One-pot multistep synthesis of trisubstituted alkenes from N -tosylhydrazones and alcohols

Article abstract of DOI:10.1055/s-0034-1378231

A one-pot procedure for the synthesis of trisubstituted alkenes from N-tosylhydrazones and alcohols is reported. This procedure combines the aerobic oxidation reaction and Wittig reaction in one pot, which avoids using of environmentally toxic oxidants and isolation of the intermediates. The simple procedure makes it very attractive for the synthesis of trisubstituted alkenes when alcohols are used as starting materials. A variety of trisubstituted alkenes as well as trifluoromethyl-substituted alkenes were obtained in moderate to good yields (up to 84%) with good E-selectivity (up to 99%). Georg Thieme Verlag Stuttgart.New York.

Full text of DOI:10.1055/s-0034-1378231

PAPER
▌2353
pOapnere-Pot Multistep Synthesis of Trisubstituted Alkenes from N-Tosylhydrazones
and Alcohols
One-Pot Multistep Synthesis of Trisubstituted Alkenes
Qiang Sha, Yunyang Wei*
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China
Fax +86(25)84317078; E-mail: ywei@mail.njust.edu.cn
Received: 17.03.2014; Accepted after revision: 06.05.2014
chloride (ClFeTPP) catalyzed Wittig reaction of alde-
Abstract: A one-pot procedure for the synthesis of trisubstituted
hyde-derived tosylhydrazones with aldehydes. The
alkenes from N-tosylhydrazones and alcohols is reported. This pro-
alkenes were formed in high yields and high E-selectivity
cedure combines the aerobic oxidation reaction and Wittig reaction
in one pot, which avoids using of environmentally toxic oxidants
(Scheme 1). In 2004, Zhu and co-workers7 described a
and isolation of the intermediates. The simple procedure makes it straightforward method for the synthesis of trans-penta-
very attractive for the synthesis of trisubstituted alkenes when alco-
hols are used as starting materials. A variety of trisubstituted
alkenes as well as trifluoromethyl-substituted alkenes were ob-
catalyst (Scheme 1). But the two reported methods can
tained in moderate to good yields (up to 84%) with good E-selectiv-
ity (up to 99%).
fluorophenyl-containing alkenes from aldehydes in mod-
erate to good yields using rhodium(II) acetate as the
only be used to synthesize disubstituted alkenes. Recently
(Scheme 1), we reported the copper(II) acetylacetonate
Key words: hydrazones, alkenes, olefination, Wittig reaction, di-
catalyzed Wittig reaction of ketone-derived tosylhydra-
azo compounds
zones with aldehydes8 and copper(I) iodide catalyzed
Wittig reaction of tosylhydrazones with trifluoromethyl
ketones,9 from which various trisubstituted alkenes were
Carbon–carbon double bonds exist widely in natural prod-
obtained in good yields and good E-selectivity.
ucts, pharmaceuticals, agricultural chemicals, and organic
However, the starting materials of all these procedures are
materials. Moreover, they occupy a pivotal position in or-
limited to carbonyl compounds, the direct use of alcohols
ganic chemistry due to their facile transformation in many
as starting substance has not been developed. For exam-
kinds of organic reactions. Many methods have been de-
ple, in our reported copper(I) iodide catalyzed Wittig re-
veloped for their synthesis. The Wittig reaction, together
action of tosylhydrazones with trifluoromethyl ketones,9
with the Horner–Wadsworth–Emmons reaction and the
the trifluoromethyl ketones were prepared from the addi-
Schlosser modification, is one of the most commonly used
methods.1 However, the stereoselective synthesis of tri-
substituted olefins is a long-standing challenge in organic
chemistry and, since the trisubstituted alkene motif is
ubiquitous in organic chemistry, it is highly desirable to
develop new and expeditious approaches to these com-
pounds.2
tion of trimethyl(trifluoromethyl)silane to aldehydes, fol-
lowed by oxidation using Dess–Martin reagent. A large
excess of the Dess–Martin reagent was used and we need
to isolate the trifluoromethyl ketones in a pure form. The
whole procedure was cumbersome, uneconomical, and
environmentally unconscientious.
One-pot multistep processes10 have attracted much atten-
tion in recent years due to their two obvious advantages.
Firstly, they can minimize the use of the amount of sol-
vent and reagents needed for the reactions and purifica-
tions. Secondly, there is no need to isolate the potentially
sensitive intermediates. This encouraged us to develop a
one-pot multistep procedure for the synthesis of trisubsti-
tuted alkenes from N-tosylhydrazones and alcohols. In a
continuation of our work on the development of new ap-
plications of N-tosylhydrazones,8,9,11 herein, we report our
successful attempt to achieve this goal (Scheme 1).
Diazo compounds emerged as a new type of Wittig reac-
tion substrates from the end of the 1980s, and they have
been used extensively in Wittig reaction in recent years.3
However diazo compounds without an electron-with-
drawing group are usually unstable and thus difficult to
handle, which significantly limits the scope of this type of
reaction. N-Tosylhydrazones, which could be utilized as
safe diazo precursors, have been used in organic synthesis
for a long time.4 Nowadays, they are widely used in cross-
coupling reactions and X–H (X = C, O, S, N, P) insertion
reactions.5
Copper-catalyzed aerobic oxidation of alcohols into car-
bonyl compounds is a well-developed process.12 Markó et
al.13 have developed an efficient catalytic oxidation of al-
cohols to aldehydes and ketones using catalytic amounts
of copper(I) chloride/1,10-phenanthroline and molecular
oxygen. We attempted to combine this method with the
Wittig reaction in one pot. Phenylmethanol and acetophe-
none-derived tosylhydrazones were chosen as model sub-
strates. Conditions similar to the literature13 were used for
The Wittig reaction of N-tosylhydrazones with carbonyl
compounds is meaningful because it provides a new way
to couple two different carbonyl groups, forming olefins
directly. In 2003, Aggarwal and co-workers6 reported
the (5,10,15,20-tetraphenyl-21H,23H-porphine)iron(III)
SYNTHESIS 2014, 46, 2353–2361
Advanced online publication: 10.06.2014
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0034-1378231; Art ID: ss-2014-h0185-op
© Georg Thieme Verlag Stuttgart · New York

2354
Q. Sha, Y. Wei
PAPER
NNHTs
H
previous work
R1
ClFeTPP
P(OMe)3
R1CHO
Aggarwal 2003
+
R2
R2
TsNHNH2
Rh2(OAc)4
Ar
Zhu 2004
C6F5CHO
C6F5
AsPh3
ArCHO
our previous work
NNHTs
R2
O
R2
R3
Cu(acac)2, Ph3P, LiOt-Bu
H
R1
R3
R1
toluene, 90 °C, N2
R2
CF3
NNHTs
R2
O
CuI, Ph3P, LiOt-Bu
CF3
R1
R3
toluene, 90 °C, N2
R1
R3
this work
R2
NNHTs
R3
O
OH
R1
R1
R1
R2
R3
CuCl
O2
or
or
F3C
or
CF3
CF3
OH
CuI, Ph3P, N2
O
R2
R1
R1
R1
Scheme 1 Wittig reaction of in situ generated diazo compounds with carbonyl compounds
this one-pot transformation and the corresponding prod- Encouraged by this result, a variety of copper catalysts
uct 3a was obtained in only 10% yield (Table 1, entry 1). and bases were then screened, (entries 4–11), which indi-
This indicated that copper(I) chloride/1,10-phenanthro- cated that copper(I) iodide and lithium tert-butoxide were
line was not suitable for the Wittig reaction. Then we add- the best (entry 4). Using copper(I) iodide or lithium tert-
ed copper(II) acetylacetonate and potassium carbonate in butoxide separately in the second step, the desired product
the second step, the yield increased slightly (entry 2). 3a was obtained in very low yield (entries 12 and 13),
With lithium tert-butoxide instead of potassium carbonate which reveals that both copper(I) iodide and lithium tert-
as the base, we were delighted to find the product 3a was butoxide are essential to the overall efficiency of this
obtained in 55% yield with 89% E-selectivity (entry 3). transformation.
Table 1 Model Reaction Phenylmethanol with Acetophenone-Derived Tosylhydrazone Using Different Reaction Conditionsa
CuCl/Phen (5 mol%),
EtO2CNH–NHCO2Et (25 mol%)
acetophenone-derived
N-tosylhydrazone
OH
O
K2CO3 (2 equiv), O2,
toluene, 90 °C, 1 h
catalyst, Ph3P, base,
N2
, 90 °C, 10 h
1
3a
Entry
Catalyst
Base
Yieldb (%)
Ratioc E/Z
1
2
3
4
5
6
–
–
10
21
55
67
17
12
87:13
89:11
89:11
88:12
89:11
89:11
Cu(acac)2
Cu(acac)2
CuI
K2CO3
LiOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
CuCl
CuCl2
Synthesis 2014, 46, 2353–2361
© Georg Thieme Verlag Stuttgart · New York

PAPER
One-Pot Multistep Synthesis of Trisubstituted Alkenes
2355
Table 1 Model Reaction Phenylmethanol with Acetophenone-Derived Tosylhydrazone Using Different Reaction Conditionsa (continued)
CuCl/Phen (5 mol%),
EtO2CNH–NHCO2Et (25 mol%)
acetophenone-derived
N-tosylhydrazone
OH
O
K2CO3 (2 equiv), O2,
toluene, 90 °C, 1 h
catalyst, Ph3P, base,
N2
, 90 °C, 10 h
1
3a
Entry
Catalyst
Base
Yieldb (%)
Ratioc E/Z
7
8
Cu(OAc)2
LiOt-Bu
LiOt-Bu
NaOt-Bu
KOt-Bu
DBU
47
44
40
61
11
13
11
88:12
89:11
89:11
89:11
89:11
89:11
89:11
Cu(MeCN)4PF6
9
CuI
CuI
CuI
CuI
–
10
11
12
13
–
LiOt-Bu
a Reaction conditions: 1 (0.6 mmol), CuCl (0.025 mmol), Phen (0.025 mmol), EtO2CNH-NHCO2Et (0.125 mmol), K2CO3 (1 mmol), toluene
(5 mL), O2 atmosphere, 90 °C, 1 h; acetophenone-derived tosylhydrazone (0.5 mmol), catalyst (0.05 mmol), Ph3P (0.6 mmol), base (0.7 mmol),
N2 atmosphere, 90 °C, 10 h.
b Isolated yield, yield of Z + E.
c Determined by GC.
With the optimized conditions in hand, the scope of this none-derived tosylhydrazones were tested, and the corre-
one-pot multistep reaction was investigated (Scheme 2). sponding products 3b,c were obtained in moderate yields
1-(4-Chlorophenyl)ethanone- and 1-(thiophen-2-yl)etha- and good E-selectivity. 4-Chlorobenzaldehyde was also
i. CuCl/Phen (5 mol%), EtO2CNH–NHCO2Et (25 mol%)
K2CO3 (2 equiv), O2, toluene, 90 °C, 1–3 h
R2
OH
R1
R1
ii. ketone-derived N-tosylhydrazones
CuI, Ph3P, LiOt-Bu, N2, 90 °C, 10 h
R3
1
3
Cl
S
Cl
3a
3b
3c
3d
67%, E/Z = 88:12
57%, E/Z = 81:19
58%, E/Z = 84:16
66%, E/Z = 89:11
Br
F3C
3e
3f
3g
3h
55%, E/Z = 99:1
52%, E/Z = 99:1
56%, E/Z = 99:1
40%, E/Z = 99:1
S
3i
3j
3k
3l
51%, E/Z = 99:1
59%, E/Z = 99:1
47%, E/Z = 99:1
0%
Scheme 2 Copper-catalyzed oxidation–olefination tandem process of primary alcohols. Reagents and conditions: 1 (0.6 mmol), CuCl (0.025
mmol), Phen (0.025 mmol), EtO2CNH-NHCO2Et (0.125 mmol), K2CO3 (1 mmol), toluene (5 mL), O2 atmosphere, 90 °C, 1–3 h; ketone-derived
tosylhydrazone (0.5 mmol), CuI (0.05 mmol), Ph3P (0.6 mmol), LiOt-Bu (0.7 mmol), N2 atmosphere, 90 °C, 10 h. Isolated yield of Z + E, ratio
E/Z (1H NMR).
© Georg Thieme Verlag Stuttgart · New York
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Q. Sha, Y. Wei
PAPER
tested and 3d was obtained in 66% yield with 89% E-se- due to their highly desirable physical, physiological, and
lectivity. Then propiophenone and 1-phenylbutan-1-one pharmacokinetic properties. However, trifluoromethyl-
(with longer alkyl chains) derived tosylhydrazones were bearing compounds are absent in the natural world. There-
used, we were delighted to find that the products 3e,f were fore, it is highly important to develop general and practi-
obtained with up to 99% E-selectivity. Then various alde- cal methods to introduce the trifluoromethyl group into
hydes, including 4-bromobenzaldehyde, 4-(trifluorometh- organic molecules.14 The scope of the one-pot multistep
yl)benzaldehyde, thiophene-2-carbaldehyde, and 1- reaction of N-tosylhydrazones with trifluoromethyl-sub-
naphthaldehyde, were used to react with propiophenone- stituted carbinols was also studied. We investigated the
derived tosylhydrazone, the products 3g–j were all ob- scope of the process with respect to the N-tosylhydrazone
tained in moderate yields with high E-selectivity. When substrates first (Scheme 3). A variety of N-tosylhydra-
ortho-position-blocked aldehyde 2-methylbenzaldehyde zones derived from aromatic aldehydes were allowed to
was used, 3k was also formed with high E-selectivity react with 2,2,2-trifluoro-1-phenylethanol under the opti-
(99%). An attempt to use an aliphatic ketone derived to- mized reaction conditions. The N-tosylhydrazone pos-
sylhydrazone, cyclohexanone-derived tosylhydrazone, as sessing an electron-donating group (methyl) gives
the substrate led to no desired product 3l.
product 4b in 73% yield with 89% E-selectivity. N-Tosyl-
hydrazones possessing a weak electron-withdrawing
group (bromo, chloro, cyano), no matter on the ortho,
Trifluoromethylated compounds are important synthetic
targets in the pharmaceutical and agrochemical industries
CF3
i. CuCl/Phen (5 mol%), EtO2CNH–NHCO2Et (25 mol%)
K2CO3 (2 equiv), O2, toluene, 90 °C, 2–4 h
OH
CF3
ii. aldehyde-derived N-tosylhydrazones
CuI, Ph3P, LiOt-Bu, N2, 90 °C, 10 h
R1
R1
R2
4
2
CF3
CF3
CF3
CF3
Br
Br
4a
4b
4c
4d
80%, E/Z = 92:8
73%, E/Z = 89:11
76%, E/Z = 90:10
54%, E/Z = 92:8
CF3
CF3
CF3
CF3
Br
O
Br
NC
4e
4f
4g
4h
63%, E/Z = 92:8
60%, E/Z = 90:10
30%, E/Z = 88:12
70%, E/Z = 85:15
CF3
CF3
CF3
CF3
Br
Br
Cl
O
4i
4j
4k
4l
81%, E/Z = 92:8
70%, E/Z =89:11
71%, E/Z = 92:8
57%, E/Z = 83:17
CF3
CF3
CF3
S
4m
4n
4o
84%, E/Z = 89:11
74%, Z/E =93:7
0%
Scheme 3 Copper-catalyzed oxidation–olefination tandem process of trifluoromethyl-substituted carbinols. Reagents and conditions: 2 (0.6
mmol), CuCl (0.025 mmol), Phen (0.025 mmol), EtO2CNH-NHCO2Et (0.125 mmol), K2CO3 (1 mmol), toluene (5 mL), O2 atmosphere, 90 °C,
2–4 h; aldehyde-derived tosylhydrazone (0.5 mmol), CuI (0.05 mmol), Ph3P (0.6 mmol), LiOt-Bu (0.7 mmol), N2 atmosphere, 90 °C, 10 h.
Isolated yield of Z + E, ratio E/Z (19F NMR or GC).
Synthesis 2014, 46, 2353–2361
© Georg Thieme Verlag Stuttgart · New York

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One-Pot Multistep Synthesis of Trisubstituted Alkenes
2357
The solvent was removed under reduced pressure and the crude al-
kene was purified by flash chromatography (silica gel).
meta, or the para position, all give the products 4c–e,g in
moderate to good yields with good E-selectivity. Furan-2-
carbaldehyde derived tosylhydrazone was also investigat-
ed, the product 4f was obtained in 60% yield with 90% E-
selectivity.
(E)-Prop-1-ene-1,2-diyldibenzene (3a)17
Colorless liquid; yield (Z/E): 65.0 mg (67%); ratio Z/E 12:88 (1H
NMR); Rf = 0.41 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.57–7.55 (m, 2 H),
7.42–7.39 (m, 6 H), 7.33–7.26 (m, 2 H), 6.87 (d, J = 1 Hz, 1 H), 2.32
(d, J = 1 Hz, 3 H).
Then the effects of substituents attached to the trifluoro-
methyl-substituted carbinols in the reaction were investi-
gated. It was found that electron-withdrawing groups
(bromo, chloro), no matter in the ortho, meta, or the para
position, were tolerated in the reaction; the products 4h–k
were obtained in good yields with good E-selectivity. Tri-
fluoromethyl-substituted carbinols with electron-donating
groups (methyl, methoxy) on the aromatic ring were also
tolerated and gave 4l,m. 2,2,2-Trifluoro-1-(thiophen-2-
yl)ethanol was also tested, and the desired product 4n was
obtained in 74% yield with 93% Z-selectivity. However,
when an aliphatic aldehyde butyraldehyde-derived tosyl-
hydrazone was used, no desired product was obtained.
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.51 (s, 0.14 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 144.06, 138.45,
137.51, 129.23, 128.40, 128.25, 127.79, 127.26, 126.54, 126.09,
17.55.
(E)-1-Chloro-4-(1-phenylprop-1-en-2-yl)benzene (3b)18
Colorless liquid; yield (Z/E): 65.0 mg (57%); ratio Z/E 19:81 (1H
NMR); Rf = 0.41 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.50 (d, J = 8.5 Hz, 2
H), 7.44–7.38 (m, 6 H), 7.32–7.29 (m, 1 H), 6.88 (s, 1 H), 2.31 (s, 3
H).
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.56 (s, 0.23 H).
In conclusion, a one-pot multistep procedure for the syn-
thesis of trisubstituted alkenes from tosylhydrazones and
alcohols was developed. Compared to the previous report
methods, this procedure avoids the separate oxidation of
alcohols, which make it economically sustainable and en-
vironmentally conscientious. The present procedure pro-
vides an attractive alternative method for the synthesis of
trisubstituted alkenes when alcohols are used as starting
materials. A variety of trisubstituted alkenes as well as tri-
fluoromethyl-substituted alkenes were obtained in moder-
ate to good yields (up to 84%) with good E-selectivity (up
to 99%).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 142.43, 138.11,
136.30, 133.02, 129.22, 128.51, 128.31, 128.23, 127.36, 126.76,
17.46.
(E)-2-(1-Phenylprop-1-en-2-yl)thiophene (3c)19
Colorless liquid; yield (Z/E): 58.0 mg (58%); ratio Z/E 16:84 (1H
NMR); Rf = 0.41 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.43–7.41 (m, 4 H),
7.32–7.30 (m, 1 H), 7.25 (d, J = 5 Hz, 1 H), 7.20 (d, J = 3.5 Hz, 1
H), 7.09 (s, 1 H), 7.37 (s, 3 H).
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.60 (s, 0.19 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 148.04, 137.70,
131.11, 129.34, 128.30, 127.57, 126.72, 126.21, 124.05, 123.43,
17.46.
Toluene was distilled from Na prior to use. N-Tosylhydrazones
were prepared by condensation of carbonyl compounds with
4-methylbenzenesulfonohydrazide,15 Trifluoromethyl-substituted
carbinols were prepared from the addition of trifluoro(trimethysi-
lyl)methane on aldehydes.16 Other chemicals (AR grade) were ob-
tained from commercial sources and were used without further
purification. Petroleum ether (PE) refers to the fraction boiling in
the 60–90 °C range. The progress of the reactions was monitored by
TLC (silica gel, Polygram SILG/UV 254 plates). Column chroma-
tography was performed on Silicycle silica gel (200–300 mesh).
Melting points were obtained using a Yamato melting point appara-
tus Model MP-21 and are uncorrected. 1H, 13C, and 19F NMR spec-
tra were obtained using a Bruker DRX 500 (500 MHz) spectrometer
in CDCl3 with TMS as the internal standard. MS spectra were re-
corded using a Thermo Scientific TSQ Quantum analyzer. The
known compounds were identified by comparison of their physical
and spectral data with those reported in the literature.
(E)-1-Chloro-4-(2-phenylprop-1-enyl)benzene (3d)18
Colorless liquid; yield (Z/E): 75.2 mg (66%); ratio Z/E 11:89 (1H
NMR); Rf = 0.41 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.53 (d, J = 8 Hz, 2 H),
7.41–7.37 (m, 4 H), 7.35–7.27 (m, 3 H), 6.79 (s, 1 H), 2.28 (s, 3 H).
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.43 (s, 0.12 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 143.69, 138.20,
136.79, 132.19, 130.46, 128.42, 128.38, 127.43, 126.50, 126.02,
17.54.
(E)-But-1-ene-1,2-diyldibenzene (3e)20
Colorless liquid; yield (Z/E): 57.2 mg (55%); ratio Z/E 1:99 (1H
NMR); Rf = 0.46 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.57 (d, J = 8 Hz, 2 H),
7.48–7.43 (m, 6 H), 7.40–7.33 (m, 2 H), 6.81 (s, 1 H), 2.85 (q, J =
7 Hz, 2 H), 1.18 (t, J = 7 Hz, 3 H).
Catalytic One-Pot Oxidation-Olefination; General Procedure
CuCl (2.5 mg, 0.025 mmol) and 1,10-phenanthroline (4.5 mg, 0.025
mmol) were placed in a vessel and toluene (5 mL) was added. The
resulting solution was stirred at r.t. until the solution became green
and clear (5 to 10 min). Then K2CO3 (138 mg, 1 mmol) and
EtO2CNH-NHCO2Et (18.5 mg, 0.125 mmol) were added. The solu-
tion was stirred at r.t. for another 10 min. Alcohol (0.60 mmol) was
added, the mixture was heated at 90 °C under an O2 atmosphere (O2
balloon) until the reaction was completed (TLC analysis). The ves-
sel was backfilled with N2, Ph3P (157.2 mg, 0.6 mmol), CuI (9.5
mg, 0.05 mmol), LiOt-Bu (56.0 mg, 0.7 mmol), and tosylhydrazone
(0.5 mmol) were added. The solution was stirred at 90 °C for 10 h.
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.49 (s, 0.01 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 144.61, 142.85,
138.45, 128.86, 128.48, 128.38, 127.75, 127.29, 126.66, 23.41,
13.63.
(E)-Pent-1-ene-1,2-diyldibenzene (3f)21
Colorless liquid; yield (Z/E): 57.7 mg (52%); ratio Z/E 1:99 (1H
NMR); Rf = 0.49 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.48 (d, J = 8 Hz, 2 H),
7.40–7.34 (m, 6 H), 7.32–7.26 (m, 2 H), 6.73 (s, 1 H), 2.71 (t, J =
8 5Hz, 2 H), 1.54–1.46 (m, 2 H), 0.92 (d, J = 7.5 Hz, 3 H).
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.46 (s, 0.01 H).
© Georg Thieme Verlag Stuttgart · New York
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Q. Sha, Y. Wei
PAPER
13C NMR (125 MHz, CDCl3, E-isomer): δ = 143.29, 143.22,
138.40, 128.83, 128.36, 128.27, 127.14, 126.67, 126.52, 32.23,
21.99, 14.09.
13C NMR (125 MHz, CDCl3, E-isomer): δ = 144.19, 142.40,
137.75, 136.76, 129.82, 128.77, 128.37, 127.37, 127.14, 126.89,
126.76, 125.51, 23.25, 20.11, 13.49.
(E)-1-Bromo-4-(2-phenylbut-1-enyl)benzene (3g)
Colorless liquid; yield (Z/E): 80.1 mg (56%); ratio Z/E 1:99 (1H
NMR); Rf = 0.49 (PE).
(E)-(3,3,3-Trifluoroprop-1-ene-1,2-diyl)dibenzene (4a)23
Colorless liquid; yield (Z/E): 99.2 mg (80%); ratio Z/E 8:92 (1H
NMR); Rf = 0.69 (PE).
IR (film): 1651, 1466, 1378, 1155, 1011, 696 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.44–7.43 (m, 3 H),
7.36–7.34 (m, 2 H), 7.28 (s, 1 H), 7.24 (d, J = 7 Hz, 1 H), 7.21–7.18
(m, 2 H), 7.05 (d, J = 7.5 Hz, 2 H).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.53–7.49 (m, 4 H),
7.43–7.40 (m, 2 H), 7.35 (d, J = 7.5 Hz, 1 H), 7.23 (d, J = 8 Hz, 2
H), 6.64 (s, 1 H), 2.75 (q, J = 7.5 Hz, 2 H), 1.10 (t, J = 7.5 Hz, 3 H).
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 7.10 (s, 0.09 H).
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.39 (s, 0.01 H).
(E)-1-Methyl-4-(3,3,3-trifluoro-2-phenylprop-1-enyl)benzene
(4b)23
13C NMR (125 MHz, CDCl3, E-isomer): δ = 145.38, 142.44,
137.25, 131.45, 130.44, 128.49, 127.46, 126.68, 126.43, 120.46,
23.37, 13.50.
Colorless liquid; yield (Z/E): 95.6 mg (73%); ratio Z/E 11:89 (1H
NMR); Rf = 0.66 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.45–7.44 (m, 3 H),
7.37–7.36 (m, 2 H), 7.25 (s, 1 H), 7.03–7.01 (m, 2 H), 6.96–6.95 (m,
2 H), 2.31 (s, 3 H).
MS (EI, 70 eV): m/z = 286.
HRMS (EI, 70 eV): m/z [M]+ calcd for C16H15Br: 286.0357; found:
286.0360.
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 7.10 (s, 0.12 H).
(E)-1-(2-Phenylbut-1-enyl)-4-(trifluoromethyl)benzene (3h)22
Colorless liquid; yield (Z/E): 55.2 mg (40%); ratio Z/E 1:99 (1H
NMR); Rf = 0.49 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.63 (d, J = 8 Hz, 2 H),
7.48 (d, J = 7.5 Hz, 2 H), 7.44–7.38 (m, 4 H), 7.35–7.32 (m, 1 H),
6.69 (s, 1 H), 2.73 (q, J = 7.5 Hz, 2 H), 1.07 (t, J = 7.5 Hz, 3 H).
(E)-1-Bromo-2-(3,3,3-trifluoro-2-phenylprop-1-enyl)benzene
(4c)
Colorless liquid; yield (Z/E): 85.9 mg (76%); ratio Z/E 10:90 (19F
NMR); Rf = 0.70 (PE).
IR (film) :1651, 1463, 1379, 1295, 1129, 962, 724 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.58 (dd, J = 8 Hz, 1.5
Hz, 1 H), 7.48 (d, J = 1.5 Hz, 1 H), 7.33–7.32 (m, 3 H), 7.28–7.26
(m, 2 H), 7.06 (td, J = 7.5 Hz, 1.5 Hz, 1 H), 6.97 (td, J = 7.5 Hz, 1
Hz, 1 H), 6.81 (dd, J = 8 Hz, 1.5 Hz, 1 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 134.43, 133.08 (J = 5
Hz), 133.04, 132.71, 131.93, 131.17, 129.88, 128.83, 128.69,
126.92, 124.83.
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.44 (s, 0.01 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 146.59, 142.13,
141.92, 128.98, 128.52, 128.35, 127.66, 126.71, 126.24, 125.24,
23.38, 13.49.
(E)-2-(2-Phenylbut-1-enyl)thiophene (3i)22
Colorless liquid; yield (Z/E): 54.6 mg (51%); ratio Z/E 1:99 (1H
NMR); Rf = 0.35 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.49 (d, J = 7.5 Hz, 2
H), 7.39–7.36 (m, 2 H), 7.31–7.29 (m, 2 H), 7.09–7.05 (m, 2 H),
6.85 (s, 1 H), 2.93 (q, J = 7.5 Hz, 2 H), 1.17 (t, J = 7.5 Hz, 3 H).
19F NMR (470 MHz, CDCl3): δ = –65.41 (s, 0.90 F, E-isomer),
–56.75 (s, 0.10 F, Z-isomer).
MS (EI, 70 eV): m/z = 326.
HRMS (EI, 70 eV): m/z [M]+ calcd for C15H10BrF3: 325.9918;
found: 325.9921.
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.62 (s, 0.01 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 142.75, 142.61,
140.91, 128.44, 127.69, 127.23, 126.99, 126.42, 125.01, 120.37,
24.57, 12.99.
(E)-1-Bromo-3-(3,3,3-trifluoro-2-phenylprop-1-enyl)benzene
(4d)
Colorless liquid; yield (Z/E): 61.0 mg (54%); ratio Z/E 8:92 (19F
NMR); Rf = 0.70 (PE).
(E)-1-(2-Phenylbut-1-enyl)naphthalene (3j)22
Colorless liquid; yield (Z/E): 76.1 mg (59%); ratio Z/E 1:99 (1H
NMR); Rf = 0.28 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 8.04 (dd, J = 7 Hz, 1.5
Hz, 1 H), 7.89 (dd, J = 7 Hz, 2 Hz, 1 H), 7.82 (d, J = 8 Hz, 1 H), 7.60
(d, J = 7.5 Hz, 2 H), 7.52–7.49 (m, 3 H), 7.46–7.43 (m, 3 H), 7.37–
7.34 (m, 1 H), 7.12 (s, 1 H), 2.61 (q, J = 7 Hz, 2 H), 0.98 (t, J = 7.5
Hz, 3 H).
IR (film): 1592, 1469, 1293, 1158, 960, 668 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.43–7.40 (m, 3 H),
7.35–7.33 (m, 1 H), 7.30–7.28 (m, 2 H), 7.18–7.17 (m, 2 H), 7.02 (t,
J = 7.5 Hz, 1 H), 6.91 (d, J = 8 Hz, 1 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 135.66, 132.99,
131.81, 131.75, 131.70, 129.73, 129.12, 128.44, 122.34.
19F NMR (470 MHz, CDCl3): δ = –66.08 (s, 0.92 F, E-isomer),
–56.30 (s, 0.08 F, Z-isomer).
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.71 (s, 0.01 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 145.83, 142.15,
135.84, 133.60, 132.33, 129.83, 128.49, 128.41, 127.35, 127.28,
126.80, 126.04, 125.88, 125.56, 125.45, 125.30, 23.63, 13.71.
MS (EI, 70 eV): m/z = 326.
HRMS (EI, 70 eV): m/z [M]+ calcd for C15H10BrF3: 325.9918;
found: 325.9922.
(E)-1-Methyl-2-(2-phenylbut-1-enyl)benzene (3k)22
Colorless liquid; yield (Z/E): 52.2 mg (47%); ratio Z/E 1:99 (1H
NMR); Rf = 0.48 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.53–7.51 (m, 2 H),
7.42–7.39 (m, 2 H), 7.34–7.31 (m, 1 H), 7.26–7.22 (m, 4 H), 6.69
(s, 1 H), 2.61 (q, J = 7.5 Hz, 2 H), 2.31 (s, 3 H), 0.99 (t, J = 7.5 Hz,
3 H).
(E)-1-Bromo-4-(3,3,3-trifluoro-2-phenylprop-1-enyl)benzene
(4e)
Colorless liquid; yield (Z/E): 71.2 mg (63%); ratio Z/E 8:92 (19F
NMR); Rf = 0.70 (PE).
IR (film): 1588, 1464, 1379, 1267, 1128, 1073, 958, 819, 702 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.42–7.41 (m, 3 H),
7.31–7.29 (m, 4 H), 7.18 (s, 1 H), 6.87 (d, J = 8 Hz, 2 H).
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 6.53 (s, 0.01 H).
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One-Pot Multistep Synthesis of Trisubstituted Alkenes
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13C NMR (125 MHz, CDCl3, E-isomer): δ = 132.50, 132.36, 132.02
(J = 5 Hz), 131.57, 131.51, 129.77, 129.14, 129.06, 123.22.
19F NMR (470 MHz, CDCl3): δ = –65.96 (s, 0.92 F, E-isomer),
–56.27 (s, 0.08 F, Z-isomer).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 134.80, 134.11 (J = 5
Hz), 133.04, 132.74, 132.05, 130.54, 130.10, 129.31, 128.80,
128.49, 122.92.
19F NMR (470 MHz, CDCl3): δ = –65.62 (s, 0.92 F, E-isomer),
–56.31 (s, 0.08 F, Z-isomer).
MS (EI, 70 eV): m/z = 326.
MS (EI, 70 eV): m/z = 326.
HRMS (EI, 70 eV): m/z [M]+ calcd for C15H10BrF3: 325.9918;
HRMS (EI, 70 eV): m/z [M]+ calcd for C15H10BrF3: 325.9918;
found: 325.9916.
found: 325.9924.
(E)-2-(3,3,3-Trifluoro-2-phenylprop-1-enyl)furan (4f)
Colorless liquid; yield (Z/E): 71.4 mg (60%); ratio Z/E 10:90 (19F
NMR); Rf = 0.67 (PE).
IR (film): 1650, 1468, 1369, 1296, 1167, 1122, 668 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.47–7.45 (m, 3 H),
7.35–7.32 (m, 3 H), 7.12 (d, J = 1.5 Hz, 1 H), 6.24 (dd, J = 3.5 Hz,
2 Hz, 1 H), 5.73 (d, J = 3.5 Hz, 1 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 149.60, 143.63,
132.83, 129.57, 128.96, 128.38, 128.32, 121.87, 121.84 (J = 5 Hz),
113.23, 118.85.
(E)-1-Bromo-4-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl)ben-
zene (4j)
Colorless liquid; yield (Z/E): 114.1 mg (70%); ratio Z/E 11:89 (19F
NMR); Rf = 0.68 (PE).
IR (film): 1464, 1379, 1274, 1127, 960, 822, 731 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.54 (d, J = 8 Hz, 2 H),
7.28 (s, 1 H), 7.26–7.19 (m, 5 H), 7.05 (d, J = 7.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 133.86, 133.22,
132.30, 131.67, 130.05, 129.18, 128.48, 123.28.
19F NMR (470 MHz, CDCl3): δ = –65.70 (s, 0.89 F, E-isomer),
–56.39 (s, 0.11 F, Z-isomer).
19F NMR (470 MHz, CDCl3): δ = –65.88 (s, 0.90 F, E-isomer),
–58.69 (s, 0.10 F, Z-isomer).
MS (EI, 70 eV): m/z = 326.
MS (EI, 70 eV): m/z = 238.
HRMS (EI, 70 eV): m/z [M]+ calcd for C15H10BrF3: 325.9918;
found: 325.9919.
HRMS (EI, 70 eV): m/z [M]+ calcd for C13H9F3O: 238.0605. found
238.0606.
(E)-1-Chloro-4-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl)ben-
zene (4k)
(E)-4-(3,3,3-Trifluoro-2-phenylprop-1-enyl)benzonitrile (4g)
Colorless liquid; yield (Z/E): 41.0 mg (30%); Rf = 0.08 (PE).
IR (film): 1681, 1463, 1379, 1268, 1132, 701 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.44–7.40 (m, 4 H),
7.32 (d, J = 2 Hz, 1 H), 7.26–7.23 (m, 3 H), 7.09 (d, J = 7.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 138.17, 133.85,
133.69, 132.00, 131.68, 131.36 (J = 5 Hz), 130.41, 129.58, 129.41,
129.23, 128.75, 128.55, 128.50.
Colorless liquid; yield (Z/E): 100.1 mg (71%); ratio Z/E 8:92 (19F
NMR); Rf = 0.72 (PE).
IR (film): 1465, 1379, 1274, 1126, 960, 824, 692 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.38 (d, J = 8.5 Hz, 2
H), 7.28–7.25 (m, 4 H), 7.21 (d, J = 7.5 Hz, 2 H), 7.04 (d, J = 7.5
Hz, 2 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 135.05, 133.89 (J = 5
Hz), 133.25, 131.40, 131.20, 130.05, 129.35, 129.17, 128.47.
19F NMR (470 MHz, CDCl3): δ = –66.33 (s, 1 F, E-isomer).
MS (EI, 70 eV): m/z = 273.
HRMS (EI, 70 eV): m/z [M]+ calcd for C16H10F3N: 273.0765;
19F NMR (470 MHz, CDCl3): δ = –65.72 (s, 0.92 F, E-isomer),
–56.38 (s, 0.08 F, Z-isomer).
found: 273.0761.
MS (EI, 70 eV): m/z = 282.
(E)-1-Bromo-2-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl)ben-
zene (4h)
HRMS (EI, 70 eV): m/z [M]+ calcd for C15H10ClF3: 282.0423;
found: 282.0420.
Colorless liquid; yield (Z/E): 79.1 mg (70%); ratio Z/E 15:85 (19F
NMR); Rf = 0.53 (PE).
(E)-1-Methoxy-4-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl)ben-
zene (4l)
IR (film): 1464, 1379, 1274, 1127, 736 cm–1.
Colorless liquid; yield (Z/E): 79.2 mg (57%); ratio Z/E 17:83 (19F
NMR); Rf = 0.20 (PE).
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.67 (d, J = 8 Hz, 1 H),
7.42–7.36 (m, 3 H), 7.33 (s, 1 H), 7.25 (d, J = 7 Hz, 1 H), 7.21–7.18
(m, 2 H), 7.02 (d, J = 7.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 141.18, 135.14 (J = 5
Hz), 133.50, 131.85, 130.53, 129.62, 129.44, 128.53, 128.33,
127.91, 124.76.
IR (film): 1611, 1463, 1379, 1272, 1173, 693 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.38–7.33 (m, 2 H),
7.21–7.17 (m, 4 H), 7.04 (d, J = 7.5 Hz, 2 H), 6.91 (d, J = 7.5 Hz, 2
H), 3.83 (s, 3 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 159.94, 133.81, 132.99
(J = 5 Hz), 132.94, 131.13, 130.04, 129.59, 128.78, 128.61, 128.55,
128.49, 128.29, 128.13, 114.45, 113.85, 55.25.
19F NMR (470 MHz, CDCl3): δ = –65.58 (s, 0.85 F, E-isomer),
–57.02 (s, 0.15 F, Z-isomer).
MS (EI, 70 eV): m/z = 326.
HRMS (EI, 70 eV): m/z [M]+ calcd for C15H10BrF3: 325.9918;
19F NMR (470 MHz, CDCl3): δ = –66.01 (s, 0.83 F, E-isomer),
–56.50 (s, 0.17 F, Z-isomer).
found: 325.9913.
MS (EI, 70 eV): m/z = 278.
(E)-1-Bromo-3-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl)ben-
zene (4i)
HRMS (EI, 70 eV): m/z [M]+ calcd for C16H13F3O: 278.0918;
found: 278.0914.
Colorless liquid; yield (Z/E): 91.5 mg (81%); ratio Z/E 8:92 (19F
NMR); Rf = 0.72 (PE).
(E)-1-Methyl-4-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl)ben-
zene (4m)
IR (film): 1466, 1379, 1274, 1128, 965, 779, 719 cm–1.
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.55 (d, J = 7.5 Hz, 1
H), 7.50 (s, 1 H), 7.27–7.20 (m, 6 H), 7.03 (d, J = 7.5 Hz, 2 H).
Colorless liquid; yield (Z/E): 110.0 mg (84%); ratio Z/E 11:89 (19F
NMR); Rf = 0.53 (PE).
IR (film): 1651, 1463, 1379, 1273, 1126, 960, 814, 693 cm–1.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 2353–2361

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Q. Sha, Y. Wei
PAPER
1H NMR (500 MHz, CDCl3, E-isomer): δ = 7.25–7.19 (m, 8 H),
7.07 (d, J = 7.5 Hz, 2 H), 2.42 (s, 3 H).
13C NMR (125 MHz, CDCl3, E-isomer): δ = 138.71, 133.79, 132.98
(J = 5 Hz), 130.10, 129.75, 128.84, 128.30, 21.37.
19F NMR (470 MHz, CDCl3): δ = –65.85 (s, 0.89 F, E-isomer),
–56.30 (s, 0.11 F, Z-isomer).
Chem. Soc. 2007, 129, 1494. (k) Cao, P.; Li, C. Y.; Kang, Y.
B.; Xie, Z.; Sun, X. L.; Tang, Y. J. Org. Chem. 2007, 72,
6628. Rh-catalyzed Wittig reaction of diazo compound with
carbonyl compounds, see: (l) Lebel, H.; Paquet, V.; Proulx,
C. Angew. Chem. Int. Ed. 2001, 40, 2887. (m) Lebel, H.;
Paquet, V. J. Am. Chem. Soc. 2004, 126, 320. (n) Lebel, H.;
Guay, D.; Paquet, V.; Huard, K. Org. Lett. 2004, 6, 3047.
(o) Lebel, H.; Paquet, V. Org. Lett. 2002, 4, 1671. Ru-
catalyzed Wittig reaction of diazo compound with carbonyl
compounds, see: (p) Fujimura, O.; Honma, T. Tetrahedron
Lett. 1998, 39, 625. (q) Sun, W.; Yu, B.; Kühn, F. E.
Tetrahedron Lett. 2006, 47, 1993. (r) Lebel, H.; Paquet, V.
Organometallics 2004, 23, 1187. (s) Pedro, F. M.; Santos,
A. M.; Baratta, W.; Kühn, F. E. Organometallics 2007, 26,
302. (t) Chen, J.; Che, C. M. Angew. Chem. Int. Ed. 2004,
43, 4950. (u) Jiang, G.; Chen, J.; Thu, H. Y.; Huang, J. S.;
Zhu, N.; Che, C. M. Angew. Chem. Int. Ed. 2008, 47, 6638.
(v) Murelli, R. P.; Snapper, M. L. Org. Lett. 2007, 9, 1749.
Co-catalyzed Wittig reaction of diazo compound with
carbonyl compounds, see: (w) Lee, M. Y.; Chen, Y.; Zhang,
X. P. Organometallics 2003, 22, 4905. (x) Ertürk, E.; Demir,
A. S. Tetrahedron 2008, 64, 7555. Cu-catalyzed Wittig
reaction of diazo compound with carbonyl compounds, see:
(y) Lebel, H.; Davi, M.; Díez-González, S.; Nolan, S. P.
J. Org. Chem. 2007, 72, 144. (z) Lebel, H.; Davi, M. Adv.
Synth. Catal. 2008, 350, 2352. (aa) Lebel, H.; Davi, M.
Chem. Commun. 2008, 4974. Ir-catalyzed Wittig reaction of
diazo compound with carbonyl compounds, see: (ab) Lebel,
H.; Ladjel, C. Organometallics 2008, 27, 2676.
MS (EI, 70 eV): m/z = 262.
HRMS (EI, 70 eV): m/z [M]+ calcd for C16H13F3: 262.0969; found:
262.0972.
(Z)-2-(3,3,3-Trifluoro-1-phenylprop-1-en-2-yl)thiophene (4n)
Colorless liquid; yield (Z/E): 94.0 mg (74%); ratio Z/E 93:7 (19F
NMR); Rf = 0.53 (PE).
IR (film): 1466, 1379, 1274, 1133, 985, 700 cm–1.
1H NMR (500 MHz, CDCl3, Z-isomer): δ = 7.41 (d, J = 5 Hz, 1 H),
7.34 (s, 1 H), 7.30–7.24 (m, 3 H), 7.17 (d, J = 7.5 Hz, 2 H), 7.10–
7.08 (m, 2 H).
13C NMR (125 MHz, CDCl3, Z-isomer): δ = 135.58 (J = 5 Hz),
133.49, 132.33, 129.98, 129.41, 129.34, 128.46, 127.94, 127.50.
19F NMR (470 MHz, CDCl3): δ = –66.54 (s, 0.93 F, Z-isomer),
–57.62 (s, 0.07 F, E-isomer).
MS (EI, 70 eV): m/z = 254.
HRMS (EI, 70 eV): m/z [M]+ calcd for C13H9F3S: 254.0377; found:
254.0382.
Acknowledgment
(4) (a) Bamford, W. R.; Stevens, T. S. J. Chem. Soc. 1952, 4735.
(b) Shapiro, R. H.; Lipton, M. F.; Kolonko, K. J.; Buswell,
R. L.; Capuano, L. A. Tetrahedron Lett. 1975, 16, 1811.
(5) (a) Barluenga, J.; Valdés, C. Angew. Chem. Int. Ed. 2011,
50, 7486. (b) Shao, Z. H.; Zhang, H. B. Chem. Soc. Rev.
2012, 41, 560. (c) Xiao, Q.; Zhang, Y.; Wang, J. B. Acc.
Chem. Res. 2013, 46, 236. (d) Zhang, Y.; Wang, J. B. Top.
Curr. Chem. 2012, 327, 239.
(6) Aggarwal, V. K.; Fulton, J. R.; Sheldon, C. G.; Vicente, J. D.
J. Am. Chem. Soc. 2003, 125, 6034.
(7) Zhu, S. F.; Liao, Y. X.; Zhu, S. Z. Org. Lett. 2004, 6, 377.
(8) Sha, Q.; Ling, Y. F.; Wang, W. Y.; Wei, Y. Y. Adv. Synth.
Catal. 2013, 355, 2145.
We thank the Project Funded by the Priority Academic Program
Development of Jiangsu Higher Education Institutions (PAPD). We
also thank Shanghai Institute of Organic Chemistry, Chinese Aca-
demy of Sciences for testing MS and HRMS.
Supporting Information for this article is available online
at
http://www.thieme-connect.com/products/ejournals/journal/
10.1055/s-00000084.SunpfgIpi
o
o
nr
i
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