Imination of sulfides and sulfoxides with sulfonylimino- λ3-bromane under mild, metal-free conditions

Article abstract of DOI:10.1002/chem.201000759

Exposure of sulfides and sulfoxides to trifluoromethanesulfonylimino(aryl)- λ³-bromane in dichloromethane at 0°C results in a facile transfer of the sulfonylimino group to sulfur atoms and affords N-triflylsulfilimines and -sulfoximines in high yields under transition-metal-free conditions. Imination of (R)-methyl p-tolyl sulfoxide proceeded with predominant retention of configuration at the stereogenic sulfur center. The Hammett plot afforded ρ values of -0.58 for para-substituted thioanisoles and -0.49 for their equivalent sulfoxides, which suggests a buildup of positive charge on the sulfur atoms of sulfides and sulfoxides in the transition state. Calculations suggest a bimolecular nucleophilic-substitution mechanism on the negatively charged nitrogen atom of the sulfonylimino- λ³-bromane, which involves the attack of a sulfide from the opposite side to bromine(III).

Full text of DOI:10.1002/chem.201000759

FULL PAPER
DOI: 10.1002/chem.201000759
Imination of Sulfides and Sulfoxides with Sulfonylimino-l3-Bromane under
Mild, Metal-Free Conditions
Masahito Ochiai,*[a] Masao Naito,[a] Kazunori Miyamoto,[a] Satoko Hayashi,[b] and
Waro Nakanishi*[b]
Abstract: Exposure of sulfides and
with predominant retention of configu-
ration at the stereogenic sulfur center.
The Hammett plot afforded 1 values of
À0.58 for para-substituted thioanisoles
and À0.49 for their equivalent sulfox-
ides, which suggests a buildup of posi-
tive charge on the sulfur atoms of sul-
fides and sulfoxides in the transition
state. Calculations suggest a bimolecu-
lar nucleophilic-substitution mechanism
on the negatively charged nitrogen
atom of the sulfonylimino-l3-bromane,
which involves the attack of a sulfide
sulfoxides
trifluoromethanesulfonyliminoAHCUTNGTERNNUNG
to
(aryl)-l3-
bromane in dichloromethane at 08C re-
sults in a facile transfer of the sulfony-
limino group to sulfur atoms and af-
fords N-triflylsulfilimines and -sulfoxi-
mines in high yields under transition-
metal-free conditions. Imination of
(R)-methyl p-tolyl sulfoxide proceeded
Keywords: bromine · hypervalent
compounds · imination · sulfides ·
sulfoxides
from the opposite side to bromineACHTUNGTRENNUNG(III).
Introduction
nucleophiles, which include nitrogen heterocycles, sulfides,
and sulfoxides.[4–7] In the absence of metal catalysts, the ni-
trenoid-transfer reaction of imino-l3-iodanes does not take
place or requires harsh reaction conditions,[8] partly due to
their insoluble nature in common organic media, evoked by
the highly aggregated polymeric zigzag structure.[9]
To introduce nitrogen functionalities directly into aliphatic
molecules, hypervalent aryl(sulfonylimino)-l3-iodanes and
their derivatives are most frequently employed as the nitro-
gen sources in transition-metal-catalyzed nitrenoid reac-
tions.[1] Recent developments in simple methodologies for
the generation of imino-l3-iodanes in situ have greatly en-
hanced research activity in this area.[2] Sulfonylimino-l3-io-
danes readily generate active metal–nitrenoid species under
mild conditions[1] because of the hyper-leaving-group ability
Recently, we reported the synthesis of Group 17 analogue
trifluoromethanesulfonyliminoACHTUNGTRNEUNG
(aryl)-l3-bromane (1).[10] The
sulfonylimino-l3-bromane 1 functions as an electrophilic
imido-group donor and directly undergoes stereospecific
aziridination of olefins with retention of stereochemistry
and transylidation to iodobenzenes and pyridines.[11] Impor-
tantly, all of these reactions do not require the use of any
transition-metal catalysts and proceed smoothly at room
temperature. The iminobromane 1 is a dimeric species in
the solid state and, therefore, is readily soluble in dichloro-
methane and acetonitrile.[10] In addition, the vastly enhanced
nucleofugality of aryl-l3-bromanyl groups[12] relative to aryl-
l3-iodanyl groups will result in the highly increased activity
of 1 as an electrophilic nitrenoid species. Herein, we report
a facile oxidative transfer of the sulfonylimino group of
imino-l3-bromane 1 to a wide range of sulfides and sulfox-
ides. The reaction affords excellent yields of N-triflylsulfili-
mines and -sulfoximines at 08C under metal-free conditions.
Both sulfilimines and sulfoximines have found many appli-
cations as valuable synthons and reagents in organic synthe-
sis and as chiral ligands, particularly for transition-metal cat-
alysis.[13]
of aryl-l3-iodanyl groups.[3] These species catalytically under-
go both amination of unactivated aliphatic (sp ) C H bonds
and transfer of the imino groups to olefins and heteroatom
3
À
[a] Prof. Dr. M. Ochiai, M. Naito, Prof. Dr. K. Miyamoto
Graduate School of Pharmaceutical Sciences
University of Tokushima
1-78 Shomachi, Tokushima 770-8505 (Japan)
Fax : (+81)88-633-9504
E-mail: mochiai@ph.tokushima-u.ac.jp
[b] Prof. Dr. S. Hayashi, Prof. Dr. W. Nakanishi
Department of Material Science and Chemistry
Faculty of Systems Engineering, Wakayama University
930 Sakaedani, Wakayama 640-8510 (Japan)
Fax : (+81)73-457-8253
E-mail: nakanisi@sys.wakayama-u.ac.jp
Supporting Information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201000759.
Chem. Eur. J. 2010, 16, 8713 – 8718
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
8713

Results and Discussion
Changing the solvent to noncoordinating dichloromethane
promoted the imination of thioanisole and afforded 2a
quantitatively within 10 min (Table 1, entry 2). No formation
Sulfonylimino-l3-bromane
(difluoro)-l3-bromane by facile ligand exchange with tri-
1 was prepared from aryl-
1
N
of sulfoximine 3b was detected by H NMR spectroscopy of
fluoromethanesulfonamide (TfNH2) on the bromane
(III) in
the crude reaction mixture. Thioanisoles substituted with
electron-donating (MeO or Me) or -withdrawing groups (Cl,
Br, C(O)Me, CF3, CN, or NO2) were efficiently transformed
into N-triflylsulfilimines 2b–j under equimolar conditions.
Benzyl, isopropyl, and diphenyl sulfides and cyclic sulfides
such as tetrahydrothiophene, pentamethylene sulfide, and
1,4-oxathiane afforded the respective sulfilimines 2 in high
yields. It is noted that use of imino-l3-iodane analogue p-
CF3C6H4I=NSO2CF3, instead of 1, produced only trace
amounts of sulfilimine 2a under the reaction conditions and
a large amount of thioanisole was recovered. These results
clearly demonstrate a greater reactivity of imino-l3-bromane
1 toward thioanisole than that of the imino-l3-iodane
(Table 1, entry 2 versus 3).
Oxidation of 1,3-dithiane afforded monosulfilimine 2t se-
lectively, whereas a 2:3 mixture of mono- and bis-sulfili-
mines 2u/2v was produced from 1,4-dithiane (Table 1, en-
tries 22 and 23). The triflylimino group (=NTf) in 2t consid-
erably decreases the nucleophilicity of the remaining sulfur
atom toward the transimination because of its highly elec-
tron-withdrawing nature[15] but the extent of this induced
effect is considerably reduced in monosulfilimine 2u. The
use of excess 1,4-dithiane (2 equiv) afforded 2u predomi-
nantly, whereas excess l3-bromane 1 (2.5 equiv) gave 2v ex-
clusively (cis/trans=69:31) in a high yield (Table 1, en-
a high yield (Scheme 1).[10] Transimination between triflyli-
Scheme 1. Synthesis of sulfonylimino-l3-bromane 1 from difluoro-l3-bro-
mane and its transimination with thioanisole.
mino-l3-bromane 1 and sulfides occurs even at 08C under
transition-metal-free conditions. Exposure of thioanisole to
1 (1.1 equiv) in acetonitrile at 08C for 1 h under argon re-
sulted in the formation of N-triflylsulfilimine 2a in 64%
yield, along with a small amount of N-triflylsulfoximine 3b
(2%) (Table 1, entry 1). ESI mass spectra of 1 in acetonitrile
solution indicated coordination of a solvent molecule to the
positively charged bromineACHTNUGRTNEUNG
(III) atom.[11a] The acetonitrile
coordination enhances the thermal stability of 1 but proba-
bly reduces the nucleofugality of the aryl-l3-bromanyl
group,[14] which, in turn, decreases the nitrenoid reactivity of
the imino-l3-bromane 1.
Table 1. Synthesis of N-triflylsulfilimines 2.[a]
Entry
Sulfide
t [min]
2
Yield [%][b]
Entry
Sulfide
t [min]
2
Yield [%][b]
1[c]
2
PhSMe
PhSMe
PhSMe
p-MeOC6H4SMe
p-MeC6H4SMe
60
10
10
10
10
2a
2a
2a
2b
2c
64
100
2
90
81
14
15
16
17
18
iPrSPh
PhSCH2Ph
PhSPh
PhSCH=CH2
PhCH2SCH2Ph
10
10
10
10
10
2l
90
81
79
88
89
2m
2n
2o
2p
3[d]
4
5
6
o-ClC6H4SMe
10
2d
97
19
20
2q
92
7
p-ClC6H4SMe
10
2e
79
20
10
2r
93
8
9
p-BrC6H4SMe
10
10
2 f
2g
74
90
21
22
10
10
2s
2t
93
83
p-MeCOC6H4SMe
10
11
12
p-CF3C6H4SMe
p-NCC6H4SMe
p-NO2C6H4SMe
10
10
10
2h
2i
2j
90
92
85
23
60
2u, 2v
2u, 2v
2v
22, 31
84, 5
89
24[e]
25[g]
120[f]
10
13
2,4,6-Me3C6H2SMe
20
2k
89
26
60
2w
78
[a] Conditions: sulfide/bromane 1 (1.1 equiv), CH2Cl2, 08C. [b] Isolated yield. [c] MeCN used as solvent. [d] p-CF3C6H4I=NTf, which is poorly soluble in
dichloromethane, was used. [e] 1,4-Dithiane (2 equiv) was used. [f] Conditions: À78 to 08C over 2 h. [g] Bromane 1 (2.5 equiv) was used.
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Chem. Eur. J. 2010, 16, 8713 – 8718

Metal-Free Imination of Sulfides and Sulfoxides
FULL PAPER
tries 24 and 25). Conjugation in thianthrene makes the selec-
tive monoimination to 2w possible.
two competing substrates was used (Table 3). Ratios of
products 2 (or 3) were analyzed by H NMR spectroscopy of
the crude reaction mixture. The electron-releasing p-Me
1
Imino-transfer reaction to sulfoxides with imino-l3-bro-
mane 1 occurs smoothly under comparable conditions and
the results given in Table 2 indicate the high yields obtained
Table 3. Relative rates of thioanisoles and their sulfoxides.
Table 2. Transimination of imino-l3-bromane 1 with sulfoxides.[a]
Entry
Sulfide
krel
1
2
3
4
5
6
7
8
p-MeC6H4SMe
PhSMe
1.3
1.0
Entry
Sulfoxide
Solvent t [min]
3
Yield [%][b]
95
1
2
3
4
5
6
7
8
MeS(O)Me
PhS(O)Me
p-MeC6H4S(O)Me
p-BrC6H4S(O)Me
p-NCC6H4S(O)Me
2,4,6-Me3C6H2S(O)Me CH2Cl2
PhS(O)Ph
PhS(O)CH=CH2
MeCN
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
10
10
10
10
30
3a
p-BrC6H4SMe
p-CH3C(O)C6H4SMe
p-CF3C6H4SMe
p-NCC6H4SMe
p-NO2C6H4SMe
p-MeC6H4S(O)Me
PhS(O)Me
0.81
0.56
0.49
0.39
0.32
1.1
1.0
0.82
0.45
3b 99
3c 99
3d 85
3e
3 f
3g
98
94
87
360
10
30
CH2Cl2
CH2Cl2
9
10
11
3h 91
p-BrC6H4S(O)Me
p-NCC6H4S(O)Me
9
CH2Cl2
20
3i 93
[a] Conditions: Sulfoxide/bromane 1 (1.1 equiv), 08C. [b] Isolated yield.
group increased the relative rates (krel) of the imino-transfer
reaction slightly, both to the sulfide and the sulfoxide,
whereas electron-withdrawing p-CN and p-NO2 groups
slowed down the reaction remarkably. The Hammett plot
showed good correlations of the relative-rate factors with
the sp constants of substituents[17] and afforded the reaction
constants 1=À0.58 (r=0.99) and À0.49 (r=0.99) for the
imination of thioanisoles and sulfoxides, respectively. These
negative 1 values suggest that imino-l3-bromane 1 functions
as an electrophilic imino-transfer agent toward sulfur atoms.
Comparable 1 values (À0.77 for thioanisoles and À0.76 for
their sulfoxides) were reported in the oxenoid-transfer reac-
tions with dimethyldioxirane in acetone at room tempera-
ture.[18] These 1 values evaluated in our imino-group transfer
of 1 suggest a lesser buildup of positive charge on the sulfur
atoms of sulfides and sulfoxides in the transition state rela-
tive to the oxenoid-transfer reactions and, therefore, earlier
transition states.
for the formation of N-triflylsulfoximines 3. The attempted
FeIII-catalyzed imination of sterically demanding mesityl
methyl sulfoxide with p-nosylamide and iodosylbenzene led
to the recovery of the sulfoxide,[7d] however, sulfoximine 3 f
was obtained in high yield under our mild conditions
(Table 2, entry 6). Similarly to the selective transimination
of phenyl vinyl sulfide (Table 1, entry 17), the oxidative sulf-
oxide imination tolerates the double bond in phenyl vinyl
sulfoxide (Table 2, entry 8).[16]
Scheme 2 depicts the stereochemical outcome of our
metal-free transimination to sulfoxides. Comparison of the
optical rotation of the product obtained from the reaction of
The results from competitive iminations, which show that
the more nucleophilic sulfides are much more reactive than
sulfoxides, are in line with the above mechanistic considera-
tions (Scheme 3). Similar preference for the formation of
sulfilimines over sulfoximines was reported for transition-
metal-catalyzed iminations with sulfonylimino-l3-ioda-
nes.[7c,d]
Scheme 2. Retention of configuration in the imination of chiral (R)-
methyl p-tolyl sulfoxide.
(R)-methyl p-tolyl sulfoxide to that of authentic (R)-3c, pre-
pared by triflylation of (R)-methyl p-tolyl sulfoximine,[7f]
demonstrated predominant retention of configuration at the
stereogenic sulfur center in the imination of the chiral sulf-
oxide with 1.
To gain some insight into the mechanism, relative rates of
the imino-group transfer for a series of para-substituted thi-
oanisoles and their sulfoxides were measured by competitive
reactions, in which a mixture of tenfold excess of each of
Scheme 3. Competitive iminations between sulfides and sulfoxides.
Chem. Eur. J. 2010, 16, 8713 – 8718
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
8715

M. Ochiai, W. Nakanishi et al.
Figure 1 shows the results for quantum chemical calcula-
tions[19] at the MP2 level[20,21] on the reaction of dimethyl
rived from pentamethylene sulfide, over that of iminoammo-
nium ylide 7 was observed in the reaction with bromane 1.
sulfide with iminoACHTUNGTRENNUNG
(phenyl)-l3-bromane 4, a model of 1. The
Conclusion
A facile oxidative transfer of the sulfonylimino group of
imino-l3-bromane 1 to a variety of sulfides and sulfoxides
was developed. The reaction affords excellent yields of N-
triflylsulfilimines 2 and -sulfoximines 3 in dichloromethane
at 08C under metal-free, equimolar conditions. Our results
clearly indicate greater reactivity of the sulfonylimino-l3-
bromane 1 than that of the equivalent imino-l3-iodane. Re-
action of (R)-methyl p-tolyl sulfoxide demonstrated pre-
dominant retention of configuration at the stereogenic
sulfur center after the imination with imino-l3-bromane 1.
Small negative 1 values (À0.58 and À0.49 for thioanisoles
and their sulfoxides, respectively) evaluated in the imino-
group transfer of 1 suggest a slight buildup of positive
charge on the sulfur atoms of sulfides and sulfoxides in the
transition state, hence, very early transition states, which
were also predicted by quantum chemical calculations at the
MP2 level. Calculations also indicated that the reaction in-
volves nucleophilic attack of the sulfur atom on the low-
Figure 1. a) Energy profile for the reaction of imino-l3-bromane 4 with
dimethyl sulfide. b) Calculated structures of 4, transition state 5, and sul-
filimine 6 at the MP2 level of theory.
3
À
lying s*
U
type manner with a very low energy barrier.
transition-state structure 5, with a roughly linear Br-N-S
bond angle (150.48), was obtained and the activation energy
for the transimination is predicted to be only 1.6 kcalmolÀ1.
The reaction involves nucleophilic attack of the sulfur lone-
À
Experimental Section
General procedure for synthesis of N-triflyl-sulfilimines (2) and -sulfoxi-
mines (3)
Compound 2a: A solution of thioanisole (6.5 mg, 0.052 mmol) in di-
chloromethane (0.5 mL) was added dropwise to a stirred solution of 1
(21 mg, 0.058 mmol) in dichloromethane (0.6 mL) at 08C under argon
and the mixture was stirred for 10 min. After addition of water (2 mL),
the reaction mixture was extracted with dichloromethane (4ꢂ). The com-
bined organic phases were dried over anhydrous Na2SO4, filtered, and
concentrated under vacuum to give an oil, which was purified by prepara-
tive TLC (hexane/dichloromethane 1:3) to give 2a as a colorless oil
(14.1 mg, 100%). 1H NMR (400 MHz, CDCl3): d=7.89–7.81 (m, 2H),
7.73–7.60 (m, 3H), 3.03 ppm (s, 3H); 13C NMR (75 MHz, CDCl3): d=
pair of electrons on the low-lying s*ACTHNUTRGNEUNG(N Br) orbital of 4 in
an SN2-type manner.[22] The length of the breaking N Br
À
bond (2.053 ꢁ) in 5 is comparable to that of 4 (1.862 ꢁ),
À
whereas the length of the N S bond that is formed
(2.544 ꢁ) is longer relative to that of sulfilimine
6
(1.647 ꢁ).[23] These calculations suggest a very early transi-
tion state for the imination of dimethyl sulfide, which is di-
rectly reflected in a small negative 1 value of À0.58 for the
reaction of thioanisoles (Table 3).
134.6, 133.6, 130.5, 126.0, 120.2 (q, J
ACHTUNGTRNE(NUNG C,F)=323 Hz), 39.7 ppm; IR (neat):
n˜ =3024, 2929, 1583, 1475, 1446, 1415, 1336, 1136, 1012, 739, 685,
Direct transfer of the trifluoromethanesulfonylimino
group of the imino-l3-bromane 1 to aliphatic trialkylamines
also proceeds smoothly, even at 08C, under metal-free con-
ditions and results in the selective formation of ammonium
ylides in high yields.[11a] Scheme 4 shows the results for com-
petitive transimination between a dialkyl sulfide and a terti-
ary alkylamine. Preferential formation of sulfilimine 2r, de-
611 cmÀ1
; HRMS (ESI): m/z: calcd for C8H8F3NNaO2S2: 293.9846
[M+Na]+; found: 293.9856; elemental analysis calcd (%) for
C8H8F3NO2S2: C 35.42, H 2.97, N 5.16; found: C 35.31, H 3.12, N 5.26.
Compound 2k: Colorless prisms (recrystallized from dichloromethane/
hexane); m.p. 127–1298C; 1H NMR (400 MHz, CDCl3): d=6.99 (s, 2H),
3.16 (s, 3H), 2.69 (s, 6H), 2.33 ppm (s, 3H); 13C NMR (75 MHz, CDCl3):
d=144.6, 140.5, 131.7, 126.8, 120.2 (q,
JACTHNGUTRENNU(G C,F)=323 Hz), 34.9, 21.2,
20.2 ppm; IR (KBr): n˜ =3049, 2941, 1741, 1600, 1333, 1213, 1171, 1130,
1010, 972, 856, 768, 744, 627, 609 cmÀ1; elemental analysis calcd (%) for
C11H14F3NO2S2: C 42.16, H 4.50, N 4.47; found: C 42.02, H 4.39, N 4.46.
Compound 2o: Colorless plates (recrystallized from dichloromethane/
hexane); m.p. 56–588C; 1H NMR (400 MHz, CDCl3): d=7.80–7.76 (m,
2H), 7.71–7.59 (m, 3H), 6.55–6.45 (m, 2H), 6.29–6.18 ppm (m, 1H);
13C NMR (75 MHz, CDCl3): d=133.7, 133.2, 132.1, 130.5, 127.4, 127.3,
120.2 ppm (q, J
ACHTUNGTREN(NGNU C,F)=323 Hz); IR (KBr): n˜ =3105, 3070, 1473, 1446,
1335, 1203, 1174, 1132, 1011, 991, 957, 779, 756, 742, 687, 619, 607 cmÀ1
;
Scheme 4. Competitive transimination between pentamethylene sulfide
and N-methylpiperidine.
elemental analysis calcd (%) for C9H8F3NO2S2: C 38.16, H 2.85, N 4.94;
found: C 38.09, H 2.98, N 5.08.
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Metal-Free Imination of Sulfides and Sulfoxides
FULL PAPER
1
Compound 2q: Colorless oil; H NMR (400 MHz, CDCl3): d=3.42–3.31
analysis calcd (%) for C11H14F3NO3S2: C 40.11, H 4.28, N 4.25; found: C
39.99, H 4.21, N 4.20.
(m, 2H), 3.28–3.19 (m, 2H), 2.65–2.50 (m, 2H), 2.25–2.10 ppm (m, 2H);
13C NMR (75 MHz, CDCl3): d=120.3 (q,
JACTHNGUTERNNU(G C,F)=323 Hz), 52.4,
Compound 3h: Colorless needles (recrystallized from dichloromethane/
hexane); m.p. 50–518C; 1H NMR (400 MHz, CDCl3): d=8.01 (d, J=
7.8 Hz, 2H), 7.78 (t, J=7.2 Hz, 1H), 7.67 (dd, J=7.8, 7.2 Hz, 2H), 6.85
(dd, J=16.2, 9.4 Hz, 1H), 6.64 (d, J=16.2 Hz, 1H), 6.36 ppm (d, J=
9.4 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=136.3, 136.2, 135.3, 131.1,
26.7 ppm; IR (neat): n˜ =2954, 2883, 1448, 1414, 1329, 1171, 997, 895, 768,
735, 609 cmÀ1; elemental analysis calcd (%) for C5H8F3NO2S2: C 25.53, H
3.43, N 5.95; found: C 25.52, H 3.44, N 6.25.
Compound 2s: Colorless plates (recrystallized from dichloromethane/
hexane); m.p. 84–888C; 1H NMR (400 MHz, CDCl3): d=4.52 (ddd, J=
13.2, 10.0, 2.0 Hz, 2H), 4.01 (dt, J=13.2, 3.8 Hz, 2H), 3.22 (ddd, J=14.0,
10.0, 3.8 Hz, 2H), 2.97 ppm (ddd, J=14.0, 3.8, 2.0 Hz, 2H); 13C NMR
130.2, 127.9, 119.2 ppm (q, JACTHUNRTGNEUNG(C,F)=321 Hz); IR (KBr): n˜ =3111, 3087,
3024, 2966, 1444, 1385, 1344, 1265, 1194, 1130, 1095, 1061, 997, 958, 798,
771, 742, 690, 640 cmÀ1; elemental analysis calcd (%) for C9H8F3NO3S2: C
36.12, H 2.69, N 4.68; found: C 35.86, H 2.76, N 4.89.
(75 MHz, CDCl3): d=120.2 (q,
JACTHNGUTER(NNUG C,F)=323 Hz), 59.4, 42.1 ppm; IR
(KBr): n˜ =3012, 2941, 2881, 1462, 1410, 1383, 1333, 1219, 1180, 1157,
1103, 1065, 1018, 991, 966, 833, 768, 741, 615 cmÀ1; elemental analysis
calcd (%) for C5H8F3NO3S2: C 23.90, H 3.21, N 5.57; found: C 23.77, H
3.14, N 5.62.
Compound 3i: White needles (recrystallized from ethyl acetate/hexane);
m.p. 58–598C; 1H NMR (400 MHz, CDCl3): d=3.86–3.74 (m, 2H), 3.50–
3.37 (m, 2H), 2.49–2.32 ppm (m, 4H); 13C NMR (75 MHz, CDCl3): d =
119.2 (q, JACTHNUTRGNE(NUG C,F)=321 Hz), 54.9, 23.3 ppm; IR (KBr): n˜ =3018, 2976, 2945,
1450, 1400, 1350, 1286, 1203, 1134, 1101, 1045, 903, 787, 750, 727, 656,
634 cmÀ1; elemental analysis calcd (%) for C5H8F3NO3S2: C 23.90, H
3.21, N 5.57; found: C 24.14, H 3.19, N 5.73.
Compound 2t: Colorless needles (recrystallized from dichloromethane/
hexane); m.p. 134–1358C; H NMR (400 MHz, CDCl3): d=4.29 (brd, J=
12.8 Hz, 1H), 4.10 (d, J=12.8 Hz, 1H), 3.61–3.53 (m, 1H), 3.20 (dt, J=
1
13.1, 2.6 Hz, 1H), 2.82–2.73 (m, 1H), 2.71–2.59 (m, 2H), 2.46–2.33 ppm
(m, 1H); 13C NMR (75 MHz, CDCl3): d=120.2 (q, J
ACHTNUTRGNE(NUG C,F)=323 Hz),
49.3, 49.2, 28.0, 27.7 ppm; IR (KBr): n˜ =2997, 2929, 1433, 1336, 1217,
1178, 1138, 1086, 999, 924, 891, 820, 771, 748, 727, 652, 613 cmÀ1; elemen-
tal analysis calcd (%) for C5H8F3NO2S3: C 22.47, H 3.02, N 5.24; found:
C 22.58, H 3.04, N 5.24.
Acknowledgements
We gratefully acknowledge the Ministry of Education, Culture, Sports,
Science, and Technology of Japan for financial support in the form of a
grant.
1
Compound 2u: Colorless oil; H NMR (400 MHz, [D6]acetone): d=3.72–
3.59 (m, 4H), 3.46–3.36 (m, 2H), 2.91–2.78 ppm (m, 2H); 13C NMR
(75 MHz, CDCl3): d=120.2 (q,
JACTHNGUTER(NNUG C,F)=322 Hz), 43.8, 19.1 ppm; IR
(neat): n˜ =2981, 2929, 1408, 1335, 1186, 1130, 1018, 945, 895, 771, 742,
609 cmÀ1; elemental analysis calcd (%) for C5H8F3NO2S3: C 22.47, H
3.02, N 5.24; found: C 22.23, H 3.06, N 5.01.
[1] Reviews: a) P. Dauban, R. H. Dodd, Synlett 2003, 1571–1586; b) P.
Mꢃller, C. Fruit, Chem. Rev. 2003, 103, 2905–2919; c) V. V. Zhdan-
kin, P. J. Stang, Chem. Rev. 2008, 108, 5299–5358; d) J. A. Halfen,
Curr. Org. Chem. 2005, 9, 657–669; e) Hypervalent Iodine Chemistry
(Ed.: T. Wirth), Springer, Berlin, 2003; f) J. Du Bois, Chemtracts
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L. Saniere, A. Tarrade, R. H. Dodd, J. Am. Chem. Soc. 2001, 123,
7707–7708.
Compound cis-2v: Colorless prisms (recrystallized from acetone/
hexane); m.p. 1928C (decomposition); 1H NMR (400 MHz, [D6]DMSO):
d=4.04–3.91 (m, 4H), 3.84–3.71 ppm (m, 4H); 13C NMR (75 MHz,
[D6]acetone): d=121.2 (q, J
ACHTUNGTRENN(UNG C,F)=322 Hz), 40.3 ppm; IR (KBr): n˜ =
3010, 2931, 1417, 1336, 1225, 1182, 1157, 1136, 1039, 989, 908, 775, 746,
613 cmÀ1
; HRMS (ESI): m/z: calcd for C6H8F6N2NaO4S4: 436.9169
[M+Na]+; found: 436.9167.
Compound trans-2v: White powder (recrystallized from acetone); m.p.
254–2558C (decomposition); 1H NMR (400 MHz, [D6]DMSO): d=4.07
(d, J=11.5 Hz, 4H), 3.52 ppm (d, J=11.5 Hz, 4H); 13C NMR (75 MHz,
[D6]DMSO): d=119.8 (q, JACTHNUGRTENUNG(C,F)=323 Hz), 32.0 ppm; IR (KBr): n˜ =
2991, 2947, 1412, 1333, 1223, 1180, 1119, 1003, 899, 777, 750, 627 cmÀ1; el-
emental analysis calcd (%) for C6H8F6N2O4S4: C 17.39, H 1.95, N 6.76;
found: C 17.63, H 2.22, N 7.02.
[3] a) T. Okuyama, T. Takino, T. Sueda, M. Ochiai, J. Am. Chem. Soc.
1995, 117, 3360–3367; b) M. Ochiai in Chemistry of Hypervalent
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ter 12.
Compound 2w: Colorless needles (recrystallized from dichloromethane/
hexane); m.p. 131–1328C; 1H NMR (400 MHz, CDCl3): d=8.04 (dd, J=
7.7, 1.3 Hz, 2H), 7.77 (dd, J=7.7, 1.3 Hz, 2H), 7.66 (dt, J=1.3, 7.7 Hz,
2H), 7.60 ppm (dt, J=1.3, 7.7 Hz, 2H); 13C NMR (75 MHz, CDCl3): d=
À
[4] For recent examples of C H insertion, see: a) M. R. Fructos, S. Tro-
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Angew. Chem. 2007, 119, 5276–5278; Angew. Chem. Int. Ed. 2007,
46, 5184–5186; d) C. Liang, F. Collet, F. Robert-Peillard, P. Muller,
R. H. Dodd, P. Dauban, J. Am. Chem. Soc. 2008, 130, 343–350.
[5] For olefin aziridinations, see: a) K. Guthikonda, J. Du Bois, J. Am.
Chem. Soc. 2002, 124, 13672–13673; b) Y. Cui, C. He, J. Am. Chem.
Soc. 2003, 125, 16202–16203; c) S. K.-Y. Leung, W.-M. Tsui, J.-S.
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16629–16640.
131.9, 131.3, 130.0, 129.4, 126.2, 120.3 ppm (q,
JACTHUNGTERNNU(G C,F)=323 Hz); IR
(KBr): n˜ =3078, 2999, 1572, 1450, 1338, 1217, 1165, 1132, 1043, 972, 752,
702, 611 cmÀ1; elemental analysis calcd (%) for C13H8F3NO2S3: C 42.97,
H 2.22, N 3.85; found: C 42.92, H 2.44, N 3.84.
Compound 3c: Colorless plates (recrystallized from diethyl ether/
hexane); m.p. 89–918C; 1H NMR (400 MHz, CDCl3): d=7.92 (d, J=
8.4 Hz, 2H), 7.48 (d, J=8.4 Hz, 2H), 3.49 (s, 3H), 2.51 ppm (s, 3H);
13C NMR (75 MHz, CDCl3): d=147.0, 134.1, 130.8, 127.4, 119.2 (q, J-
ACHTUNGTRENNUNG
[6] N-Heterocycles: S. L. Jain, V. B. Sharma, B. Sain, Tetrahedron Lett.
2003, 44, 4385–4387.
741, 688, 627 cmÀ1
; HRMS (ESI): m/z: calcd for C9H10F3NNaO3S2:
[7] Sulfides and sulfoxides: a) O. G. Mancheno, J. Dallimore, A. Plant,
C. Bolm, Org. Lett. 2009, 11, 2429–2432; b) F. Collet, R. H. Dodd,
P. Dauban, Org. Lett. 2008, 10, 5473–5476; c) O. G. Mancheno, C.
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Lett. 2005, 7, 4983–4985; f) H. Okamura, C. Bolm, Org. Lett. 2004,
6, 1305–1307; g) D. Leca, A. Toussaint, C. Mareau, L. Fensterbank,
E. Lacote, M. Malacria, Org. Lett. 2004, 6, 3573–3575; h) D. Leca,
K. Song, M. Amatore, L. Fensterbank, E. Lacote, M. Malacria,
323.9952 [M+Na]+; found: 323.9952; elemental analysis calcd (%) for
C9H10F3NO3S2: C 35.88, H 3.35, N 4.65; found: C 35.71, H 3.53, N 4.65.
Compound 3 f: Colorless needles (recrystallized from dichloromethane/
hexane); m.p. 93–948C; 1H NMR (400 MHz, CDCl3): d=7.06 (s, 2H),
3.56 (s, 3H), 2.72 (s, 6H), 2.35 ppm (s, 3H); 13C NMR (75 MHz, CDCl3):
d=145.2, 139.7, 133.4, 131.3, 119.2 (q, JACTHNUTRGNEU(GN C,F)=321.4 Hz), 47.0, 22.8,
21.1 ppm; IR (KBr): n˜ =3022, 2978, 2941, 1603, 1560, 1456, 1385, 1344,
1263, 1186, 1138, 1066, 958, 860, 791, 766, 741, 706, 623 cmÀ1; elemental
Chem. Eur. J. 2010, 16, 8713 – 8718
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
8717

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[21] The 6-31G basis sets were employed for H, C, O, and F and the 6-
311+G[d] basis sets for N, S, and Br.
[22] A similar SN2-type transition state was proposed in the oxygen-
transfer reaction from dimethyldioxirane to dimethyl sulfide, see:
A. G. Baboul, H. B. Schlegel, M. N. Glukhovtsev, R. D. Bach, J.
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[23] The results are also supported by the calculations on MeBr=
NSO2CF3+SMe2 with the 6-31G
ACHTUNGTNER(NUNG d,p) basis sets for H, C, O, and F
and the 6-311+G[d] basis sets for N, S, and Br.
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2893–2896.
Received: March 26, 2010
Published online: June 22, 2010
8718
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Chem. Eur. J. 2010, 16, 8713 – 8718