenyl allyl sulfide 1d with several control experiments. Based on previously reported reac-
(N-tosylimino)-phenyl-λ3-iodane 2a gave the corresponding N- tions, this reaction is probably a two-step reaction.[4b,13–14]
allylsulfenamides 3b-d in good yields (entries 1–4). In the treat- Firstly, the reaction of allyl sulfide and imino-λ3-iodane in the
ment of diallyl sulfide 2e, the desired product 3e was obtained presence of I2 generated sulfilimine as the initial intermediate,
in 82 % (entry 5). The reaction of methyl 1a or phenyl allyl and then [2,3]-sigmatropic rearrangement led to N-allyl-sulfen-
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Table 2. Reaction of allyl sulfides 1 using imino-phenyl-λ3-iodanes 2.[a]
Scheme 2. Deprotection of N-allylsulfenamide 3 under basic conditions.
amide. When the reaction of phenyl allyl sulfide 1d was per-
formed in the presence of TEMPO or BHT as radical scavengers,
the desired product 3d was not obtained, and 1d was recov-
ered in 76–85 % from the reaction mixture (Scheme 3). The
results of the reactions under dark conditions (Table 1, entry
14) imply that the radical pathway is involved in the mecha-
nism. Most likely, the generation of sulfilimine as the first inter-
mediate is induced by the amidyl radical species, which have
been reported to be generated from the combination of I2 and
imino-λ3-iodane.[14d] Through sigmatropic rearrangement, the
reactions of allyl sulfides with the methyl group at the terminal
position resulted in the shifting of the methyl group from the
terminal to the internal position (Table 2, entries 16–18). The X-
ray crystallography analysis of 3q also confirmed the presence
of the internal methyl group (Figure 1). Therefore, it is consid-
ered that [2,3]-sigmatropic rearrangement might occur during
the reaction process.
Scheme 3. Control experiments.
Figure 1. X-ray crystal structures of 3a. (CCDC 2011021) and 3q. (CCDC
2011022) Thermal ellipsoids drawn at the 50 % probability level and
hydrogen atoms were removed for clarity.
Based on the blank experiment results, and previously re-
ported relative reaction of allyl sulfides with imino-λ3-iodane,
we proposed the reaction mechanism for the formation of
N-allylsulfenamide compounds (Scheme 4).[4b,13–14] Firstly, N,N-
diiodotosylamide 5, which can be generated from (N-tosyl-
imino)-phenyl-λ3-iodane 2a with I2, is converted into the amidyl
radical 6 and iodine radical. The generated amidyl radical 6
reacts with allyl methyl sulfide 1a to generate sulfilimine spe-
[a] Reaction conditions: allyl methyl sulfide 1 (0.20 mmol, 1 equiv.), and im-
ino-λ3-iodane 2 (0.24 mmol, 1.2 equiv.), with I2 (2 mol-%) stirred in a dichloro-
methane at room temperature for 24 h. [b] Isolated yield of 3. [c] Large scale
experiment: phenyl allyl sulfide 1d (1.0 mmol, 1 equiv.), and imino-λ3-iodane
2a (1.2 mmol, 1.2 equiv.) using I2 (2 mol-%) in dichloromethane (10 mL) were
stirred for 24 hours at room temperature. [d] E/Z-ration = >99:<1.
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General Procedure for Preparation of N-allylsulfenamides 3: Im-
ino-λ3-iodane 2a (0.24 mmol) was added at room temperature to a
stirred mixture of allyl sulfide 1 (0.20 mmol) and I2 (2 mol-%) in
dichloromethane (2.0 mL). The reaction was stirred at room temper-
ature for 24 hours. After the reaction, 5 % aqueous Na2S2O3 (2.5–
5.0 mL) was added to the mixture and the solution was extracted
with ethyl acetate. The organic layer was dried with anhydrous
Na2SO4 and concentrated under reduced pressure. The residue was
separated by column chromatography using the hexane/EtOAc (1:1)
to afford the pure product 3.
cies 8 and reproduces the I2 via intermediate 7. The produced
sulfilimine 8 is immediately involved in [2,3]-sigmatropic rear-
rangement to give the desired N-allylsulfenamide product 3a.
Finally, the regenerated I2 reacts with (N-tosylimino)-phenyl-λ3-
iodane 2a to continue the next reaction cycle.
N-Allyl-4-methyl-N-(methylthio)benzenesulfonamide (3a):[13b]
Reaction of allyl methyl sulfide 1a (18 mg, 0.20 mmol) and imino-λ3-
iodane 2a (90 mg, 0.24 mmol) according to the general procedure
afforded 50 mg (97 %) of product 3a, isolated as a brown solid: m.p.
65.5–66.5 °C (lit.[13b]; m.p. 68.5–69.5 °C); IR (neat) cm–1: ν = 3067,
˜
2987, 2856, 1651, 1598, 1436, 1347, 1162, 991, 928, 735; 1H NMR
(500 MHz, CDCl3): δ = 7.79 (d, J = 8.3 Hz, 2H), 7.31 (d, J = 8.3 Hz,
2H), 5.88–5.77 (m, 1H), 5.25 (dd, J = 17.5 Hz, 10.5 Hz, 1H), 5.21 (d,
J = 10.5 Hz, 1H), 4.06 (d, J = 6.0 Hz, 2H), 2.44 (s, 3H), 2.43 (s, 3H);
13C NMR (125 MHz, CDCl3): δ = 143.8, 136.1, 133.2, 129.5, 127.8,
119.2, 56.4, 23.6, 21.6; HRMS (ESI-positive ionization): calcd. for
Scheme 4. Proposed reaction mechanism.
C
11H16NO2S2 ([M + H]+): 258.0622, found 258.0596.
Single crystals of product 3a suitable for X-ray crystallographic anal-
ysis were obtained by slow evaporation of dichloromethane solu-
tion. For details on crystal structure of compound 3a see the CIF
file in Supporting Information. CCDC 2011021.
Conclusions
In summary, we have developed the I2 catalyzed synthesis of
N-allylsulfenamides from allyl sulfides using imino-λ3-iodane
under metal-free conditions. In comparison with the previously
reported procedure using imino-λ3-iodane in the presence of
metal catalyst, our procedure generally affords higher yields.
N-Allylsulfenamide under basic conditions can be converted
into the allylamides in moderate to good yield. The reaction
N-Allyl-N-(ethylthio)-4-methylbenzenesulfonamide (3b): Reac-
tion of ethyl allyl sulfide 1b (20 mg, 0.20 mmol) and imino-λ3-
iodane 2a (90 mg, 0.24 mmol) according to the general procedure
afforded 53 mg (99 %) of product 3b, isolated as a brown oil: IR
(neat) cm–1: ν = 3093, 2978, 2929, 2871, 1647, 1597, 1495, 1329,
˜
1
1159, 925, 712; H NMR (500 MHz, CDCl3): δ = 7.79 (d, J = 8.5 Hz,
2H), 7.29 (d, J = 8.5 Hz, 2H), 5.82–5.68 (m, 1H), 5.24–5.12 (m, 2H),
mechanism involves sulfonylimino group transfer reaction to 4.04 (d, J = 6.5 Hz, 2H), 2.90 (q, J = 8.0 Hz, 2H), 2.42 (s, 3H), 1.22 (t,
J = 7.5 Hz, 3H); 13C NMR (75 MHz, CDCl3): δ = 143.8, 136.0, 133.1,
the sulfide atom of allyl sulfides followed by [2,3]-sigmatropic
rearrangement to give the corresponding N-allylsulfenamides.
129.4, 127.8, 119.2, 57.8, 34.0, 21.5, 12.2; HRMS (APCI-positive ioniza-
tion): calcd. for C12H18NO2S2 ([M + H]+): 272.0779, found 272.0789.
N-Allyl-4-methyl-N-(propylthio)benzenesulfonamide (3c): Reac-
tion of propyl allyl sulfide 1c (23 mg, 0.20 mmol) and imino-λ3-
iodane 2a (90 mg, 0.24 mmol) according to the general procedure
afforded 40 mg (70 %) of product 3c, isolated as a yellow oil: IR
Experimental Section
General Experimental Remarks: All reactions were performed un-
der dry argon atmosphere with flame-dried glassware. Dichloro-
methane was distilled immediately prior to use. All commercial rea-
gents were ACS reagent grade and used without further purifica-
tion. Melting points were determined in an open capillary tube with
a Mel-temp II melting point apparatus. Infrared spectra were
recorded on a PerkinElmer 1600 series FT-IR spectrophotometer.
1H NMR spectra were recorded on a Varian Inova 500, 300 MHz and
Bruker 400 MHz NMR spectrometer; 13C NMR spectra were recorded
on Varian Inova 500, 300 MHz and Bruker 400 MHz NMR spectrome-
(neat) cm–1: ν = 3087, 2971, 2935, 2877, 1649, 1600, 1496, 1340,
˜
1185, 995, 928, 709; 1H NMR (500 MHz, CDCl3): δ = 7.80 (d, J =
7.5 Hz, 2H), 7.30 (d, J = 7.5 Hz, 2H), 5.82–5.70 (m, 1H), 5.24–5.12 (m,
2H), 4.04 (d, J = 6.5 Hz, 2H), 2.86 (t, J = 7.5 Hz, 2H), 2.43 (s, 3H),
1.68–1.56 (m, 2H), 0.98 (t, J = 7.5 Hz, 3H); 13C NMR (75 MHz, CDCl3):
δ = 143.8, 136.0, 133.1, 129.4, 127.9, 119.2, 57.7, 42.2, 21.6, 20.6,
13.3; HRMS (APCI-positive ionization): calcd. for C13H19NO2S2 ([M +
H]+): 286.0935, found 286.0944.
ters at 125, 75 and 100 MHz, respectively. Chemical shifts are re- N-Allyl-4-methyl-N-(phenylthio)benzenesulfonamide
(3d):[4d]
ported in parts per million (ppm). 1H and 13C chemical shifts are
referenced relative to the tetramethylsilane. X-ray crystal analysis
was performed by Rigaku RAPID II XRD Image Plate using graphite-
monochromated Cu-Kα radiation (λ = 1.54187 Å) at 173 K. Please
see the supporting information or the cif file for more detailed crys-
tallography information. Cyclohex-2-en-1-yl(phenyl)sulfane 1e,[15]
(3-methylbut-2-en-1-yl)(phenyl)sulfane 1g,[16] and 2-vinyltetrahy-
Reaction of phenyl allyl sulfide 1d (30 mg, 0.20 mmol) and imino-λ3-
iodane 2a (90 mg, 0.24 mmol) according to the general procedure
afforded 51 mg (80 %) of product 3d, isolated as a light yellow oil;
IR (neat) cm–1: ν = 3062, 2987, 2919, 2865, 1643, 1597, 1582, 1352,
˜
1166, 997, 930, 741; 1H NMR (500 MHz, CDCl3): δ = 7.81 (d, J =
8.0 Hz, 2H), 7.39 (d, J = 9.0 Hz, 2H), 7.35–7.28 (m, 4H), 7.26–7.20 (m,
1H), 5.76–5.65 (m, 1H), 5.17 (dd, J = 17.0 Hz, 1.3 Hz, 1H), 5.13 (dd,
drothiophene 1h[17] were prepared according to the reported pro- J = 11.5 Hz, 1.3 Hz, 1H), 4.15 (d, J = 6.3 Hz, 2H), 2.43 (s, 3H); 13C
cedures. Various imino-λ3-iodanes 2 (2a,[18] 2b, c,[19] 2d[14h]) were
prepared according to the reported procedures. Other employed
reagents were commercially available from chemical companies.
NMR (125 MHz, CDCl3): δ = 144.0, 137.1, 136.2, 132.4, 129.6, 128.9,
127.8, 127.4, 126.3, 119.7, 56.9, 21.6; HRMS (ESI-positive ionization):
calcd. for C16H17NNaO2S2 ([M + Na]+): 342.0598, found 342.0571.
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Large scale reaction for preparation of N-allyl-4-methyl-N-
(phenylthio)benzenesulfonamide (3d): Imino-λ3-iodane 2a
(448 mg, 1.20 mmol) was added at room temperature to a stirred
mixture of phenyl allyl sulfide 1d (150 mg, 1.00 mmol) and I2 (5 mg,
0.02 mmol) in dichloromethane (10.0 mL) and the reaction was
stirred at room temperature for 24 hours. After the reaction, 5 %
aqueous Na2S2O3 (20 mL) was added, and the mixture was ex-
tracted with ethyl acetate. The organic phase was dried with anhy-
drous Na2SO4 and concentrated under reduced pressure. Purifica-
tion by column chromatography (hexane/ethyl acetate = 1:1) af-
forded 223 mg (70 %) of product 3d.
857, 739; 1H NMR (300 MHz, CDCl3): δ = 8.35 (d, J = 8.9 Hz, 2H),
8.11 (d, J = 8.9 Hz, 2H), 7.46–7.40 (m, 2H), 7.39–7.28 (m, 3H), 5.82–
5.65 (m, 1H), 5.28–5.16 (m, 2H), 4.23 (d, J = 6.6 Hz, 2H); 13C NMR
(75 MHz, CDCl3): δ = 150.3, 144.9, 135.8, 131.7, 129.2, 128.3, 127.3,
124.2, 120.4, 57.4; HRMS (APCI-positive ionization): calcd. for
C
15H15N2O4S2 ([M + H]+): 351.0473, found 351.0475.
N-Allyl-2-nitro-N-(phenylthio)benzenesulfonamide (3j): Reaction
of phenyl allyl sulfide 1d (30 mg, 0.20 mmol) and imino-λ3-iodane
2c (97 mg, 0.24 mmol) according to the general procedure afforded
13 mg (18 %) of product 3j, isolated as a light yellow oil; IR (neat)
cm–1: ν = 3090, 2929, 2856, 1641, 1540, 1365, 1348, 1169, 995, 926,
˜
N-Allyl-N-(allylthio)-4-methylbenzenesulfonamide (3e):[13b] Re- 854, 742; 1H NMR (300 MHz, CDCl3): δ = 8.20 (d, J = 6.9 Hz, 1H),
action of diallyl sulfide 1e (23 mg, 0.24 mmol) and imino-λ3-iodane 7.72–7.58 (m, 3H), 7.37–7.29 (m, 3H), 7.28–7.16 (m, 2H), 5.95–5.78
2a (90 mg, 0.24 mmol) according to the general procedure afforded
47 mg (82 %) of product 3e, isolated as a light brown oil; IR (neat)
(m, 1H), 5.32–5.18 (m, 2H), 4.34 (d, J = 6.6 Hz, 2H); 13C NMR (75 MHz,
CDCl3): δ = 147.8, 135.7, 134.1, 132.7, 132.6, 131.6, 129.0, 128.0,
cm–1: ν = 3086, 2985, 2924, 2859, 1600, 1496, 1346, 1163, 992, 930, 127.0, 124.2, 120.0, 57.2; HRMS (APCI-positive ionization): calcd. for
˜
1
726; H NMR (500 MHz, CDCl3): δ = 7.79 (d, J = 7.5 Hz, 2H), 7.30 (d,
J = 7.5 Hz, 2H), 5.90–5.67 (m, 2H), 5.26–5.12 (m, 4H), 4.07 (d, J =
6.0 Hz, 2H), 3.52 (d, J = 7.5 Hz, 2H), 2.43 (s, 3H); 13C NMR (75 MHz,
CDCl3): δ = 143.8, 136.2, 133.1, 131.4, 129.5, 127.9, 119.9, 119.1, 57.8,
43.7, 21.6; HRMS (APCI-positive ionization): calcd. for C13H17NO2S2
([M + H]+): 284.0779, found 284.0787.
C
15H15N2O4S2 ([M + H]+): 351.0473, found 351.0485.
N-Allyl-N-(phenylthio)benzenesulfonamide (3k): Reaction of
phenyl allyl sulfide 1d (30 mg, 0.20 mmol) and imino-λ3-iodane 2d
(86 mg, 0.24 mmol) according to the general procedure afforded
29 mg (47 %) of product 3k, isolated as a light brown oil; IR (neat)
cm–1: ν = 3066, 3020, 2987, 2923, 2859, 1643, 1582, 1447, 1349,
˜
N-Allyl-N-(methylthio)-4-nitrobenzenesulfonamide (3f): allyl
methyl sulfide 1a (18 mg, 0.20 mmol) and imino-λ3-iodane 2b
1169, 1000, 930, 738; 1H NMR (300 MHz, CDCl3): δ = 7.93 (d, J =
6.9 Hz, 2H), 7.64–7.56 (m, 1H), 7.55–7.47 (m, 2H), 7.39 (d, J = 6.9 Hz,
(97 mg, 0.24 mmol) according to the general procedure afforded 2H), 7.35–7.28 (m, 2H), 7.27–7.20 (m, 1H), 5.82–5.64 (m, 1H), 5.18
53 mg (92 %) of product 3f, isolated as a white solid: m.p. 111.2–
(dd, J = 13.8 Hz, 1.3 Hz, 1H), 5.13 (dd, J = 6.5 Hz, 1.3 Hz, 1H), 4.17
(dd, J = 6.5 Hz, 1.3 Hz, 2H); 13C NMR (75 MHz, CDCl3): δ = 139.2,
136.9, 133.1, 132.2, 129.0, 129.0, 127.8, 127.6, 126.5, 119.8, 56.9;
HRMS (ESI-positive ionization): calcd. for C15H15NNaO2S2 ([M + Na]+):
328.0442, found 328.0450.
112.7 °C; IR (neat) cm–1: ν = 3115, 3094, 3072, 2921, 2850, 1644,
˜
1605, 1533, 1353, 1167, 988, 929, 741; 1H NMR (500 MHz, CDCl3):
δ = 8.37 (d, J = 7.5 Hz, 2H), 8.11 (d, J = 7.5 Hz, 2H), 5.86–5.76 (m,
1H), 5.27 (dd, J = 18.0 Hz, 1.0 Hz, 1H), 5.25 (d, J = 11.0 Hz, 1H), 4.27
(dd, J = 6.5 Hz, 1.0 Hz, 2H), 2.57 (s, 3H); 13C NMR (125 MHz, CDCl3):
δ = 150.2, 144.6, 132.4, 129.1, 124.1, 120.0, 57.1, 24.2; HRMS (APCI-
positive ionization): calcd. for C10H12N2O4S2 ([M]+): 288.0238, found
288.0245.
N-(Cyclohex-2-en-1-yl)-4-methyl-N-(phenylthio)benzenesulfon-
amide (3l):[4d] Reaction of cyclohex-2-en-1-yl(phenyl)sulfane 1e
(38 mg, 0.20 mmol) and imino-λ3-iodane 2a (90 mg, 0.24 mmol)
according to the general procedure afforded 38 mg (53 %) of prod-
uct 3l, isolated as a white solid: m.p. 72.0–73.4 °C (lit.[4d]; m.p. 101–
N-Allyl-N-(methylthio)-2-nitrobenzenesulfonamide (3g): allyl
methyl sulfide 1a (18 mg, 0.20 mmol) and imino-λ3-iodane 2c
102 °C); IR (neat) cm–1: ν = 3063, 3028, 2932, 2862, 1651, 1600,
˜
(97 mg, 0.24 mmol) according to the general procedure afforded 1582, 1480, 1361, 1165, 737; 1H NMR (300 MHz, CDCl3): δ = 7.85 (d,
52 mg (89 %) of product 3g, isolated as a colorless oil; IR (neat)
J = 8.3 Hz, 2H), 7.44 (d, J = 8.3 Hz, 2H), 7.36–7.27 (m, 4H), 7.19 (t,
J = 7.1 Hz, 1H), 5.79–5.69 (m, 1H), 4.98–4.76 (m, 2H), 2.43 (s, 3H),
1.98–1.52 (m, 6H); 13C NMR (125 MHz, CDCl3): δ = 144.0, 139.5,
137.1, 132.5, 129.7, 128.7, 127.7, 127.0, 126.6, 124.4, 59.9, 28.6, 24.2,
21.6, 21.2; HRMS (ESI-positive ionization): calcd. for C19H21NNaO2S2
([M + Na]+): 382.0911, found 382.0883.
cm–1: ν = 3096, 3022, 2986, 2921, 1649, 1591, 1540, 1368, 1167,
˜
999, 933, 746; 1H NMR (500 MHz, CDCl3): δ = 8.25 (d, J = 8.0 Hz,
1H), 7.77–7.66 (m, 3H), 6.0–5.89 (m, 1H), 5.37 (d, J = 17.0 Hz, 1H),
5.29 (d, J = 10.0 Hz, 1H), 4.22 (d, J = 6.5 Hz, 2H), 2.44 (s, 3H); 13C
NMR (125 MHz, CDCl3): δ = 147.8, 134.0, 133.5, 132.8, 131.9, 131.5,
124.2, 120.0, 57.0, 23.0; HRMS (ESI-positive ionization): calcd. for
N-(Cyclohex-2-en-1-yl)-4-nitro-N-(phenylthio)benzenesulfon-
amide (3m): Reaction of cyclohex-2-en-1-yl(phenyl)sulfane 1e
C
10H13N2O4S2 ([M]+): 289.0317, found 289.0292.
N-Allyl-N-(methylthio)benzenesulfonamide (3h): allyl methyl (38 mg, 0.20 mmol) and imino-λ3-iodane 2b (97 mg, 0.24 mmol)
sulfide 1a (18 mg, 0.20 mmol) and imino-λ3-iodane 2d (86 mg, according to the general procedure afforded 19 mg (24 %) of prod-
0.24 mmol) according to the general procedure afforded 44 mg
(89 %) of product 3h, isolated as a light yellow oil; IR (neat) cm–1
uct 3m, isolated as a colorless solid: m.p. 137.7–138.3 °C; IR (neat)
:
cm–1: ν = 3065, 3031, 2937, 2864, 1609, 1583, 1531, 1479, 1350,
˜
ν = 3069, 2988, 2919, 2859, 1643, 1587, 1479, 1349, 1166, 999, 931, 1170, 738; 1H NMR (500 MHz, CDCl3): δ = 8.36 (d, J = 8.3 Hz, 2H),
˜
757; 1H NMR (500 MHz, CDCl3): δ = 7.92 (d, J = 8.5 Hz, 2H), 7.60
(t, J = 7.8 Hz, 1H), 7.55–7.49 (m, 2H), 5.88–5.77 (m, 1H), 5.25 (d, J = 7.24 (d, J = 7.5 Hz, 1H), 5.84–5.77 (m, 1H), 5.01–4.95 (m, 2H), 2.01–
17.0 Hz, 1H), 5.22 (d, J = 10.5 Hz, 1H), 4.08 (d, J = 6.5 Hz, 2H), 2.46
1.87 (m, 3H), 1.79–1.71 (m, 1H), 1.69–1.52 (m, 2H); 13C NMR
(s, 3H); 13C NMR (125 MHz, CDCl3): δ = 139.0, 133.1, 133.0, 128.9, (125 MHz, CDCl3): δ = 150.3, 145.5, 138.1, 133.4, 129.0, 128.9, 127.4,
8.17 (d, J = 8.3 Hz, 2H), 7.47 (d, J = 8.0 Hz, 2H), 7.37–7.31 (m, 2H),
127.7, 119.3, 56.5, 23.7; HRMS (ESI-positive ionization): calcd. for
126.3, 124.3, 60.5, 28.7, 24.2, 21.1; HRMS (ESI-positive ionization):
C10H14NO2S2 ([M + H]+): 244.0466, found 244.0453.
calcd. for C18H18N2NaO4S2 ([M + Na]+): 413.0606, found 413.0580.
N-Allyl-4-nitro-N-(phenylthio)benzenesulfonamide (3i): Reaction
of phenyl allyl sulfide 1d (30 mg, 0.20 mmol) and imino-λ3-iodane
N-(Cyclohex-2-en-1-yl)-2-nitro-N-(phenylthio)benzenesulfon-
amide (3n): Reaction of cyclohex-2-en-1-yl(phenyl)sulfane 1e
2b (97 mg, 0.24 mmol) according to the general procedure afforded (38 mg, 0.20 mmol) and imino-λ3-iodane 2c (97 mg, 0.24 mmol)
35 mg (50 %) of product 3i, isolated as a white solid; IR (neat) cm–1
:
according to the general procedure afforded 12 mg (16 %) of prod-
ν = 3112, 3070, 2923, 1609, 1480, 1531, 1350, 1312, 1169, 997, 929, uct 3n, isolated as a light yellow oil; IR (neat) cm–1: ν = 3063, 3032,
˜
˜
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2936, 2865, 1583, 1542, 1481, 1368, 1171, 744; 1H NMR (500 MHz,
CDCl3): δ = 8.19 (d, J = 7.5 Hz, 1H), 7.69–7.55 (m, 3H), 7.36 (d, J =
8.0 Hz, 2H), 7.22 (t, J = 7.5 Hz, 1H), 7.18–7.11 (m, 2H), 5.91–5.84 (m,
1H), 5.44–5.35 (m, 1H), 5.07–5.00 (m, 1H), 2.06–1.89 (m, 3H), 1.81–
1.59 (m, 3H); 13C NMR (125 MHz, CDCl3): δ = 147.8, 138.1, 134.0,
132.9, 132.6, 132.3, 131.5, 128.7, 127.5, 127.1, 125.5, 124.0, 60.2, 29.1,
24.3, 21.2; HRMS (ESI-positive ionization): calcd. for C18H18N2NaO4S2
([M + Na]+): 413.0606, found 413.0582.
128.3, 126.5, 124.3, 112.7, 69.3, 28.5, 27.6, 21.5; HRMS (ESI-positive
ionization): calcd. for C18H22NO2S2 ([M + H]+): 348.1092, found
348.1063.
(Z)-2-Tosyl-3,6,7,8-tetrahydro-2H-1,2-thiazocine (3s):[20] Reaction
of 2-vinyltetrahydrothiophene 1h (23 mg, 0.20 mmol) and imino-λ3-
iodane 2a (90 mg, 0.24 mmol) according to the general procedure
afforded 11 mg (20 %) of product 3s, isolated as a white solid: m.p.
62.9–64.4 °C (lit.[20]; m.p. 68–69 °C); IR (neat) cm–1: ν = 3026, 2932,
˜
1
2853, 1652, 1599, 1351, 1162, 937, 747; H NMR (500 MHz, CDCl3):
N-(Cyclohex-2-en-1-yl)-N-(phenylthio)benzenesulfonamide (3o):
Reaction of cyclohex-2-en-1-yl(phenyl)sulfane 1e (38 mg,
0.20 mmol) and imino-λ3-iodane 2d (86 mg, 0.24 mmol) according
to the general procedure afforded 39 mg (57 %) of product 3o,
δ = 7.79 (d, J = 8.5 Hz, 2H), 7.30 (d, J = 8.5 Hz, 2H), 6.02–5.83 (m,
2H), 4.36–4.02 (m, 2H), 2.92–2.82 (m, 2H), 2.62–2.36 (m, 5H), 1.88
(quint, J = 6.0 Hz, 2H); 13C NMR (125 MHz, CDCl3): δ = 143.7, 136.5,
135.5, 129.5, 128.0, 128.0, 51.0, 38.4, 30.3, 24.4, 21.6.
isolated as a colorless oil; IR (neat) cm–1: ν = 3063, 3027, 2934, 2863,
˜
1582, 1479, 1359, 1167, 1044, 943; 1H NMR (500 MHz, CDCl3): δ =
7.98 (d, J = 8.0 Hz, 2H), 7.60 (t, J = 7.5 Hz, 1H), 7.55–7.49 (m, 2H),
7.45 (d, J = 7.5 Hz, 2H), 7.35–7.29 (m, 2H), 7.20 (t, J = 7.3 Hz, 1H),
5.78–5.71 (m, 1H), 4.99–4.90 (m, 2H), 2.00–1.84 (m, 3H), 1.75–1.68
(m, 1H), 1.66–1.50 (m, 2H); 13C NMR (125 MHz, CDCl3): δ = 140.0,
139.3, 133.1, 132.6, 129.1, 128.8, 127.7, 126.9, 126.7, 124.6, 60.0, 28.6,
24.2, 21.2; HRMS (ESI-positive ionization): calcd. for C18H19NNaO2S2
([M + Na]+): 368.0755, found 368.0727.
Deprotection of N-allylsulfenamides: N-Allylsulfenamide 3a or 3l
was added at room temperature to a stirred mixture of 10 % KOH
in methanol (1.0 mL) and the reaction was stirred at room tempera-
ture for overnight. After the reaction, 10 % HCl solution (5 mL) was
added, and the mixture was extracted with ethyl acetate. The or-
ganic phase was dried with anhydrous Na2SO4 and concentrated
under reduced pressure. Purification by column chromatography
(hexane/ethyl acetate = 4:1 to 1:1) afforded to afford the pure prod-
uct 4a, b.
N-(But-3-en-2-yl)-4-methyl-N-(phenylthio)benzenesulfonamide
(3p):[13b] Reaction of (E)-but-2-en-1-yl(phenyl)sulfane 1f (15 mg,
0.10 mmol) and imino-λ3-iodane 2a (45 mg, 0.12 mmol) according
to the general procedure afforded 21 mg (64 %) of product 3p,
N-Allyl-4-methylbenzenesulfonamide (4a):[21] Reaction of
N-allyl-4-methyl-N-(methylthio)benzenesulfonamide 3a (50 mg,
0.194 mmol) was added at room temperature to a stirred mixture
of 10 % KOH in methanol (1.0 mL) and according to the general
procedure afforded 33 mg (81 %) of product 4a, isolated as a color-
isolated as a colorless oil; IR (neat) cm–1: ν = 3068, 2981, 2938, 2876,
˜
1598, 1582, 1479, 1354, 1165, 991, 938, 741; 1H NMR (500 MHz,
CDCl3): δ = 7.83 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 7.5 Hz, 2H), 7.33–
7.27 (m, 4H), 7.20 (t, J = 7.3 Hz, 1H), 5.86–5.43 (m, 1H), 5.15–4.85
(m, 3H), 2.42 (s, 3H), 1.35–1.00 (s, 3H); 13C NMR (125 MHz, CDCl3):
δ = 143.9, 139.0, 137.2, 136.8, 129.5, 128.7, 127.9, 126.9, 125.3, 117.0,
60.1, 21.6, 18.9; HRMS (ESI-positive ionization): calcd. for
less solid: m.p. 59.7–60.8 °C (lit.[21]; m.p. 60–62 °C); IR (neat) cm–1
:
ν = 3366, 3127, 3091, 3006, 2923, 2852, 1685, 1560, 1445, 1387;
˜
1H NMR (500 MHz, CDCl3): δ = 7.76 (d, J = 8.5 Hz, 2H), 7.31 (d, J =
8.5 Hz, 2H), 5.77–5.67 (m, 1H), 5.17 (dd, J = 15.5 Hz, 1.3 Hz, 1H),
5.09 (dd, J = 10.5 Hz, 1.3 Hz, 1H), 4.71 (s, 1H), 3.61–3.55 (m, 2H),
2.43 (s, 3H); 13C NMR (125 MHz, CDCl3): δ = 143.5, 136.9, 133.0,
129.7, 127.1, 117.7, 45.8, 21.5; HRMS (ESI-positive ionization): calcd.
for C10H14NO2S ([M + H]+): 212.0745, found 212.0739.
C
17H20NO2S2 ([M + Na]+): 334.0935, found 334.0906.
N-(But-3-en-2-yl)-4-nitro-N-(phenylthio)benzenesulfonamide
(3q): Reaction of (E)-but-2-en-1-yl(phenyl)sulfane 1f (15 mg,
0.10 mmol) and imino-λ3-iodane 2b (49 mg, 0.12 mmol) according
to the general procedure afforded 17 mg (47 %) of product 3q,
N-(Cyclohex-2-en-1-yl)-4-methylbenzenesulfonamide (4b):[22] Re-
action of N-(cyclohex-2-en-1-yl)-4-methyl-N-(phenylthio)benzene-
sulfonamide 3l (18 mg, 0.05 mmol) was added at room temperature
to a stirred mixture of 10 % KOH in methanol (1.0 mL) and accord-
ing to the general procedure afforded 12 mg (92 %) of product 4b,
isolated as a colorless solid: m.p. 106.2–107.5 °C; IR (neat) cm–1: ν =
˜
3105, 3067, 2985, 2934, 2868, 1607, 1582, 1531, 1350, 1169, 991,
961, 938, 738; 1H NMR (500 MHz, CDCl3): δ = 8.33 (d, J = 8.8 Hz,
2H), 8.13 (d, J = 8.8 Hz, 2H), 7.48 (d, J = 7.5 Hz, 2H), 7.39 (d, J =
7.5 Hz, 2H), 7.28–7.23 (m, 1H), 5.70–5.50 (m, 1H), 5.40–4.95 (m, 3H),
1.24 (d, J = 6.0 Hz, 2H); 13C NMR (125 MHz, CDCl3): δ = 150.2, 145.1,
137.7, 136.6, 129.3, 129.0, 127.6, 126.0, 124.0, 117.7, 61.0, 19.2; HRMS
(ESI-positive ionization): calcd. for C16H16N2NaO4S2 ([M + Na]+):
387.0449, found 387.0421.
isolated as a colorless oil; IR (neat) cm–1: ν = 3279, 3033, 2933, 1600,
˜
1430, 1318, 1156, 998; 1H NMR (400 MHz, CDCl3): δ = 7.77 (d, J =
8.0 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 5.83–5.71 (m, 1H), 5.42–5.28 (m,
1H), 4.53 (d, J = 8.0 Hz, 1H), 3.89–3.74 (m, 1H), 2.43 (s, 3H), 2.16–
1.86 (m, 2H), 1.83–1.68 (m, 1H), 1.65–1.48 (m, 3H); 13C NMR
(100 MHz, CDCl3): δ = 143.3, 138.4, 131.6, 129.7, 127.1, 127.0, 49.0,
30.3, 24.5, 21.5, 19.3; HRMS (ESI-positive ionization): calcd. for
C13H18NO2S ([M + H]+): 252.1058, found 252.1058.
Single crystals of product 3q suitable for X-ray crystallographic anal-
ysis were obtained by slow evaporation of ethyl acetate solution.
For details on crystal structure of compound 3q see the CIF file in
Supporting Information. CCDC 2011022.
Deposition Numbers 2011021 and 2011022 contain the supplemen-
tary crystallographic data for this paper. These data are provided
free of charge by the joint Cambridge Crystallographic Data Centre
and Fachinformationszentrum Karlsruhe Access Structures service
www.ccdc.cam.ac.uk/structures.
4-Methyl-N-(2-methylbut-3-en-2-yl)-N-(phenylthiol)benzene-
sulfonamide (3r):[4d] Reaction of (3-methylbut-2-en-1-yl)(phenyl)-
sulfane 1g (18 mg, 0.10 mmol) and imino-λ3-iodane 2a (45 mg,
0.12 mmol) according to the general procedure afforded 23 mg
(66 %) of product 3r, isolated as a colorless oil; IR (neat) cm–1: ν = Acknowledgments
˜
3066, 2983, 2926, 2872, 1600, 1582, 1479, 1347, 1165, 990, 919, 740;
This work was supported by a research grants from the Russian
1H NMR (500 MHz, CDCl3): δ = 7.82 (d, J = 8.8 Hz, 2H), 7.34 (d, J =
8.0 Hz, 2H), 7.30–7.25 (m, 2H), 7.23 (d, J = 8.8 Hz, 2H), 7.16 (t, J =
7.3 Hz, 1H), 6.11 (dd, J = 17.3 Hz, 10.8 Hz, 1H), 5.08 (d, J = 17.3 Hz,
1H), 5.04 (d, J = 10.8 Hz, 1H), 2.39 (s, 3H), 1.62–1.45 (m, 6H); 13C
Science Foundation (RSF-16-13-10081-P) and the National Sci-
ence Foundation (CHE-1759798). A. S. is thankful to JSPS Fund
for the Promotion of Joint International Research (Grant No
NMR (125 MHz, CDCl3): δ = 143.6, 143.6, 139.9, 138.1, 129.1, 128.7, 16KK0199) and JST CREST (No. JRMJCR19R2). Some research
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Keywords: Hypervalent compounds · Iodine · Sigmatropic
rearrangement · Sulfilimines · Synthetic methods
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Received: July 9, 2020
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© 2020 Wiley-VCH GmbH

Full Paper
doi.org/10.1002/ejoc.202000961
EurJOC
European Journal of Organic Chemistry
Iodine-mediated Reactions
C. L. Makitalo, A. Yoshimura,*
G. T. Rohde, I. A. Mironova,
R. Y. Yusubova, M. S. Yusubov,
V. V. Zhdankin, A. Saito .................... 1–8
Imino-λ3-iodane and catalytic I2-medi- producing N-allysulfenamiides has
ated facile metal-free [2,3]-sigmatropic been developed
rearrangement reaction of allyl sulfides
Imino-λ3-iodane
and
Catalytic
Amount of I2-Mediated Synthesis of
N-Allylsulfenamides via [2,3]-Sigma-
tropic Rearrangement
doi.org/10.1002/ejoc.202000961
Eur. J. Org. Chem. 0000, 0–0
www.eurjoc.org
8
© 2020 Wiley-VCH GmbH