Mechanochemical aminochlorination of electron-deficient olefins with chloramine-T promoted by (diacetoxyiodo)benzene

Article abstract of DOI:10.1002/adsc.200700020

A direct and convenient procedure for the solvent-free mechanochemical aminochlorination of electron-deficient olefins promoted by (diacetoxyiodo) benzene [PhI(OAc)₂] was described using commercially available and cheap chloramine-T as a nitrogen and chlorine source. The vicinal chloramine derivatives were obtained in high regio- and stereoselectivity with good yields. PhI(OAc)₂ was superior to metal salts for the aminochlorination of electron-deficient olefins.

Full text of DOI:10.1002/adsc.200700020

FULL PAPERS
DOI: 10.1002/adsc.200700020
Mechanochemical Aminochlorination of Electron-Deficient
Olefins with Chloramine-T Promoted by (Diacetoxyiodo)benzene
Guan-Wu Wanga,* and Xue-Liang Wua
a
Hefei National Laboratory for Physical Sciences at Microscale, Joint Laboratory of Green Synthetic Chemistry and
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, Peopleꢀs Republic of
China
Fax : (+86)-551-360-7864; e-mail: gwang@ustc.edu.cn
Received: January 12, 2007; Revised: May 15, 2007
Abstract: A direct and convenient procedure for the selectivity with good yields. PhI(OAc)2 was superior
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solvent-free mechanochemical aminochlorination of to metal salts for the aminochlorination of electron-
electron-deficient olefins promoted by (diacetoxyio- deficient olefins.
do)benzene [PhI(OAc)2] was described using com-
T
mercially available and cheap chloramine-T as a ni- Keywords: aminochlorination; chloramine-T; elec-
trogen and chlorine source. The vicinal chloramine tron-deficient compounds; hypervalent compounds;
derivatives were obtained in high regio- and stereo- mechanochemistry; solid-state reactions
Introduction
fromlow yields and utilization of heavy metal cata-
lysts.[7]
The aminohalogenation of olefins has been recog-
N-Chloro-N-sodio-o-nitrobenzenesulfonamide,
a
nized as a very important transformation in organic chloramine-T analogue, was used to aminochlorinate
chemistry because the resulting vicinal haloamines cinnamic esters, trans-stilbene, and styrene, again re-
are very versatile intermediates for the synthesis of quiring a transition metal catalyst.[8] Very recently,
numerous pharmacologically active compounds.[1] Minakata, Komatsu, and co-workers reported the
Early efforts on the preparation of vicinal haloamine unique CO2-induced vicinal aminochlorination of ole-
derivatives by the addition of N-halo and N,N-dihalo fins, even though the role of the pressurized CO2 re-
compounds to olefins under non-catalytic conditions mains to be clarified.[9] In spite of the fact that the re-
confronted significant limitations such as narrow sulting vicinal haloaminated carbonyl compounds are
scope of substrates, poor yield and selectivity.[2] The synthetically important intermediates, which can be
highly regioselective and stereoselective aminohaloge- converted to numerous useful organic molecules by
nation of olefins is still a challenging task for organic replacing the halo atomwith a series of nucleophiles,
chemists and continues to be an active research area. the aminohalogenation of enones with chloramine-T
Recently, Liꢀs group[3] and others[4] have successfully has not been realized until now.
established the aminohalogenation of various olefins
Hypervalent iodine compounds have been used for
under different catalytic systems. Particularly, Liꢀs various organic reactions such as oxidations, carbon-
group has developed the elegant methodology on the carbon, carbon-heteroatom, and heteroatom-heteroa-
transition metal-catalyzed aminohalogenation of cin- tombond formations, oxidative fragmentations and
namates[3a–e] and a,b-unsaturated ketones[3f] by using rearrangements, etc.[10] RNH2 and (diacetoxyiodo)-
N,N-dichloro-p-toluenesulfonamide[3a,c–f] and N,N-di- benzene [PhI
ACHTREUNG
AHCTREUNG
well as chlorine sources. On the other hand, N-chloro- catalyst-free intermolecular aziridination of a series of
N-sodio-p-toluenesulfonamide, known as chloramine- alkenes with N-substituted hydrazines mediated by
T, is a cheap, commercially available, and highly reac- PhI
N
T has been extensively utilized as a nitrene-transfer trogen source to react with electron-deficient olefins
agent to aziridinate olefins.[6] In sharp contrast, only a has not been reported.
few examples for chloramine-T as an aminohalogena-
Solvent-free organic reactions have drawn the at-
tion agent were reported, and these protocols suffered tention of the chemical community for many years
Adv. Synth. Catal. 2007, 349, 1977 – 1982
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1977

Guan-Wu Wang and Xue-Liang Wu
FULL PAPERS
Table 1. Aminochlorination of 1,3-diphenylpropenone with
due to the publicꢀs increasing concern about environ-
mentally benign processes, low costs, simplicity in pro-
cess and handling, and even higher selectivity.[13] One
of our contributions to solvent-free organic reactions
is focused on mechanochemical reactions.[14] In con-
tinuation of our interest in solvent-free mechano-
chemical reactions, herein we report the successful ap-
plication of the ball-milling technique to the highly
regio- and stereoselective aminohalogenation of chal-
cones, cinnamate and cinnamide with chloramine-T
various additives.[a]
Yield [%][b]
dr (anti/syn)[c]
promoted by PhI(OAc)2.
G
Entry
Additive
1
2
3
4
5
6
7
8
PhI
PhI
PhI
PhI
PhI
CuCl
CuCl2·2H2O
CuI
C
77
53
76
75
53
29
55
0
91/9
91/9
92/8
91/9
92/8
89/11
91/9
/
Results and Discussion
At the onset, we chose 1,3-diphenylpropenone (1a) as
a model compound, and conducted its reaction with
chloramine-T trihydrate (TsNClNa·3H2O, 2) and
varied amounts of PhI
ball-milling conditions.[14] As shown in entries 1–5 of
Table 1, the PhI(OAc)2-mediated reaction of 1a with 2
(OAc)2 under our solventless
9
MnCl2·4H2O
ZnCl2
7
90/10
87/13
87/13
92/8
93/7
90/10
89/11
90/10
87/13
89/11
10
11
12
13
14
15
16
17
11
51
24
20
62
69
57
42
75
ACHTREUNG
FeCl3·6H2O
CoCl2·6H2O
NiCl2·6H2O
CrCl3·6H2O
CeCl3·7H2O
SnCl2·2H2O
SnCl4·5H2O
InCl3·4H2O
did not produce any aziridine derivative, but rather af-
forded chloramino ketone 3a. With 0.5 equivs. of PhI-
A
and efficiently under mechanical milling conditions to
give 3a with good yield (77%) and diastereoselectivity
(91/9) (entry 1, Table 1). Decreasing the amount of
PhI
uct yield (entry 2, Table 1), while increasing the
amount of PhI(OAc)2 up to 1.0 equiv. did not improve
A
[a]
Unless otherwise specified, all the reactions were per-
formed with 0.2 mmol of 1a, 0.4 mmol of 2, 0.1 mmol of
the employed additive.
ACHTREUNG
the product yield and diastereoselectivity (entries 3
and 4, Table 1). Two equivs. of 2 were necessary to
obtain good product yield (entry 1 vs. entry 5, Table 1).
Readily available and cheap copper salts CuCl,[6a,g]
[b]
[c]
[d]
[e]
[f]
Isolated yields by flash column chromatography.
1
Determined by H NMR.
0.05 mmol of PhI
0.15 mmol of PhI
ACHTREUNG
CuCl2 and CuI[6g] have been applied to the catalytic
[6a]
AHCTREUNG
0.2 mmol of PhI
ACHTREUNG
aziridinations of styrene, substituted styrenes, nor-
bornene,1,2-dihydronaphthalene, and cyclohexene by
chloramine-T with either acetonitrile[6a] or water[6g] as
the solvent. However, these copper salts have not
[g]
(OAc)2.
been examined for the reactions of chalcones with the substrate to substituted chalcones. Representative
chloramine-T. In order to compare the efficiency of chalcones 1b–e and 1f–i, which were prepared from
PhI(OAc)2 and metal salts, we examined the mecha- the reaction of acetophenone with various aromatic
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nochemical reaction of 1a with 2 promoted by aldehydes bearing either an electron-donating group
0.5 equivs. of CuCl, CuCl2·2H2O, and CuI (entries 6– or an electron-withdrawing group on the phenyl ring,
8, Table 1) as well as other inorganic salts (entries 9– and fromthe reaction of 4 ’-methoxyacetophenone or
18, Table 1). All of the investigated metal salts except 4’-chloroacetophenone with benzaldehyde or 4-chloro-
for CuI showed certain activity towards the formation benzaldehyde, respectively, were investigated. The
of 3a. Again, an aziridine derivative was not obtained yields and diastereoselectivity for the reactions of 1a–
in all cases. InCl3·4H2O exhibited the highest yield j with 2 are listed in Table 2.
(75%) and good diastereoselectivity (89/11), but still
As seen fromTable 2, all of the examined reactions
did not exceed those of PhI(OAc)2. Furthermore, of chalcones afforded vicinal chloramino ketones in
AHCTREUNG
when trying to extend the substrate scope with moderate to good yields with good to excellent diaste-
InCl3·4H2O, it was disappointing to observe that the reoselectivity except for 3b. It is interesting to note
reaction process of unactivated chalcones was rather that an electron-withdrawing group on either the R1-
sluggish, and the yield was unsatisfactory.
With the satisfactory result for the PhI(OAc)2- ity (entries 3–6, 9, 10). Products 3c–f, 3i, and 3j were
or the R2-phenyl ring increased the diastereoselectiv-
G
mediated reaction of 1a with 2 in hand, we extended practically obtained as a single isomer.
1978
asc.wiley-vch.de
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2007, 349, 1977 – 1982

Aminochlorination of Electron-Deficient Olefins with Chloramine-T
FULL PAPERS
Table 2. Solvent-free mechanochemical synthesis of vicinal chloroamino compounds promoted by PhI
(OAc)2.[a]
A
Entry
R1
R2
Product
Yield [%][b]
dr (anti/syn)[c]
1
2
3
4
5
6
7
8
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3a
3b
3c
3d
3e
3f[d]
3g
3h
3i
3j
3k
3l
3m
3n
3o
77
59
75
63
73
63
72
78
70
75
41
0
91/9
4-MeO-C6H4
4-Cl-C6H4
2-Cl-C6H4
3,4-Cl2-C6H4
4-NO2-C6H4
Ph
4-Cl-C6H4
Ph
4-Cl-C6H4
Ph
75/25
>99/1
>99/1
>99/1
>99/1
91/9
90/10
>99/1
>99/1
96/4
4-MeO-C6H4
4-MeO-C6H4
4-Cl-C6H4
4-Cl-C6H4
Me
Ph
Me
OMe
NEt2
9
10
11
12
13
14
15
Et
i-Bu
Ph
Ph
-
-
0
65
52
>99/1
>99/1
[a]
Unless otherwise specified, all the reactions were performed with 0.2 mmol of 1a, 0.4 mmol of 2, 0.1 mmol of PhI
the reaction time was 1.5 h.
A
[b]
[c]
[d]
Isolated yield by flash column chromatography.
Determined by the analysis of 1H NMR.
0.8 mmol of 2 was used, and the reaction time was 3 h.
Furthermore, other electron-deficient olefins in- single crystal, which was grown frompetroleumether/
cluding aliphatic enones, cinnamate and cinnamide ethyl acetate (6:1) (Figure 1).
were investigated to show the scope and limitation of
To demonstrate the advantages of the solvent-free
the present method. When the R2 group of the mechanochemical reactions and explore the feasibility
enones was an alkyl substituent, the yield of chlorami- of this chloramination reaction in solution, we chose
no ketone decreased rapidly, yet good diasteroselec- 1a as the representative substrate to react with 2 pro-
tivity was observed (entry 11). The reactions of moted by different additives in several solvents. PhI-
enones with alkyl substituents attached to the C=C
A
double bond failed to give any products (entries 12, CuCl2·2H2O, CuCl and CuI were examined as the ad-
13). Much to our delight, cinnamate 1n reacted
smoothly under our conditions to give chloramino
ester 3n in 65% yield with excellent diasteroselectivi-
ty (entry 14). Further studies disclosed that cinnamide
1o, which was considered as a more challenging sub-
strate due to the reduced electrophilicity of the C=C
double bond, was able to be aminochlorinated with
moderate yield and excellent diasteroselectivity
(entry 15).
Compounds 3a,[3f] 3d,[3f] 3f,[3f] 3g,[3f] 3i,[3f] 3k[3f] and
3n[3a,c,d] have been previously reported and were con-
firmed by the comparison with their reported data.
New products 3b, 3c, 3e, 3h, 3j and 3o were fully char-
1
acterized by HR-MS, FT-IR, H NMR, and 13C NMR.
The spectral data were consistent with their molecular
structures. The anti configuration of 3c was further
unequivocally established by the X-ray structure of its Figure 1. ORTEP diagramof 3c.
Adv. Synth. Catal. 2007, 349, 1977 – 1982
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1979

Guan-Wu Wang and Xue-Liang Wu
FULL PAPERS
Scheme 1. Proposed reaction mechanism for the PhI(OAc)2-promoted aminochloration of olefins.
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ditives. PhI
CH3CN, which was used as a privileged solvent for which continues to react with olefin 1 again. The pro-
chloramine-T,[6] either at roomtemperature or at posed ring-opening process of aziridinium 6 by ClÀ
reflux conditions. PhI(OAc)2 afforded none or only via an SN2 route can fully explain the observed regio-
A
AHCTREUNG
trace amount of product 3a in THF, DMF, MeOH, selectivity and exclusive or dominant formation of the
CCl4, toluene and hexane. It is only in CH2Cl2 that anti-diastereoisomer. The reason for the preferred nu-
product 3a could be obtained in 53% yield with good cleophilic ring opening by ClÀ over other species such
diastereoselectivity (92/8) for the PhI(OAc)2-mediat- as hydroxide coexisted in the reaction systemis not
G
ed reaction of 1a with 2 for 6 h. InCl3·4H2O, CuCl known[3b] and needs further investigation.
and CuI could not promote the reaction in neither
CH3CN nor CH2Cl2. While CuCl2·2H2O did not give
any product in CH2Cl2, it indeed generated product Conclusions
3a in CH3CN after reaction for 24 h with 50% yield
and the same diastereoselectivity. Even though it was In summary, an efficient, simple and solvent-free
possible to promote the reaction of 1a with 2 in or- method for the aminochlorination of electron-defi-
ganic solvents by PhI
vent-free PhI(OAc)2-promoted mechanochemical re- enones, a representative cinnamate and cinnamide
action was the most efficient one in term of product promoted by PhI(OAc)2 under ball-milling conditions
yield and reaction time. has been developed. The use of inexpensive and
Although the exact reaction mechanism is not clear stable chloramine-T as a nitrogen and chlorine source
right now, a possible pathway for the PhI(OAc)2-pro- makes the reaction very convenient and easy to
moted aminochlorination of electron-deficient olefins handle. PhI(OAc)2 was superior to metal salts for the
is shown in Scheme 1. Chloramine-T attacks PhI- aminochlorination of electron-deficient olefins.
(OAc)2 and CuCl2·2H2O, the sol- cient olefins including various a,b-unsaturated
ACHTREUNG
AHCTREUNG
AHCTREUNG
AHCTREUNG
A
give N-aceto-N-chloro-p-toluenesulfonamide 5.[10]
Subsequent electrophilic reaction of intermediate 5
with olefin 1 produces aziridinium 6 and ClÀ,[3,8] due
to the fact that chloride is a better leaving group than
acetate. The b-position of the aziridinium 6 has more
Experimental Section
General Remarks
Reagents and solvents were obtained from commercial sup-
pliers and were used without further purification. All melt-
ing points were determined on an XT-4 binocular micro-
scope (Beijing Tech Instrument Co., China) and are not cor-
rected. Infrared spectra were recorded on a Vector-12 infra-
red spectrometer in KBr pellet and reported in cmÀ1.
1H NMR spectra were recorded on Bruker AV300
positive charge than the a-position due to the stabili-
[3]
zation effect fromthe phenyl ring.
Thus, the ring
opening of 6 by in situ formed nearby ClÀ via an SN2
route preferably occurs at b-position to give inter-
mediate 7. Then, intermediate 7 reacts with another
molecule of chloramine-T in the presence of a proton
source (most probably water present in the system) to (300 MHz) spectrometer, chemical shifts (d) are reported in
1980
asc.wiley-vch.de
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2007, 349, 1977 – 1982

Aminochlorination of Electron-Deficient Olefins with Chloramine-T
parts per million relative to tetramethylsilane. Splitting pat-
FULL PAPERS
3-Chloro-3-(3,4-dichlorophenyl)-1-phenyl-2-(tosylamino)-
terns are designated as s, singlet; d, doublet; t, triplet; m,
multiplet. 13C NMR spectra were recorded on Bruker
AV300 (75 MHz) spectrometer with complete proton decou-
pling, chemical shifts are reported in parts per million rela-
tive to the solvent resonance as the internal standard
(CDCl3, d=77.16 ppm). High-resolution mass spectra (HR-
MS) were recorded on a Bruker VPEXII spectrometer with
EI mode. Analytical TLC and column chromatography were
performed on silica gel GF254, and silica gel H60, respec-
tively.
propan-1-one (3e): white solid, mp 136–1388C. IR (KBr):
n=3178, 2925, 1673, 1595, 1448, 1336, 1251, 1162, 1088, 971,
917, 791, 663, 572, 544 cmÀ1 1H NMR (300 MHz, CDCl3):
;
d=7.83 (d, J=7.5 Hz, 2H), 7.62 (t, J=7.5 Hz, 1H), 7.44–
7.48 (m, 4H), 7.28–7.25 (m, 2H), 7.05–7.09 (m, 3H), 5.63 (d,
J=9.9 Hz, 1H), 5.31 (dd, J=9.9, 7.5 Hz, 1H), 4.95 (d, J=
7.5 Hz, 1H, exchangeable with D2O), 2.32 (s, 3H); 13C NMR
(75 MHz, CDCl3, all 1C unless indicated): d=196.8, 144.0,
136.8, 136.7, 135.4, 134.6, 133.4, 132.8, 130.5, 130.2, 129.6
(2C), 129.1 (2C), 128.9 (2C), 127.5, 126.9 (2C), 60.8, 60.2,
21.6; HR-MS (EI-TOF): m/z=445.0297 [M+ÀHCl], calcd.
for C22H17NO3SCl2: 445.0306.
3-Chloro-3-(4-chlorophenyl)-1-(4-methoxylphenyl)-2-(to-
sylamino)propan-1-one (3h): white solid, mp 61–638C. IR
(KBr): n=3258, 2924, 1670, 1599, 1341, 1267, 1160, 1090,
General Procedure for the Aminochlorination of
Electron-Deficient Olefins
832, 812, 664, 527 cmÀ1 1H NMR (300 MHz, CDCl3): d=
;
A mixture of electron-deficient olefin 1 (0.2 mmol), chlora-
mine-T trihydrate 2 (112.6 mg, 0.4 mmol), and a given
7.78 (d, J=8.7 Hz, 2H), 7.46 (d, J=8.4 Hz, 1H), 7.20–7.13
(m, 4H), 7.05 (d, J=8.4 Hz, 2H), 6.91 (d, J=8.7 Hz, 2H),
5.53 (d, J=9.9 Hz, 1H), 5.30 (dd, J=9.9, 7.0 Hz, 1H), 5.02
(d, J=7.0 Hz, 1H, exchangeable with D2O), 3.90 (s, 3H),
2.31 (s, 3H); 13C NMR (75 MHz, CDCl3, all 1C unless indi-
cated): d=194.5, 164.7, 143.7, 136.9, 135.1, 135.0, 131.5 (2C),
129.5 (4C), 128.7 (2C), 128.2, 127.0 (2C), 114.2 (2C), 61.1,
60.8, 55.8, 21.5; HR-MS (EI-TOF): m/z=441.0796
[M+ÀHCl], calcd. for C23H20NO4SCl: 441.0802.
amount of PhI(OAc)2 along with a stainless ball of 7.0 mm
G
diameter were introduced into a stainless steel jar (5 mL).
The same mixture was also introduced into a second parallel
jar. The two reaction vessels were milled simultaneously in a
Retsch MM200 mixer mill (Retsch GmbH, Haan, Germany)
at a frequency of 1800 revolutions per minute for 1.5 h. The
resulting mixture from the two reaction vessels was extract-
ed with ethyl acetate twice (10 mL”2). The extraction was
filtrated to remove the insoluble material and the filtrate
was evaporated to dryness under vacuum. The residual was
separated on a silica gel column with petroleum ether/ethyl
acetate (8:1) as the eluent to get the desired product 3.
Compounds 3a,[3f] 3d,[3f] 3f,[3f] 3g,[3f] 3i,[3f] 3k[3f] and 3n[3a,c,d]
have been previously reported and were characterized by
comparison with their reported data. Physical and spectro-
scopic data of the newly synthesized compounds are given
below.
3-Chloro-1,3-bis(4-chlorophenyl)-2-(tosylamino)propan-1-
one (3j): white solid, mp 146–1488C. IR (KBr): n=3219,
2923, 1685, 1588, 1492, 1337, 1161, 1090, 805, 674, 555 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=7.76 (d, J=8.7 Hz, 2H),
7.41–7.44 (m, 4H), 7.20–7.14 (m, 4H), 7.05 (d, J=8.1 Hz,
2H), 5.57 (d, J=9.6 Hz, 1H), 5.27 (dd, J=9.6, 8.1 Hz, 1H),
4.97 (d, J=8.1 Hz, 1H, exchangeable with D2O), 2.27 (s,
3H); 13C NMR (75 MHz, CDCl3, all 1C unless indicated):
d=196.0, 144.0, 141.2, 136.7, 135.3, 135.0, 133.8, 130.4 (2C),
129.6 (2C), 129.5 (2C), 129.2 (2C), 128.8 (2C), 127.0 (2C),
60.8, 60.7, 21.6; HR-MS (EI-TOF): m/z=445.0302
[M+ÀHCl], calcd. for C22H17NO3SCl2: 445.0306.
3-Chloro-3-(4-methoxylphenyl)-1-phenyl-2-(tosylamino)-
propan-1-one (3b): white solid, mp 132–1348C. IR (KBr):
n=3269, 2924, 1668, 1595, 1514, 1447, 1335, 1263, 1161,
1090, 1029, 812, 671, 553, 531 cmÀ1 1H NMR (300 MHz,
;
3-Chloro-N,N-diethyl-3-phenyl-2-(tosylamino)propiona-
mide (3o): white solid, mp 185–1878C. IR (KBr): n=3179,
2981, 2937, 1629, 1442, 1341, 1164, 1089, 928, 814, 721, 668,
CDCl3): d=7.76 (d, J=7.2 Hz, 2H), 7.60 (t, J=7.7 Hz, 1H),
7.51 (d, J=8.5 Hz, 2H), 7.43 (t, J=7.2 Hz, 2H), 7.13 (d, J=
8.5 Hz, 2H), 7.03 (d, J=7.7 Hz, 2H), 6.75 (d, J=8.5 Hz,
2H), 5.51 (d, J=9.9 Hz, 1H), 5.38 (dd, J=9.9, 6.6 Hz, 1H),
5.07 (d, J=6.6 Hz, 1H, exchangeable with D2O), 3.79 (s,
3H), 2.28 (s, 3H); 13C NMR (75 MHz, CDCl3, all 1C unless
indicated): d=196.5, 160.2, 143.6, 136.9, 135.4, 134.2, 129.6,
129.5 (2C), 129.4 (2C), 128.9 (2C), 128.8 (2C), 127.2 (2C),
114.0 (2C), 61.7, 61.6, 55.4, 21.5; HR-MS (EI-TOF): m/z=
407.1182, [M+ÀHCl], calcd. for C23H21NO4S: 407.1191.
3-Chloro-3-(4-chlorophenyl)-1-phenyl-2-(tosylamino)pro-
pan-1-one (3c): white solid, mp 147–1498C. IR (KBr): n=
3267, 2922, 1666, 1596, 1494, 1452, 1337, 1241, 1163, 1092,
1
567, 554, 526 cmÀ1; H NMR (300 MHz, CDCl3): d=7.39 (d,
J=8.1 Hz, 2H), 7.33–7.24 (m, 5H), 7.10 (d, J=8.1 Hz, 2H),
6.07 (d, J=9.3 Hz, 1H), 4.98 (d, J=9.3 Hz, 1H), 4.73 (t, J=
9.3 Hz, 1H), 3.43–3.33 (m, 3H), 3.23–3.14 (m, 1H), 2.35 (s,
3H), 1.19 (t, J=7.2 Hz, 3H), 1.02 (t, J=7.1 Hz); 13C NMR
(75 MHz, CDCl3, all 1C unless indicated): d=168.5, 143.3,
137.4, 137.2, 129.4 (2C), 128.9, 128.6 (2C), 128.4 (2C), 126.9
(2C), 62.4, 57.3, 42.5, 40.9, 21.5, 14.0, 12.4; HR-MS (EI-
TOF): m/z=372.1507 [M+ÀHCl], calcd. for C20H24N2O3S:
372.1508.
809, 684, 665, 546, 527 cmÀ1 1H NMR (300 MHz, CDCl3):
;
d=7.76 (d, J=8.0 Hz, 2H), 7.59 (t, J=7.2 Hz, 1H), 7.40–
7.47 (m, 4H), 7.18–7.11 (m, 4H), 7.03 (d, J=8.0 Hz, 2H),
5.52 (d, J=9.6 Hz, 1H), 5.34 (dd, J=9.6, 6.6 Hz, 1H), 5.01
(d, J=6.6 Hz, 1H, exchangeable with D2O), 2.29 (s, 3H);
13C NMR (75 MHz, CDCl3, all 1C unless indicated): d=
196.5, 143.9, 136.8, 135.3, 135.2, 134.9, 134.4, 129.6 (2C),
129.5 (2C), 129.0 (2C), 128.9 (2C), 128.8 (2C), 127.1 (2C),
61.2, 61.1, 21.6; HR-MS (EI-TOF): m/z=411.0697
[M+ÀHCl], calcd. for C22H18NO3SCl: 411.0696.
Procedure for Aminochlorination of Chalcone 1a in
Solution
To a solution of chalcone 1a (208.0 mg, 1.0 mmol) in CH2Cl2
(5 mL) was added chloramine-T trihydrate 2 (563.5 mg,
2.0 mmol) and PhI(OAc)2 (322.3 mg, 1.0 mmol). This mix-
A
ture was allowed to stir at roomtemperature for 6 h. The
same work-up afforded 3a; yield: 220.7 mg (53%).
Adv. Synth. Catal. 2007, 349, 1977 – 1982
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1981

Guan-Wu Wang and Xue-Liang Wu
FULL PAPERS
Replacing PhI
153.0 mg) and CH2Cl2 with CH3CN, and prolonged reaction
time (24 h) also gave 3a; yield: 207.3 mg (50%).
G
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Determination of the X-Ray Crystal Structure of
Compound 3c
Crystal was grown by slowly evaporating a solution of 3c in
petroleumether/ethyl acetate (6:1). Refinement details: em -
pirical formula: C22H19Cl2NO3S; formula weight: 448.34; T=
153(2) K; wavelength: 0.71070 Š; crystal system: monoclin-
ic; space group: C2/c; unit cell dimensions: a=19.603(3) Š,
a=908, b=10.4638(14) Š, b=92.116(3)8, c=20.380(2) Š,
g=908; V=4177.5(10) Š3; Z=8; density (calculated):
1.426 mgmÀ3; absorption coefficient: 0.435 mmÀ1; F
(000)=
1856; crystal size: 0.50”0.48”0.30 mm3; q range for data
collection: 3.0 to 25.3; index ranges: À23 ꢀ h ꢀ 23, À12 ꢀ
k ꢀ 12, À20 ꢀ l ꢀ 24; reflections collected: 19735; inde-
pendent reflections: 3826 [R(int)=0.0221]; completeness to
q=25.34: 99.5%; absorption correction: multi-scan; max.
and min. transmission: Full-matrix least-squares on F2;
data/restraints/parameters: 3826/0/268; goodness-of-fit on
F2: 1.104; final R indices [I>2s(I)]: R1=0.0339, wR2=
0.0819; R indices (all data): R1=0.0361, wR2=0.0832; larg-
est diff. peak and hole: 0.307 and À0.355 eŠÀ3.
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Crystallographic data for the structure reported in this
paper have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication no.
CCDC-614095. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK [fax.: (internat.) + 44 1223/336–033; e-mail:
deposit@ccdc.cam.ac.uk].
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Acknowledgements
The authors are grateful for the financial support from Na-
tional Natural Science Foundation ofChina (No. 20621061)
and Specialized Research Fund for the Doctoral Program of
Higher Education (No. 20050358021).
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1982
asc.wiley-vch.de
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2007, 349, 1977 – 1982