Ru(II)-Catalyzed rearrangement of 2-aryl-2-(phenylthio)penta-3,4-dienyl 2,2,2-trichloroacetimidates

Article abstract of DOI:10.1016/j.jorganchem.2010.08.014

[RuCl₂(p-cymene)]₂ efficiently catalyzes the rearrangement of 2-aryl-2-(phenylthio)penta-3,4-dienyl 2,2,2- trichloroacetimidate to afford (Z)-2,2,2-trichloro-N-(4-aryl-1-(phenylthio) penta-2,4-dien-2-yl)acetamide. Ru carbene is assum

Full text of DOI:10.1016/j.jorganchem.2010.08.014

Journal of Organometallic Chemistry 696 (2011) 118e122
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Ru(II)-Catalyzed rearrangement of 2-aryl-2-(phenylthio)penta-3,4-dienyl
2,2,2-trichloroacetimidates
*
Lingling Peng, Xiu Zhang, Jie Ma, Jianbo Wang
Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry,
Peking University, Beijing 100871, China
a r t i c l e i n f o
a b s t r a c t
Article history:
[RuCl2(p-cymene)]2 efficiently catalyzes the rearrangement of 2-aryl-2-(phenylthio)penta-3,4-dienyl
2,2,2-trichloroacetimidate to afford (Z)-2,2,2-trichloro-N-(4-aryl-1-(phenylthio)penta-2,4-dien-2-yl)
acetamide. Ru carbene is assumed as the reactive intermediate in this rearrangement.
Ó 2010 Elsevier B.V. All rights reserved.
Received 27 July 2010
Received in revised form
12 August 2010
Accepted 12 August 2010
Available online 20 August 2010
Keywords:
Allene
Ru(II) catalysis
Rh(II) carbene
1,4-Thio shift
Rearrangement
1. Introduction
2. Results and discussion
Allene chemistry is a hot research topic in synthetic organic
chemistry in recent years. In particular, the transition-metal-cata-
lyzed reaction of allene derivatives has led to many synthetically
useful transformations [1e26]. However, there are rare reported
examples in which metal carbene is supposed as intermediates in
transition-metal-catalyzed reactions of allenes [27e36].
The reaction shown in Scheme 1 demonstrates that Ru(II) carbene
is generated efficiently from -carbonyl allenic sulfides. The electron-
deficient Ru(II) carbene is then trapped by carbonyl oxygen to afford
furan derivative as final product. To further extend this chemistry, we
conceived that novel transformations should be possible by convert-
ing the carbonyl group into various nucleophilic functional groups.
b
We have recently reported the reaction of [RuCl2(p-cymene)]2-
A series of
b
-allenic sulfide esters or ketones were prepared
-diazo carbonyl
or PtCl2-catalyzed rearrangement of
b
-carbonyl allenic sulfides
from Cu(I)- or Rh(II)- catalyzed reaction of a
which afford furan products in high yields [31]. The reaction
proceeds through 1,4-migration of the sulfanyl group and
presumably involves a metal carbene intermediate which is trap-
ped intramolecularly by a carbonyl group (Scheme 1).
compounds and propargyl sulfide [37,38]. The ester or ketone
group was subsequently converted into various functional groups.
Allenic sulfide derivatives 1, 2, 3, and 4a are prepared and their
reactions with transition metals were investigated. Preliminary
study shows that no reaction occurs for allenic sulfide derivatives 1,
2 and 3 under the catalysis with [RuCl2(p-cymene)]2 or PtCl2. To our
delight, we found that [RuCl2(p-cymene)]2-catalyzed reaction of
substrate 4a leads to clean rearrangement. We then proceeded to
study this rearrangement in details.
Since the carbonyl group of b-carbonyl allenic sulfides can be
easily transferred into other functional group, we proceed to extend
this investigation by exploring transition-metal-catalyzed reactions
of various allenic sulfide derivatives. In this paper we report
[RuCl2(p-cymene)]2-catalyzed rearrangement of allenic sulfides
bearing a
b-trichloroethanimidyl group. The reaction gives 1,
3-butadiene derivatives in high yields.
PhS
Ph
PhS
Ph
PhS
Ph
PhS
Ph
OH
O
CCl3
NH
OH
RO
O
R = OAc or TMS
3
* Corresponding author. Tel.: þ8610 6275 7248; fax: þ8610 6275 1708.
E-mail address: wangjb@pku.edu.cn (J. Wang).
4a
1
2
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.08.014

L. Peng et al. / Journal of Organometallic Chemistry 696 (2011) 118e122
119
R1
trichloroethanimidate under heating condition (Overman rear-
rangement) is a general process [39].
R1
[RuCl2(p-cymene)]2
SPh
(5 mol %)
PhS
R
PhMe, 80 oC
R
O
Ph
O
SPh
HN
SPh
SPh
MLn
LnM
4a
LnM
R1
O
5a
MLn
O
Cl3C
Ru(II)
SPh
COR
SPh
R1
COR
O
R1
R1
Ph
Ru
R
Metal carbene
R
Ru
intermediate
PhS
Ph
O
Cl3C
O
NH
CCl3
SPh
NH
Scheme 1. Ru(II)-Catalyzed reaction of b-carbonyl allenic sulfides.
A
According to the previous reaction condition for furan formation,
allenic sulfide 4a was firstly treated with 5 mol% [RuCl2(p-cym-
ene)]2. It afforded a diene product 5a in 88% yield in DCE at 60 ꢀC
(Table 1, entry 1). The reaction took only 30 min to complete at 60 ꢀC,
while the reaction needed 4 h when carried out at room tempera-
ture (entry 2). We also examined the reactions of 4a with other
transition metal catalysts in DCE at 60 ꢀC. PtCl2 was also an effective
catalyst and afforded 5a in 50% yield (entry 3). Rh2(O2CCF3)4 only
gave 5a in 8% yield (entry 4). Au catalysts werefound not effective for
this rearrangement (entries 5e9). AgOTf and Pd(II) catalysts were
also not effective (entries 10e12).
D
Ph
Ru
O
SPh
Ph S
Ph
Ru
O
NH
CCl3
N
H
Cl3C
C
B
Scheme 2. Mechanistic hypothesis for the formation of diene product.
To examine the scope of this novel rearrangement, we then
Table 1
Reaction of 4a with various transition-metal complexes.
prepared a series of
DBU-catalyzed reaction of
chloroacetonitrile (eq. (1)) [40].
b
-trichloroethanimidyl allenic sulfides 4b-k by
b-allenic sulfide alcohols 6b-k with tri-
Ph
PhS
Catalyst
SPh
HN
Ph
O
CCl3
NH
DCE
PhS
R
O
PhS
R
DBU (0.2 eq)
Cl3C
O
CCl3
NH
+
CCl3CN
2.0 eq
(1)
OH
6b-k
CH2Cl2, rt
0.5-1 h
4a
5a
4b-k
Entry
Catalysta
T(ꢀC)
t(h)
yield(%)b
The [RuCl2(p-cymene)2]-catalyzed reaction of 4b-k was then
investigated under the optimized reaction conditions and the
results are collected in Table 2. When R is an aryl group, the
1
2
3
4
5
6
7
8
[RuCl2(p-cymene)]2
[RuCl2(p-cymene)]2
PtCl2
Rh2(CO2CF3)4
AuCl
60
25
60
60
60
60
60
60
60
60
60
60
0.5
4
4
4
5
88
90
50
8
c
–
Table 2
AuPPh3Cl
19
e
[RuCl2(p-cymene)]2-catalyzed reaction of 4b-k.
AuCl þ AgOTf
AuCl þ AgBF4
AuCl þ AgSbF6
AgOTf
Pd(OAc)2
Pd2(dba)3
22
22
22
24
19
22
traced
trace
trace
trace
trace
trace
R
9
PhS
R
[RuCl2(p-cymene)]2
10
11
12
(5 mol %)
SPh
O
CCl3
NH
HN
DCE
O
Cl3C
5b-k
a
Reactions were carried out with 5 mol % catalyst except for Rh(II) catalyst, in
which case 1 mol % catalyst was used.
4b-k
b
Isolated yields after column chromatography.
No product 5a can be identified by TLC.
Small amount of product 5a can be identified from TLC, most starting material
c
d
Entry
4b-k, R
T(ꢀC)
t(h)
yield (%)a
remained or decomposed.
1
2
3
4
5
6
7
8
4b, p-BrC6H4
4c, p-MeOC6H4
4d, 3,4-Cl2C6H3
4d, 3,4-Cl2C6H3
4e, p-ClC6H4
4f, p-O2NC6H4
4g, m-MeC6H4
4h, m-MeOC6H4
4i, m-ClC6H4
4i, m-ClC6H4
4j, 1-naphthyl
4k, H
25
25
25
60
25
60
25
25
25
60
25
60
4
4
5
0.5
4
3
5
5
5
93
94
86
84
89
70
86
88
81
80
The structure of 5a was unambiguously confirmed by X-ray
analysis of single crystal (Fig. 1) [Appendix A].
Based on our previous study [31], a mechanism for the forma-
tion of diene product is proposed as shown in Scheme 2. The metal
carbene intermediate C is first formed through a similar process as
described in Scheme 1. From C, the nitrogen atom of the tri-
chloroethanimidyl group interacts with the electron-deficient car-
bene carbon atom to give D, subsequent rearrangement leads to the
formation of 5a, with release of the metal catalyst. As comparison, it
is noted that the [33] rearrangement of allyl or propargyl
9
10
11
12
0.5
23
72
b
–
e
a
Isolated yields after column chromatography.
The starting material decomposed, but no diene product 5j or 5k was identified.
b

120
L. Peng et al. / Journal of Organometallic Chemistry 696 (2011) 118e122
Fig. 1. The X-ray structure of 5a.
reaction proceeds smoothly and affords the corresponding diene
products in excellent yields (entries 1e8), except in the case
when R is 1-naphthyl group (entry 9). It is noted that when there
is electron-deficient substitute on the R group, the reaction is too
sluggish at room temperature and the reaction temperature
needs to be increased to 60 ꢀC (entries 3, 5). When the R is H, the
reaction gave complex mixture after a long reaction time (entry
10). We have also attempted to extend the reaction substrates to
1H and 13C NMR spectra were recorded at 300 MHz (or 200 MHz)
and 75 MHz (or 50 MHz) with Varian Mercury 300 spectrometer.
Chemical shifts are reported in ppm using tetramethylsilane as
internal standard. IR spectra were recorded with a Nicolet 5MX-S
infrared spectrometer. Mass spectra were obtained on a VG ZAB-HS
mass spectrometer.
4.2. Preparation of 2-aryl-2-(phenylthio)penta-3,4-dienyl 2,2,2-
trichloroacetimidate 4a-i
these derived from secondary
However, we failed to synthesize these substrates by the reaction
of secondary -allenic sulfide alcohols with trichloroacetonitrile,
b-allenic sulfide alcohols.
b
Under a nitrogen atmosphere, 2-phenylthio-3,4-pentadienyl
alcohol 6a-i (2.0 mmol) and trichloroacetonitrile (4.0 mmol) were
mixed in anhydrous CH2Cl2 (20 mL) in a 50 mL round-bottomed
flask. To the solution was then added DBU (0.4 mmol) at 0 ꢀC (ice-
bath). The reaction was continued at room temperature until
completed as judged by TLC. Removal of the solvent in vacuo gave
a crude residue, which was purified by silica gel column. Elution
with petroleum ether/ethyl acetate (200:1) afforded pure product
of 4a-i.
presumably due to the steric hindrance of the secondary
alcohols.
3. Conclusion
In summary, we have reported the [RuCl2(p-cymene)]2-cata-
lyzed reaction of 2-aryl-2-(phenylthio)penta-3,4-dienyl 2,2,2-tri-
chloroacetimidate, which affords 1,3-diene derivatives in excellent
yields [41e45]. The reaction proceeds through 1,4-migration of the
sulfanyl group and presumably involves a Ru carbene intermediate
which interacts with tethered trichloroethanimidyl group to
complete the transformation. This result further demonstrates the
diverse reactivity of metal carbene generated from allenic sulfide
precursors.
2-Phenyl-2-(phenylthio)penta-3,4-dienyl 2,2,2-trichloroacetimidate
(4a).yield 90%; IR (film) 3338, 3058, 1953, 1663, 1303, 1086, 796,
749, 694 cmꢁ1
;
1H NMR (CDCl3, 300 MHz)
d
¼ 4.43 (d, J ¼ 11.1
Hz, 1H), 4.51 (dd, J ¼ 11.1, 6.6 Hz, 1H), 4.62 (d, J ¼ 11.1 Hz, 1H),
4.81 (dd, J ¼ 11.1, 6.6 Hz, 1H), 5.67 (t, J ¼ 6.6 Hz, 1H), 7.24e7.45
(m, 8H), 7.60e7.63 (m, 2H), 8.19 (s, 1H); 13C NMR (CDCl3,75
MHz)
d
¼ 56.85, 72.04, 78.80, 91.15, 93.56, 127.61,127.96, 128.03,
4. Experimental section
128.44, 129.33, 130.83, 137.98, 140.02, 162.30, 207.68. EI-MS (m/
z, relative intensity): 411 (Mþ, 0.6), 302 (35), 250 (27), 141
(100), 115 (77), 109 (32), 91 (24), 77 (27), 44 (63). HRMS calcd
for C19H16O35Cl3SN [Mþ] 411.0018; Found: 411.0000.
4.1. General
All reactions were performed under a nitrogen atmosphere in
a flame-dried reaction flask. All solvents were distilled prior to use.
Toluene and THF was distilled over sodium, DCE was distilled over
NaH. For chromatography, 200e300 mesh silica gel (Yantai, China).
2-(4-Bromophenyl)-2-(phenylthio)penta-3,4-dienyl 2,2,2-tri-
chloroacetimidate (4b). yield 74%; IR (film) 3337, 1953, 1663, 1488,
1302,1079,1009, 825, 796, 750, 734, 693 cmꢁ1; 1H NMR (CDCl3, 300
MHz)
d
¼ 4.42 (d, J ¼ 11.1 Hz,1H), 4.51e4.59 (m, 2H), 4.81 (dd, J ¼ 11.1,

L. Peng et al. / Journal of Organometallic Chemistry 696 (2011) 118e122
121
6.6 Hz,1H), 5.60 (t, J ¼ 6.6 Hz,1H), 7.26e7.50 (m, 9H), 8.22 (s,1H); 13
C
(CDCl3, 300 MHz)
d
¼ 3.80 (s, 3H), 4.41 (d, J ¼ 11.1 Hz, 1H), 4.50
NMR (CDCl3, 75 MHz)
d
¼ 56.40, 71.78, 79.06, 91.00, 93.22, 121.67,
(dd, J ¼ 11.1, 6.6 Hz, 1H), 4.59 (d, J ¼ 11.1 Hz, 1H), 4.80 (dd, J ¼ 11.1,
128.51, 129.46, 129.78, 130.34, 131.02, 137.87, 139.18, 162.07, 207.61.
EI-MS (m/z, relative intensity): 491 (Mþ, 1), 414 (3), 382 (44), 330
(30), 318 (18), 249 (29), 219 (95), 140 (100), 109 (85), 44 (61). HRMS
calcd for C19H15ONS35Cl739Br [Mþ] 488.9123; Found: 488.9119.
2-(4-Methoxyphenyl)-2-(phenylthio)penta-3,4-dienyl 2,2,2-tri-
chloroacetimidate (4c). yield 85%; IR (film) 3341, 2955, 2835, 1953,
6.6 Hz, 1H), 5.66 (t, J ¼ 6.6 Hz, 1H), 6.80e6.84 (m, 1H), 7.20e7.47
(m, 8H), 8.19 (s, 1H); 13C NMR (CDCl3, 75 MHz)
d
¼ 55.23, 56.85,
72.03, 78.80, 91.13, 93.50, 113.18, 113.89, 120.25, 128.42, 128.95,
129.33, 130.79, 137.97, 141.60, 159.22, 162.25, 207.60. EI-MS (m/
z, relative intensity): 441 (Mþ, 0.4), 332 (16), 280 (17), 171 (100),
141 (25), 44 (20). HRMS calcd for C20H18O2NS35Cl3 [Mþ] 441.0124;
Found: 441.0126.
1663, 1510, 1300, 1252, 1182, 1086, 1031, 828, 795, 750, 693 cmꢁ1
1H NMR (CDCl3, 300 MHz)
;
d
¼ 3.79 (s, 3H), 4.40 (d, J ¼ 11.1 Hz, 1H),
2-(3-Chlorophenyl)-2-(phenylthio)penta-3,4-dienyl 2,2,2-tri-
chloroacetimidate (4i). Yield 92%; IR (film) 3339, 1952, 1664,
4.50 (dd, J ¼ 10.8, 6.6 Hz, 1H), 4.58 (d, J ¼ 11.1 Hz, 1H), 4.79 (dd, J ¼
10.8, 6.6 Hz, 1H), 5.65 (t, J ¼ 6.6 Hz, 1H), 6.83e6.88 (m, 2H),
1302, 1086, 999, 854, 829, 795, 750, 692 cmꢁ1 1H NMR (CDCl3,
;
7.25e7.56 (m, 7H), 8.19 (s, 1H); 13C NMR (CDCl3, 75 MHz)
d
¼ 55.21,
300 MHz)
4.84 (dd, J ¼ 11.1, 6.9 Hz, 1H), 5.61 (t, J ¼ 6.9 Hz, 1H), 7.25e7.52
(m, 8H), 7.63 (s, 1H), 8.22 (s, 1H); 13C NMR (CDCl3, 75 MHz)
d
¼ 4.40 (d, J ¼ 11.1 Hz, 1H), 4.52e4.58 (m, 2H),
56.47, 72.10, 78.73, 91.18, 93.75, 113.31, 128.42, 129.15, 129.26,
131.01, 132.02, 137.92, 158.89, 162.31, 207.60. EI-MS (m/z, relative
intensity): 441 (Mþ, 8), 332 (15), 318 (14), 280 (66), 171 (50), 133
(100), 77 (22), 44 (92). HRMS calcd for C20H18O325Cl3SN [Mþ]
441.0124; Found: 441.0114.
d
¼
56.44, 71.78, 79.14, 91.01, 93.17, 126.13, 127.79, 128.56, 129.22,
129.56, 130.26, 133.92, 137.99, 142.15, 162.14, 207.64. EI-MS (m/z,
relative intensity): 445 (Mþ, 5), 368 (15), 336 (12), 284 (11), 175
(100), 139 (22), 109 (28). HRMS calcd for C19H15ONS35Cl4 [Mþ]
444.9629; Found: 444.9636.
2-(3,4-Dichlorophenyl)-2-(phenylthio)penta-3,4-dienyl 2,2,2-
trichloroacetimidate (4d). Yield 87%; IR (film) 3340, 1953, 1664,
1469, 1380, 1302, 1086, 1029, 855, 824, 795, 751, 693 cmꢁ1 1H
;
NMR (CDCl3, 300 MHz)
d
¼ 4.40 (d, J ¼ 11.1 Hz, 1H), 4.52 (d, J ¼ 11.1
Hz, 1H), 4.58 (dd, J ¼ 11.1, 6.6 Hz, 1H), 4.85 (dd, J ¼ 11.1, 6.6 Hz, 1H),
4.3. General procedure for [RuCl2(p-cymene)]2-catalyzed reaction
of 2-aryl-2-(phenylthio)penta-3,4-dienyl 2,2,2-trichloroacetimidate
4a-i
5.57 (t, J ¼ 6.6 Hz, 1H), 7.26e7.48 (m, 7H), 7.72 (d, J ¼ 2.1 Hz, 1H),
8.25 (s, 1H); 13C NMR (CDCl3, 75 MHz)
d
¼ 56.08, 71.68, 79.35,
90.98, 93.04, 127.47, 128.67, 129.72, 129.83, 130.04, 130.48, 131.71,
132.10, 137.93, 140.49, 162.09, 207.69. EI-MS (m/z, relative inten-
sity): 479 (Mþ, 0.4), 370 (13), 318 (8), 209 (100), 175 (21), 139 (36),
109 (52). HRMS calcd for C19H14ONS35Cl5 [Mþ] 478.9239; Found:
478.9255.
Under
a nitrogen atmosphere, [RuCl2(p-cymene)]2 (0.025
mmol) and 2-aryl-2-(phenylthio)penta-3,4-dienyl 2,2,2-tri-
chloroacetimidate 4a-i were mixed in anhydrous DCE (5 mL) in a 25
mL round-bottomed flask. The reaction was continued at room
temperature [for some examples the reaction temperature was 60
ꢀC (oil-bath)] until completed as judged by TLC. Removal of the
solvent in vacuo gave a crude residue, which was purified by silica
gel column. Elution with petroleum ether/ethyl acetate (200:1)
afforded pure product of 5a i.
2-(4-Chloroheny)-2-(phenylthio)penta-3,4-dienyl
chloroacetimidate (4e). Yield 82%; IR (film) 3341, 1953, 1663, 1491,
1303, 1093, 1013, 827, 795, 750, 693 cmꢁ1 1H NMR (CDCl3, 300
MHz)
¼ 4.42 (d, J ¼ 11.1 Hz, 1H), 4.52e4.59 (m, 2H), 4.82 (dd, J ¼
11.1, 6.6 Hz,1H), 5.61 (t, J ¼ 6.6 Hz,1H), 7.26e7.44 (m, 7H), 7.52e7.57
(m, 2H), 8.22 (s, 1H); 13C NMR(CDCl3, 75 MHz)
79.08, 91.05, 93.33, 128.11, 128.56, 129.49, 130.44, 133.48, 137.92,
138.68, 162.19, 207.68. EI-MS (m/z, relative intensity): 445
(Mþ, 0.6), 336 (43), 272 (18), 193 (27), 175 (100), 139 (68), 109 (93).
HRMS calcd for C19H15ONS35Cl4 [Mþ] 444.9629; Found: 444.9632.
2,2,2-tri-
;
d
d
¼ 56.39, 71.91,
(Z)-2,2,2-Trichloro-N-(4-phenyl-1-(phenylthio)penta-2,4-dien-
2-yl)acetamide (5a). IR (film) 3357, 3058, 1724, 1644, 1494, 902,
811, 766, 744, 706, 692 cmꢁ1
;
1H NMR (CDCl3, 300 MHz)
d
¼ 4.18
(s, 2H), 5.21 (s, 1H), 5.52 (s, 1H), 5.64 (s, 1H), 6.96e6.99 (m, 2H),
7.21e7.50 (m, 8H), 7.94 (s, 1H); 13C NMR (CDCl3, 75 MHz)
d
¼
2-(4-Nitrophenyl)-2-(phenylthio)penta-3,4-dienyl
2,2,2-tri-
38.53, 92.46, 117.84, 120.21, 126.58, 127.49, 128.38, 128.76, 129.03,
132.40, 132.63, 134.01, 138.68, 142.23, 158.38. EI-MS (m/z, relative
intensity): 411 (Mþ, 22), 302 (79), 230 (26), 156 (44), 141 (100), 115
(56), 77 (44). HRMS calcd for C19H16O35Cl3SN [Mþ] 411.0018;
Found: 411.0020.
chloroacetimidate (4f). Yield 89%; IR (film) 3338, 1953, 1665, 1520,
1348, 1302,1085, 855, 833, 795, 750, 693 cmꢁ1; 1H NMR (CDCl3, 300
MHz)
d
¼ 4.51 (d, J ¼ 11.1 Hz, 1H), 4.62e4.68 (m, 2H), 4.89 (dd, J ¼
11.1, 6.6 Hz, 1H), 5.63 (t, J ¼ 6.6 Hz, 1H), 7.27e7.43 (m, 5H), 7.76 (dd, J
¼ 6.9, 2.1 Hz, 2H), 8.18 (dd, J ¼ 6.9, 2.1 Hz, 2H), 8.28 (s, 1H); 13C NMR
(Z)-2,2,2-Trichloro-N-(4-(4-bromophenyl)-1-(phenylthio)
penta-2,4-dien-2-yl)acetamide (5b). IR (film) 3365, 3073, 1725,
(CDCl3, 75 MHz)
d
¼ 56.48, 71.69,79.54, 90.89, 92.89, 123.06,128.75,
129.20, 129.72, 129.85, 137.86, 147.09, 147.61, 162.01, 207.79. EI-MS
(m/z, relative intensity): 456 (Mþ, 2), 379 (6), 347 (32), 295 (34), 218
(27), 186 (100), 139 (61), 109 (76), 44 (77). HRMS calcd for
C19H15O3N2S35Cl3 [Mþ] 455.9869; Found: 455.9859.
1645, 1487, 1071, 1009, 902, 834, 817, 744, 692 cmꢁ1 1H NMR
;
(CDCl3, 300 MHz)
d
¼ 4.14 (s, 2H), 5.23 (s, 1H), 5.54 (s, 1H), 5.59
(s, 1H), 6.80 (d, J ¼ 8.7 Hz, 2H), 7.33e7.49 (m, 7H), 7.93 (s, 1H); 13C
NMR (CDCl3, 75 MHz)
d
¼ 38.62, 92.51, 117.88, 119.96, 122.44,
2-(3-Methylphenyl)-2-(phenylthio)penta-3,4-dienyl 2,2,2-tri-
chloroacetimidate (4g). Yield 97%; IR (film) 3340, 1953, 1663, 1303,
1087, 998, 852, 831, 796, 752, 702, 693 cmꢁ1; 1H NMR (CDCl3, 300
127.57, 128.18, 129.09, 131.71, 132.60, 132.75, 133.91, 137.62,
141.29, 158.38. EI-MS (m/z, relative intensity): 491 (Mþ,32), 382
(100), 347 (11), 330 (13), 301 (14), 237 (31), 109 (46), 77 (26).
HRMS calcd for C19H15ONS35Cl739Br [Mþ] 488.9123; Found:
488.9125.
MHz)
d
¼ 2.34 (s, 3H), 4.40 (d, J ¼ 11.1 Hz, 1H), 4.48 (dd, J ¼ 11.1, 6.6
Hz,1H), 4.57 (d, J ¼ 11.1 Hz,1H), 4.79 (dd, J ¼ 11.1, 6.6 Hz,1H), 5.66 (t,
J ¼ 6.6 Hz,1H), 7.07e7.09 (m,1H), 7.19e7.47 (m, 8H), 8.18 (s, 1H); 13C
(Z)-2,2,2-Trichloro-N-(4-(4-methoxyphenyl)-1-(phenylthio)
penta-2,4-dien-2-yl)acetamide (5c). IR (film) 3356, 2958, 2836,
1723, 1644, 1606, 1509, 1250, 1178, 1031, 837, 814, 744, 692 cmꢁ1; 1H
NMR (CDCl3, 75 MHz)
d
¼ 21.52, 56.78, 71.96, 78.72, 91.17, 93.62,
124.90,127.90,128.35, 128.39, 128.69, 129.29, 130.90, 137.52,138.04,
139.86, 162.27, 207.57. EI-MS (m/z, relative intensity): 425 (Mþ, 0.6),
316 (14), 264 (8), 155 (100), 128 (10), 77 (6). HRMS calcd for
C20H18ONS35Cl3 [Mþ] 425.0175; Found: 425.0161.
NMR (CDCl3, 300 MHz)
d
¼ 3.79 (s, 3H), 4.18 (s, 2H), 5.11 (s,1H), 5.46
(s, 1H), 5.61 (s, 1H), 6.77 (dd, J ¼ 6.9, 2.1 Hz, 1H), 6.91 (dd, J ¼ 6.9, 2.1
Hz, 1H), 7.32e7.38 (m, 3H), 7.46e7.50 (m, 2H), 8.03 (s, 1H); 13C NMR
2-(3-Methoxyphenyl)-2-(phenylthio)penta-3,4-dienyl
2,2,2-
(CDCl3, 75 MHz)
d
¼ 38.44, 55.32, 92.58, 114.10, 116.01, 120.29,
trichloroacetimidate (4h). Yield 92%; IR (film) 3337, 1953, 1663,
127.42, 127.84, 129.01, 131.08, 132.45, 132.57, 134.17, 141.61, 158.37,
1291, 1260, 1086, 1039, 998, 853, 831, 796, 753, 694 cmꢁ1; 1H NMR
159.88. EI-MS (m/z, relative intensity): 441 (Mþ, 5), 332 (17), 296

122
L. Peng et al. / Journal of Organometallic Chemistry 696 (2011) 118e122
(35), 187 (100), 159 (47), 115 (28), 44 (43). HRMS calcd for
C20H18O325Cl3SN [Mþ] 441.0124; Found: 441.0127.
132.56, 132.60, 133.68, 134.63, 140.67, 141.18, 158.31. EI-MS (m/z,
relative intensity): 445 (Mþ, 20), 336 (100), 300 (20), 284 (19), 218
(19), 191 (41), 175 (78), 109 (70), 77 (39). HRMS calcd for
C19H15ONS35Cl4 [Mþ] 444.9629; Found: 444.9632.
(Z)-2,2,2-Trichloro-N-(4-(3, 4-dichlorophenyl)-1-(phenylthio)
penta-2,4-dien-2-yl)acetamide (5d). IR (film) 3367, 1726, 1645,
1496, 1136, 1029, 904, 817, 744, 691 cmꢁ1 1H NMR (CDCl3, 300
;
MHz)
d
¼ 4.11 (s, 2H), 5.27 (s,1H), 5.55 (s,1H), 5.60 (s,1H), 6.74 (dd, J
Acknowledgement
¼ 8.4, 2.1 Hz, 1H), 7.20e7.49 (m, 7H), 7.93 (s, 1H); 13C NMR (CDCl3,
75 MHz)
d
¼ 38.93, 92.48, 118.74, 119.76, 126.00, 127.80, 128.39,
The project was supported by the NSFC (Grant No.
21072009, 20832002, 20772003, 20821062), 973 Program (No.
2009CB825300).
129.20, 130.48, 132.40, 132.54, 132.82, 132.91, 133.74, 138.91, 140.49,
158.40. EI-MS (m/z, relative intensity): 479 (Mþ, 35), 370 (49), 334
(25), 318 (43), 298 (20), 264 (18), 225 (87), 162 (30), 109 (100), 77
(40), 36 (64). HRMS calcd for C19H14ONS35Cl5 [Mþ] 478.9239;
Found: 478.9235.
Appendix A. Supplementary material
(Z)-2,2,2-Trichloro-N-(4-(4-chlorophenyl)-1-(phenylthio)
penta-2,4-dien-2-yl)acetamide (5e). IR (film) 3362, 3061, 1725,
1645, 1491, 1013, 902, 837, 814, 744, 692 cmꢁ1; 1H NMR (CDCl3, 300
CCDC-783984 contains the supplementary crystallographic data
for 5a. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via http://www.ccdc.cam.ac.
uk/data_request/cif.
MHz)
J ¼ 6.6, 1.8 Hz, 2H), 7.20 (dd, J ¼ 6.6, 1.8 Hz, 2H), 7.34e7.40 (m, 3H),
7.46e7.49 (m, 2H), 7.94 (s, 1H); 13C NMR (CDCl3, 75 MHz)
d
¼ 4.15 (s, 2H), 5.23 (s, 1H), 5.54 (s, 1H), 5.60 (s, 1H), 6.87 (dd,
d
¼
References
38.63, 92.53, 117.81, 120.02, 127.57, 127.88, 128.76, 129.10, 132.63,
132.76, 133.95, 134.29, 137.17, 141.23, 158.40. EI-MS (m/z, relative
intensity): 445 (Mþ, 36), 336 (63), 300 (24), 284 (37), 191 (100), 128
(38), 109(45), 77 (31). HRMS calcd for C19H15ONS35Cl4 [Mþ]
444.9629; Found: 444.9639.
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(Z)-2,2,2-Trichloro-N-(4-(4-nitrophenyl)-1-(phenylthio)penta-
2,4-dien-2-yl)acetamide (5f). IR (film) 3309, 1703, 1649, 1594, 1517,
1492, 1343, 907, 856, 742, 734 cmꢁ1; 1H NMR (CDCl3, 300 MHz)
d
¼
4.12 (s, 2H), 5.42 (s, 1H), 5.66 (s, 1H), 5.71 (s, 1H), 7.07 (d, J ¼ 8.7 Hz,
2H), 7.39e7.52 (m, 5H), 7.96 (s,1H), 8.06 (d, J ¼ 8.7 Hz, 2H); 13C NMR
(CDCl3, 75 MHz)
d
¼ 39.04, 92.40, 119.83, 120.24, 123.66, 127.37,
127.80, 129.24, 132.67, 132.97, 133.55, 140.75, 145.13, 147.41, 158.40.
EI-MS (m/z, relative intensity): 456 (Mþ, 30), 347 (98), 311 (37), 295
(31), 202 (100), 127 (38), 109 (47), 77 (26), 36 (73). HRMS calcd for
C19H15O3N2S35Cl3 [Mþ] 455.9869; Found: 455.9859.
(Z)-2,2,2-Trichloro-N-(4-(3-methylphenyl)-1-(phenylthio)
penta-2,4-dien-2-yl)acetamide (5g). IR (film) 3346, 1723, 1642,
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15016e15017.
1493, 902, 816, 768, 744, 691 cmꢁ1; 1H NMR (CDCl3, 300 MHz)
d
¼
2.29 (s, 3H), 4.17 (s, 2H), 5.19 (s,1H), 5.46 (s, 1H), 5.66 (s, 1H), 6.76 (d,
J ¼ 7.2 Hz, 1H), 6.92 (s, 1H), 7.01e7.17 (m, 2H), 7.21e7.38 (m, 3H),
7.42e7.49 (m, 2H), 7.94 (s, 1H); 13C NMR(CDCl3, 75 MHz)
d
¼ 21.33,
38.39, 92.42, 118.03, 120.29, 123.84, 127.16, 127.40, 128.78, 128.97,
129.17, 132.10, 132.36, 134.07, 138.53, 138.76, 142.43, 158.34. EI-MS
(m/z, relative intensity): 425 (Mþ, 34), 316 (100), 264 (48), 244 (43),
171 (77), 155 (78), 128 (52), 109 (44), 91 (38). HRMS calcd for
C20H18ONS35Cl3 [Mþ] 425.0175; Found: 425.0182.
(Z)-2,2,2-Trichloro-N-(4-(3-methoxyphenyl)-1-(phenylthio)
penta-2,4-dien-2-yl)acetamide (5h). IR (film) 3345, 2937, 1722,
1643, 1576,1489, 1230, 1046, 905, 815, 769, 737, 692 cmꢁ1; 1H NMR
(CDCl3, 300 MHz)
d
¼ 3.75 (s, 1H), 4.17 (s, 2H), 5.20 (s, 1H), 5.48
(s, 1H), 5.68 (s, 1H), 6.51e6.54 (m, 1H), 6.53 (d, J ¼ 7.8 Hz, 1H),
6.72e6.74 (m, 1H), 6.81e6.84 (m, 1H), 7.17 (t, J ¼ 7.8 Hz, 1H),
7.23e7.37 (m, 3H), 7.45e7.48 (m, 2H), 7.93 (s, 1H); 13C NMR
(CDCl3,75 MHz)
d
¼ 38.40, 55.19, 92.39, 112.20, 113.89, 118.41,
119.06, 120.28, 127.39, 128.98, 129.91, 132.17, 132.25, 134.09, 140.22,
142.25, 158.39, 159.96. EI-MS (m/z, relative intensity): 441 (Mþ, 12),
332 (65), 280 (33), 260 (34), 187 (61), 171 (100), 128 (32), 109 (51),
77 (46). HRMS calcd for C20H18O2NS35Cl3 [Mþ] 441.0124; Found:
441.0139.
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482e485.
(Z)-2,2,2-Trichloro-N-(4-(3-chlorophenyl)-1-(phenylthio)
penta-2,4-dien-2-yl)acetamide (5i). IR (film) 3365, 1725, 1644,
1495, 902, 813, 793, 769, 745, 692 cmꢁ1; 1H NMR (CDCl3, 300 MHz)
d
¼ 4.13 (s, 2H), 5.25 (s, 1H), 5.53 (s, 1H), 5.61 (s, 1H), 6.80e6.83 (m,
1H), 7.09e7.49 (m, 8H), 7.92 (s, 1H); 13C NMR (CDCl3, 75 MHz)
38.76, 118.76, 119.76, 124.85, 126.56, 127.72, 128.35, 129.11, 129.91,
d
¼