Pd(0)-catalyzed cross-coupling of allyl halides with α-diazocarbonyl compounds or N-mesylhydrazones: Synthesis of 1,3-diene compounds

Article abstract of DOI:10.1039/c6ob00454g

With palladium catalysis, allyl bromides or chlorides react with α-diazocarbonyl compounds or N-mesylhydrazones to afford 1,3-diene derivatives. The reaction represents a novel and efficient method for the synthesis of 1,3-butadiene derivatives. Mechanist

Full text of DOI:10.1039/c6ob00454g

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DOI: 10.1039/C6OB00454G
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Pd(0)-Catalyzed cross-coupling of allyl halides with –
diazocarbonyl compounds or N-mesylhydrazones: synthesis of
1,3-diene compounds
Received 00th January 20xx,
Accepted 00th January 20xx
Kang Wang,a Shufeng Chen,ab Hang Zhang,a Shuai Xu,a Fei Ye,a Yan Zhanga and Jianbo Wang* a
DOI: 10.1039/x0xx00000x
With palladium catalysis, allyl bromides or chlorides react with α-diazocarbonyl compounds or N-mesylhydrazones to
afford 1,3-diene derivatives. The reaction represents a novel and efficient method for the synthesis of 1,3-butadiene
derivatives. Mechanistically, the reaction is proposed to follow a pathway involving the formation of π-allylic palladium
carbene complex and subsequent migratory insertion.
www.rsc.org/
tosylhydrazones have been explored extensively in recent years
as versatile carbene precursors in these reactions. The cross-
coupling reaction involving carbene migratory insertion can
also be applied to the synthesis of 1,3-diene formations. In 2008,
we have communicated the Pd-catalyzed reaction of allyl
halides with α-diazocarbonyl compounds to form 1,3-diene
products (Scheme 1A).10 The reaction is proposed to involve
-
allylic palladium complexes and palladium carbene migratory
insertions. Late we reported a palladium-catalyzed three-
component reaction of allenes, aryl iodides and diazo
Introduction
Conjugated 1,3-dienes are basic and ubiquitous structure units
existing in natural products and functional materials.1 They are
also important intermediates in organic synthesis.2 Due to the
intensive applications of substrates with 1,3-diene motifs in
various transformations, great efforts have been devoted to the
preparation of 1,3-diene products.3 Among the many traditional
methods, the Wittig reaction or its variant olefination methods
represent convenient approaches toward conjugated dienes
from ketones or aldehydes.4 Recently, the coupling reaction of
two vinyl substrates5 and the hydrovinylation of alkynes6 have
been significantly developed which allows for the direct and
stereo-selective preparation of 1,3-dienes. Moreover,
palladium-catalyzed coupling reaction of vinyl halides with
structurally defined organometallic alkenes and Mizoroki-Heck
reaction of olefins with vinyl halides represents alternative
approaches toward 1,3-dienes.7 Despite the various well-
established methods, the synthesis of conjugated dienes,
especially those with different substitution patterns, is still
highly demanded.
compounds. The reaction mechanism involves similar -allylic
palladium complexes and migratory insertion of allyl group
(Scheme 1B).11 More recently, we have further expanded this
type of cross-coupling reactions to the non-stabilized diazo
compounds, which are generated in situ from the corresponding
N-mesylhydrazones. In this article we report the details of these
studies.
On the other hand, the transition-metal-catalyzed
transformations involving metal carbene migratory insertion
process have been established as a powerful strategy for carbon
carbon bond formations, especially for the C=C double bond
constructions.8,9 Both stable diazo compounds and non-
stabilized diazo compounds generated in situ from N-
Scheme 1 1,3-Diene synthesis through Pd-catalyzed reaction of -
allylic palladium complexes with diazo compounds
Results and discussion
The investigation started with the Pd-catalyzed reaction of allyl
bromide 1a with methyl phenyldiazoacetate 2a. Through
extensive optimization of the reaction conditions, it was
concluded that the 1,3-diene product 3a could be isolated in 77%
yield with Pd(OAc)2 (5 mol%) as the catalyst, Et3N as the base,
o
MeCN as the solvent at 25 C for 12 h (eq 1).12 It is worth
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mentioning that in the absence of palladium catalyst no reaction
occurred under the otherwise identical conditions.
View Article Online
DOI: 10.1039/C6OB00454G
Table 3 Scope of the Pd(OAc)2-catalyzed reaction with allyl
chloridesa
(1)
With the optimized reaction conditions, the substrate scope
of the reaction was studied with allyl bromide and a series of
aryldiazoacetates and aryldiazoacetones 2a-n (Table 2). The
reaction tolerates various substitutions on the aromatic ring and
moderate to good yields of the 1,3-butadiene products 3a-n
could be obtained with high stereoselectivity. It is worth
mentioning that the reaction under identical conditions with
ethyl diazoacetate (EDA) resulted in complex mixture.
Table 2 Scope of diazocarbonyl compounds for the Pd(OAc)2-
catalyzed reaction with allyl bromidea
a The reaction follows the general procedure as described in Table 2.
Encouraged by the above Pd(OAc)2-catalyzed coupling
reaction with α-diazocarbonyl compounds, we further
proceeded to expand the reaction to the N-tosylhydrazones,
which have been extensively explored as cross-coupling
partners in transition-metal-catalyzed reactions in recent
years.8,13 However, the transition-metal-catalyzed cross
coupling of N-tosylhydrazones with allyl halides has not been
reported.
In the initial studies, we found that instead of producing
dienes products, N-allylated product of N-tosylhydrazone were
found as the main products. Those products could be formed
via nucleophilic attack of N-anion of N-tosylhydrazone to allyl
halide after deprotonation. We reasoned that these N-allylated
products might be avoided by reducing the nucleophilicity of
the nitrogen. Since MeSO2 (mesyl) group has stronger electron-
withdrawing ability than its tosyl counterpart,14 we thus focused
our efforts on N-mesylhydrazones for the coupling reaction
with allyl halides.
a Unless otherwise noted, the reaction was carried out with 0.3 mmol of 1a
,
0.42 mmol of 2a-n, and 0.9 mmol of Et3N in 5 mL MeCN. All the yields
refer to the isolated products after silica gel column chromatography. The
product ratio was determined by GC-MS or 1H NMR of the crude product. b
The reaction was carried out with 1 equiv of diazo substrate and 3 equiv of
allyl bromide. c The reaction was carried out at 60 oC.
At the outset of the investigation, we chose diphenyl N-
mesylhydrazone as the carbene precursor and allyl bromide as
the coupling partner to optimize the reaction conditions. Thus,
N-mesylhydrazone 6a (0.2 mmol) and allyl bromide 1a (0.2
mmol) were treated with Pd2(dba)3 (2.5 mol%), tris(2-
furyl)phosphine L1 (20 mol%) and LiOtBu (2 equiv) in dioxane
The scope of allyl substrates was next investigated. Under
the identical reaction conditions, the reaction of methyl
phenyldiazoacetate 2a with substituted allyl bromide resulted in
low yield of the expected diene products. Gratifyingly, the
reaction with substituted allyl chloride afforded the 1,3-diene
product smoothly under the same reaction conditions. As
summarized in Table 3, a series of substituted allyl chlorides
4a-h were submitted to the reaction with methyl
phenyldiazoacetate 2a under the same reaction conditions. The
corresponding 1,3-diene products were obtained in moderately
good yields and high selectivity. It is worth mentioning that
both alkyl and aryl substituted allyl chlorides are suitable
substrates under the current reaction conditions.
o
at 80 C for 5 h (Table 4). Gratifyingly, the diene product 7a
was isolated in 20 % yield under the initial conditions (Table 4,
entry 1). We then optimized the amount of LiOtBu (entries 2, 3
and 7) and found that 5 equiv of LiOtBu was optimal, affording
the product in 47 % yield. Further screening of the solvent
suggested that THF was the most effective one while toluene
gave poorest result (entries 4-6 and 8). Through increasing the
amount of allyl bromide from 1 equiv to 1.5 equiv and adding
the N-mesylhydrazone dropwise into the reaction mixture, we
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could isolate the product in 64 % (entry 9). Finally, the effect of 7u in moderate to good yields. 3-Bromo-1-cyclohexene 1d
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DOI: 10.1039/C6OB00454G
ligands was investigated (entries 10-13), showing that tris(2,6- could also be compatible with the reaction to give the product
dimethoxyphenyl)phosphine L4 afforded the best results to in 48 % yields
give the diene product in 73% yield, while the ligands L2
and L5 were less effective.
, L3
Table 5 Scope of N-mesylhydrazonea
Table 4 Optimization of the Reaction Conditionsa
Entry 1a
(equiv)
Pd(0) /L
solvent
(mL)
LiOtBu
(equiv)
yieldb
(%)
1
2
3
4
5
6
7
8
9
1.0
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L1
Pd2(dba)3/L2
Pd2(dba)3/L3
Pd2(dba)3/L4
Pd2(dba)3/L5
dioxane (2)
dioxane (2)
dioxane (2)
dioxane (2)
DCE (2)
THF (2)
dioxane (2)
THF (2)
THF (5)
THF (5)
THF (5)
THF (5)
THF (5)
2
3
4
4
4
4
5
5
5
5
5
5
5
5
5
20
27
42
13
42
48
47
53
64
46
36
32
58
73
70
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.5
10c 2.0
11c 1.2
12c 1.5
13c 1.5
14c 1.5
15c 1.5
THF (5)
THF (5)
a
Reaction conditions: 6a-q (0.20 mmol), 1a (0.30 mmol), Pd2(dba)3 (2.5
mol%), L4 (20 mol%) and LiOtBu (5 equiv) in THF (5 mL) stirred at 80 °C
for 5 h. All the yields refer to isolated products with silica gel column
chromatography. b The Z/E ratio was determined by 1H NMR.
a If not otherwise noted, reaction conditions are as follows: 6a (0.20 mmol),
1a (0.20 mmol), Pd2(dba)3 (5 mol%), ligand (20 mol%) and LiOtBu in a
solvent stirred at 80 oC for 5 h. b Isolated product with silica gel column
chromatography. c 1a was added dropwise into the reaction system.
Table 6 Scope of Allyl Bromidesa
With the optimized reaction conditions (Table 4, entry 14),
the scope of the N-mesylhydrazones was first examined (Table
5). Symmetrical diaryl N-mesylhydrazones with para- and
meta-substituents 6a-i worked well to give 1,1-diaryl
butadienes in moderate to good yields regardless of their
electronic properties. The N-mesylhydrazone which bears two
ortho fluorine-substituents was a poor substrate for this reaction
which gave the corresponding product 7i in only 36% yield
probably due to its steric hindrance. The unsymmetrical diaryl
N-mesylhydrazones 6j-q which have two different substituted
aryl rings could also be compatible by reacting with allyl
bromides, both electronic-donating and electronic-withdrawing
groups were well tolerated.
a
Reaction conditions: 6a (0.20 mmol), 1b-e (0.30 mmol), Pd2(dba)3 (2.5
mol%), L4 (20 mol%) and LiOtBu (5 equiv) in THF (5 mL) stirred at 80 °C
for 5 h.
Finally, both allyl chloride 4a and allyl iodide 8a reacted
with N-mesylhydrazones to give 1,3-butadiene 7a in good
yields (Scheme 2).
Next, the scope of allyl halides was examined under the same
reaction conditions (Table 6). Allyl bromides with different
substitution patterns 1b-e could be well tolerated. For example,
trans-crotyl bromide, prenyl bromide and 3-bromo-2-
methylpropene all gave the corresponding 1,3-butadienes 7r-s
,
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according to the handbook Purification of Laboratory VCiehwemArtiicclaelOsn(l4inteh
DOI: 10.1039/C6OB00454G
Edition, B. Heinemann, W. L. F. Armarego and D. D. Perrin). The
boiling point of petroleum ether was between 60 and 70 oC. For
chromatography, 200-300 mesh silica gel was employed. Chemical
shifts for 1H NMR (400 MHz) and 13C{1H}NMR spectra are
reported relative to the chemical shift of tetramethylsilane (TMS):
chemical shifts (δ) were reported in ppm, and coupling constants (J)
are in Hertz (Hz). IR spectra are reported in wave numbers, cm−1.
For HRMS measurements, the mass analyzer is FT-ICR. PE:
petroleum either; EA: ethyl acetate. Unless otherwise noted,
materials obtained from commercial suppliers were used without
further purification.
Scheme 2 Reaction of allyl chloride and iodide
As illustrated in Scheme 3, a plausible reaction mechanism
is proposed according to our understanding on the palladium-
catalyzed carbene-based cross-coupling reactions.8 First,
oxidative addition of Pd(0) to allyl halide generates 1
-
-
General Procedure for the Pd(OAc)2-catalyzed reaction of allylic
halides with diazo compounds.
allylpalladium complex
A
, which is in equilibrium with 3
allylpalladium complex A'. In the case of coupling with N-
mesylhydrazone, the diazo compound is generated in situ from
N-mesylhydrazone in the presence of LiOtBu. Reaction of the
To a solution of allylic halide (0.3 mmol) in anhydrous CH3CN (5
mL) was added Et3N (0.9 mmol) and Pd(OAc)2 (0.015 mmol) at
room temperature. After 5 minutes, diazo compound (0.42 mmol)
o
diazo compound with
formation of palladium carbene complex B 8,15
insertion of the allyl group of to the carbenic carbon produces
species , from which β-H elimination occurs to generate 1,3-
-
allyllic palladium complex leads to the
was added and the mixture was stirred for several hours at 25 C.
.
Migratory
The progress of the reaction was monitored by TLC. After
completion of the reaction, solvent was removed under vacuum, and
the crude product was purified by column chromatography.
B
C
butadiene product and regenerate Pd(0) catalyst.
(E)-Methyl 2-phenylpenta-2,4-dienoate (3a).17 Yield 77% (44 mg,
purified by silica gel column chromatography using PE:EA = 30:1 as
1
eluent, Rf = 0.45); colorless oil; H NMR (300 MHz, CDCl3) δ 3.77
(s, 3H), 5.42 (ddd, J = 0.6, 1.5, 10.8 Hz, 1H), 5.66 (ddd, J = 0.6, 1.5,
16.8 Hz, 1H), 6.39 (ddd, J = 10.2, 11.4, 16.8 Hz, 1H), 7.21-7.26 (m,
2H), 7.32-7.42 (m, 3H), 7.46 (d, J = 11.4 Hz, 1H); 13C NMR (75
MHz, CDCl3) δ 52.2, 125.7, 127.7, 127.9, 128.2, 130.1, 133.1, 134.8,
140.7, 167.8.
(E)-Methyl 2-p-tolylpenta-2,4-dienoate (3b). Yield 77% (47 mg,
purified by silica gel column chromatography using PE:EA = 30:1 as
eluent, Rf = 0.45); colorless oil; IR (neat) 1718, 1514, 1435, 1245
1
cm-1; H NMR (300 MHz, CDCl3) δ 2.37 (s, 3H), 3.76 (s, 3H), 5.40
(ddd, J = 0.6, 1.5, 9.9 Hz, 1H), 5.65 (ddd, J = 0.6, 1.5, 16.8 Hz, 1H),
6.41 (ddd, J = 10.2, 11.4, 16.8 Hz, 1H), 7.11-7.28 (M, 5H), 7.45 (d, J
= 11.4 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 21.2, 52.1, 125.4,
128.7, 130.0, 131.9, 133.2, 133.3，137.5, 140.4, 168.0; EI-MS (m/z,
relative intensity): 202 (M+, 30), 143 (100). HRMS (EI) calcd for
C13H14O2+ [M]+: 202.0994; Found: 202.0992.
Scheme 3 Proposed reaction mechanism
Conclusion
In conclusion, we have developed a new route towards 1,3-
diene compounds through palladium-catalyzed coupling
reaction of allyl halides with -diazocarbonyl compounds or N-
(E)-Methyl 2-(4-methoxyphenyl)penta-2,4-dienoate (3c). Yield
53% (35 mg, purified by silica gel column chromatography using
PE:EA = 20:1 as eluent, Rf = 0.35); colorless oil; IR (neat) 1736,
mesylhydrazones.16 Mechanistically, the reaction may involve a
-allylic migratory insertion of palladium carbene intermediate.
Further studies on the development of transition-metal-
catalyzed carbene-based coupling reaction are currently
underway in our laboratory and the results will be reported in
due course.
1
1613, 1513, 1247 cm-1; H NMR (300 MHz, CDCl3) 3.78 (s, 3H),
3.84 (s, 3H), 5.41 (ddd, J = 0.6, 1.8, 10.2 Hz, 1H), 5.66 (ddd, J = 0.6,
1.8, 16.5 Hz, 1H), 6.43 (ddd, J = 10.2, 11.4, 16.5 Hz, 1H), 6.90-6.95
(m, 2H), 7.14-7.19 (m, 2H), 7.43 (d, J = 11.4 Hz, 1H); 13C NMR (75
MHz, CDCl3)  52.2, 55.2, 113.4, 125.3, 127.0, 131.3, 132.7, 133.3,
140.3, 159.1, 168.1; EI-MS (m/z, relative intensity): 218 (M+, 20),
159 (48), 121(100). HRMS (EI) calcd for C13H14O3+ [M]+: 218.0943;
Found: 218.0943.
Experimental
General methods.
(E)-Methyl 2-(3-methoxyphenyl)penta-2,4-dienoate (3d). Yield
71% (47 mg, purified by silica gel column chromatography using
PE:EA = 20:1 as eluent, Rf = 0.45); colorless oil; IR (neat) 1713,
All reactions were performed under a nitrogen atmosphere in oven-
dried reaction flasks. All solvents were freshly distilled and degassed
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30:1 as eluent, Rf = 0.45); colorless oil; IR (neat) 1668, 1619, 1491,
1601, 1585, 1246 cm-1; 1H NMR (300 MHz, CDCl3) s,
3H3.82 (s, 3H), 5.42 (ddd, J = 1.2, 1.8, 10.2 Hz, 1H), 5.66 (ddd, J
= 0.9, 1.8, 16.8 Hz, 1H), 6.40 (ddd, J = 10.2, 11.4, 16.8 Hz, 1H),
6.76-6.82 (m, 2H), 6.88-6.91 (m, 1H), 7.27-7.33 (m, 1H), 7.45 (d, J
= 11.4 Hz, 1H); 13C NMR (75 MHz, CDCl3) 52.2, 55.2, 113.2,
115.7, 122.5, 125.8, 129.0, 133.0, 133.1, 136.1, 140.8, 159.1, 167.7;
EI-MS (m/z, relative intensity): 218 (M+, 50), 159 (100). HRMS (EI)
calcd for C13H14O3+ [M]+: 218.0943; Found: 218.0944.
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-1
1
DOI: 10.1039/C6OB00454G
1250, 1090 cm ; H NMR (300 MHz, CDCl3) s, 3Hd,
J = 10.2 Hz, 1Hd, J = 16.8 Hz, 1Htd, J = 10.2, 16.8
Hz, 1Hd, J = 8.4 Hz, 2H7.26-7.29 (m, 1H),d, J =
8.4 Hz, 2H13C NMR (75 MHz, CDCl3) 27.2, 126.8, 128.4, 131.3,
133.2, 133.7, 133.8, 140.3, 140.7, 198.3; EI-MS (m/z, relative
intensity): 206 (M+, 45), 128 (75), 43 (100). HRMS (EI) calcd for
C12H11OCl+ [M]+: 206.0498; Found: 206.0496.
(E)-3-(3-Chlorophenyl)hexa-3,5-dien-2-one (3j). Yield 70% (44
mg, purified by silica gel column chromatography using PE:EA =
30:1 as eluent, Rf = 0.45); colorless oil; IR (neat) 1668, 1621, 1423,
(E)-Methyl 2-(2-chlorophenyl)penta-2,4-dienoate (3e). Yield 61%
(41 mg, purified by silica gel column chromatography using PE:EA
= 30:1 as eluent, Rf = 0.40); colorless oil; IR (neat) 1715, 1629, 1434,
1242 cm-1; 1H NMR (300 MHz, CDCl3) s, 3Hdd J =
1.5, 9.9 Hz, 1Hdd, J = 1.5, 16.8 Hz, 1Hddd, J = 10.2,
1
1250 cm-1; H NMR (300 MHz, CDCl3) s, 3Hd, J =
10.2 Hz, 1Hd, J = 16.8 Hz, 1Htd, J = 10.8, 16.8 Hz,
1H7.02-7.05 (m, 1H),s, 1Hm, 4H13C NMR
(75 MHz, CDCl3) 27.2, 127.0, 127.9, 128.2, 129.5, 129.9, 133.2,
134.1, 137.2, 140.4, 140.5, 198.1; EI-MS (m/z, relative intensity):
206 (M+, 22), 128 (49), 43 (100). HRMS (EI) calcd for C12H11OCl+
[M]+: 206.0498; Found: 206.0494.
11.4, 17.1 Hz, 1H7.17-7.46 (m, 4H), 7.51 (d, J = 11.4 Hz, 1H); 13
C
NMR (75 MHz, CDCl3) 52.3, 126.5, 126.6, 129.3, 129.4, 131.0,
131.7, 132.5, 134.0, 134.1, 141.8, 167.0; EI-MS (m/z, relative
intensity): 222 (M+, 17), 187 (59), 128 (100). HRMS (EI) calcd for
C12H11O2Cl+ [M]+: 222.0448; Found: 222.0444.
(E)-3-(4-Bromophenyl)hexa-3,5-dien-2-one (3k). Yield 63% (48
mg, purified by silica gel column chromatography using PE:EA =
30:1 as eluent, Rf = 0.40); colorless oil; IR (neat) 1667, 1615, 1487,
(E)-Methyl 2-(4-chlorophenyl)penta-2,4-dienoate (3f). Yield 73%
(49 mg, purified by silica gel column chromatography using PE:EA
= 30:1 as eluent, Rf = 0.40); colorless oil; IR (neat) 1713, 1624, 1493,
1420, 1242 cm-1; 1H NMR (300 MHz, CDCl3) s,
3Hdd J = 1.2, 10.2 Hz, 1Hdd, J = 0.9, 16.8 Hz,
1Hddd, J = 10.2, 11.4, 16.8 Hz, 1H7.15-7.19 (m, 2H),
7.35-7.38 (m, 2H), 7.47 (d, J = 11.4 Hz, 1H) ; 13C NMR (75 MHz,
CDCl3)  52.3, 126.4, 128.2, 131.5, 131.6, 131.9, 132.7, 133.1,
141.2, 167.4; EI-MS (m/z, relative intensity): 222 (M+, 28), 128
(100). HRMS (EI) calcd for C12H11O2Cl+ [M]+: 222.0448; Found:
222.0449.
1
1250 cm-1; H NMR (300 MHz, CDCl3) s, 3Hd, J =
9.9 Hz, 1Hd, J = 16.8 Hz, 1Htd, J = 10.8, 16.8 Hz,
1Hd, J = 8.4 Hz, 2H7.27 (d, J = 11.4 Hz, 1H),d, J =
8.4 Hz, 2H13C NMR (75 MHz, CDCl3) 27.1, 122.0, 126.8, 131.3,
131.6, 133.2, 134.1, 140.3, 140.7, 198.2; EI-MS (m/z, relative
intensity): 252 (M+, 19), 128 (75), 43 (100). HRMS (EI) calcd for
C12H11OBr+ [M]+: 249.9993; Found: 249.9981.
(E)-3-(3,4-Dichlorophenyl)hexa-3,5-dien-2-one (3l). Yield 60%
(44 mg, purified by silica gel column chromatography using PE:EA
= 30:1 as eluent, Rf = 0.35); yellow oil; IR (neat) 1666, 1621, 1473,
(E)-Methyl 2-(3,4-dichlorophenyl)penta-2,4-dienoate (3g). Yield
50 % (39 mg, purified by silica gel column chromatography using
PE:EA = 30:1 as eluent, Rf = 0.40); yellow oil; IR (neat) 1714, 1580,
1475, 1244 cm-1; 1H NMR (300 MHz, CDCl3) s,
3Hd J = 10.5 Hz, 1Hd, J = 16.8 Hz, 1Hddd,
J = 10.5, 11.4, 16.8 Hz, 1Hdd J = 1.8, 8.4 Hz, 1H7.27-
7.34 (m, 1H), 7.45-7.51 (m, 2H) ; 13C NMR (75 MHz, CDCl3)  52.4,
127.3, 128.0, 129.6, 130.0, 130.7, 132.0, 132.2, 132.4, 134.7, 141.8,
167.0; EI-MS (m/z, relative intensity): 256 (M+, 23), 162 (100).
1
1250 cm-1; H NMR (300 MHz, CDCl3) s, 3Hd, J =
10.2 Hz, 1Hd, J = 16.8 Hz, 1Htd, J = 10.8, 16.8 Hz,
1H d, J = 8.1 Hz, 1H7.26-7.31 (m, 2H), d, J = 8.1
Hz, 1H13C NMR (75 MHz, CDCl3) 26.9, 127.5, 129.5, 130.2,
131.8, 132.1, 132.3, 132.9, 135.1, 139.5, 141.0, 197.8; EI-MS (m/z,
relative intensity): 240 (M+, 81), 162 (100). HRMS (EI) calcd for
C12H10OCl2+ [M]+: 240.0109; Found: 240.0099.
+
HRMS (EI) calcd for C12H10O2Cl2 [M]+: 256.0058; Found:
(E)-2-(Allyloxy)phenyl 2-phenylpenta-2,4-dienoate (3m). Yield
77% (67 mg, purified by silica gel column chromatography using
PE:EA = 30:1 as eluent, Rf = 0.45); colorless oil; IR (neat) 1730,
1604, 1498, 1183, 1157 cm-1; 1H NMR (300 MHz, CDCl3) dt,
J = 1.5, 5.1 Hz, 2Hdt, J = 1.5, 10.8 Hz, 1Hddd, J =
1.8, 3.3, 17.4 Hz, 1Hd J = 9.9 Hz, 1Hd J = 16.8 Hz,
1Hmmd J = 7.5 Hz, 2H7.05-7.19
(m, 2H), 7.30-7.38 (m, 5H), 7.67d J = 11.4 Hz, 1H13C NMR (75
MHz, CDCl3) 69.3, 113.8, 117.3, 121.0, 122.9, 126.4, 126.6, 127.8,
127.9, 130.3, 132.5, 132.9, 133.1, 134.6, 140.4, 141.9, 150.0, 165.5;
EI-MS (m/z, relative intensity): 306 (M+, 12), 157 (89), 129 (100).
HRMS (EI) calcd for C20H18O3+ [M]+: 306.1256; Found: 306.1265.
256.0065.
(E)-3-Phenylhexa-3,5-dien-2-one (3h). Yield 55% (28 mg, purified
by silica gel column chromatography using PE:EA = 30:1 as eluent,
1
Rf = 0.45); colorless oil; IR (neat) 1665, 1615, 1249, 1226 cm-1; H
NMR (300 MHz, CDCl3) s, 3Hd, J = 9.9 Hz,
1Hd, J = 16.8 Hz, 1Htd, J = 10.5, 16.8 Hz,
1H7.14-7.43 (m, 6H)13C NMR (75 MHz, CDCl3) 27.6, 126.1,
127.7, 128.2, 129.9, 133.5, 135.5, 139.4, 141.8, 198.8; EI-MS (m/z,
relative intensity): 172 (M+, 36), 129 (100). HRMS (EI) calcd for
C12H12O+ [M]+: 172.0888; Found: 172.0884.
(E)-3-(4-Chlorophenyl)hexa-3,5-dien-2-one (3i). Yield 68% (42
mg, purified by silica gel column chromatography using PE:EA =
(E)-Benzhydryl 2-phenylpenta-2,4-dienoate (3n). Yield 69% (71
mg, purified by silica gel column chromatography using PE:EA =
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
30:1 as eluent, Rf = 0.40); white solid; IR (neat) 1711, 1495, 1232, 123.8, 127.2, 127.7, 128.0, 129.4, 130.4, 131.7, 133.5, 135.2, 139.1,
View Article Online
+
1175 cm-1; 1H NMR (300 MHz, CDCl3) dd, J = 0.6, 10.5 Hz,
DOI: 10.1039/C6OB00454G
140.7, 141.0, 168.0. EI-MS (m/z, relative intensity): 278 (M , 60),
219 (100). HRMS (EI) calcd for C19H18O2 [M]+: 278.1307; Found:
+
1Hd, J = 17.1 Hz, 1Hddd, J = 10.2, 11.1, 17.1, Hz,
1Hs, 1H7.23-7.44 (m, 5H), 7.54d, J = 11.1 Hz, 1H13C
278.1305.
NMR (75 MHz, CDCl3) 77.3, 125.9, 126.9, 127.1, 127.4, 127.7,
(2E,4E)-Methyl
5-(4-chlorophenyl)-2-phenylpenta-2,4-dienoate
127.9, 128.2, 128.4, 128.6, 129.3, 130.1, 133.1, 134.7, 140.3, 140.9,
166.1; EI-MS (m/z, relative intensity): 340 (M+, 17), 167 (100).
HRMS (EI) calcd for C24H20O2+ [M]+: 340.1463; Found: 340.1464.
(2E,4E)-Methyl 2-phenylhexa-2,4-dienoate (5a).18 Yield 63% (38
mg, purified by silica gel column chromatography using PE:EA =
30:1 as eluent, Rf = 0.45); colorless oil; IR (neat) 1710, 1637, 1434,
1233 cm-1; 1H NMR (300 MHz, CDCl3) d, J = 6.6 Hz,
3Hs, 3H-6.26 (m, 2H), 7.22-7.26 (m, 2H), 7.32-7.42
(m, 3H), d, J = 10.8 Hz, 1H13C NMR (75 MHz, CDCl3)
18.9, 52.1, 127.4, 127.9, 128.1, 130.1, 135.0, 135.2, 139.9, 141.1,
168.1; EI-MS (m/z, relative intensity): 202 (M+, 23), 143 (100).
HRMS (EI) calcd for C13H14O2+ [M]+: 202.0994; Found: 202.0995.
(5f). Yield 65% (58 mg, purified by silica gel column
chromatography using PE:EA = 30:1 as eluent, Rf = 0.40); white
1
solid; IR (neat) 1708, 1616, 1490, 1232 cm-1; H NMR (300 MHz,
CDCl3) s, 3Hdd, J = 11.1, 15.6 Hz, 1Hd, J =
15.6 Hz, 1H7.26-7.30 (m, 6H), 7.39-7.47 (m, 3H), d, J =
11.1 Hz, 1H13C NMR (75 MHz, CDCl3) 52.2, 125.2, 127.8,
128.1, 128.3, 128.9, 130.3, 132.8, 134.5, 134.7, 135.0, 139.0, 140.3,
167.8; EI-MS (m/z, relative intensity): 298 (M+, 64), 204 (100).
HRMS (EI) calcd for C18H15O2Cl+ [M]+: 298.0761; Found: 298.0760.
(E)-Methyl 2,5,5-triphenylpenta-2,4-dienoate (5g). Yield 65% (66
mg, purified by silica gel column chromatography using PE:EA =
30:1 as eluent, Rf = 0.40); white solid; IR (neat) 1707, 1604, 1434,
1262, 1234 cm-1; 1H NMR (300 MHz, CDCl3) s, 3Hd,
J = 11.7 Hz, 1H7.17~7.43 (m, 15H), d, J = 11.7 Hz, 1H13C
NMR (75 MHz, CDCl3) 52.1, 123.7, 127.7, 128.0, 128.2, 128.3,
128.4, 130.3, 130.5, 133.1, 135.2, 138.1, 138.8, 141.6, 150.8, 168.0;
EI-MS (m/z, relative intensity): 340 (M+, 93), 281 (100). HRMS (EI)
calcd for C24H20O2+ [M]+: 340.1463; Found: 340.1469.
(E)-Methyl 5-methyl-2-phenylhexa-2,4-dienoate (5b).19 Yield 72%
(47 mg, purified by silica gel column chromatography using PE:EA
= 30:1 as eluent, Rf = 0.45); colorless oil; 1H NMR (300 MHz,
CDCl3) s, 3Hs, 3Hs, 3Hd, J = 12.0
Hz, 1H7.20-7.23 (m, 2H), 7.29-7.42 (m, 3H), d, J = 12.0 Hz,
1H13C NMR (75 MHz, CDCl3) 19.1, 26.9, 52.0, 121.9, 127.3,
127.9, 129.4, 130.2, 135.5, 136.9, 146.8, 168.5.
(2E,4E)-2-(Allyloxy)phenyl 2,5-diphenylpenta-2,4-dienoate (5h).
Yield 70% (78 mg, purified by silica gel column chromatography
using PE:EA = 20:1 as eluent, Rf = 0.35); white solid; IR (neat) 1724,
(E)-Methyl 4-cyclohexylidene-2-phenylbut-2-enoate (5c). Yield
71 % (61 mg, purified by silica gel column chromatography using
PE:EA = 30:1 as eluent, Rf = 0.45); colorless oil; IR (neat) 2931,
1710, 1627, 1434, 1242 cm-1; 1H NMR (300 MHz, CDCl3)
br, m, 6Hbr, m, 2Hbr, m,
2Hs, 3Hd, J = 12.0 Hz, 1H7.21-7.27 (m, 2H),
7.33-7.40 (m, 3H), d, J = 12.0 Hz, 1H13C NMR (75 MHz,
CDCl3) 26.5, 27.9, 28.5, 29.9, 38.0, 52.0, 118.7, 127.3, 127.9,
129.6, 130.3, 135.5, 136.1, 154.9, 168.5; EI-MS (m/z, relative
1
1614, 1497, 1183 cm-1; H NMR (300 MHz, CDCl3) d, J =
4.8 Hz, 2Hdd, J = 1.2, 10.5 Hz, 1Hdd, J = 1.5, 17.4
Hz, 1Hddd, J = 5.4, 10.5, 12.0 Hz, 1H6.88-7.45 (m,
16H)d, J = 10.8 Hz, 1H13C NMR (75 MHz, CDCl3) 69.3,
113.8, 117.2, 121.0, 123.0, 124.7, 126.5, 127.3, 127.8, 128.0, 128.7,
129.0, 130.5, 131.5, 132.9, 134.9, 136.2, 140.6, 141.3, 142.0, 150.1,
165.6; EI-MS (m/z, relative intensity): 382 (M+, 6), 233 (100).
HRMS (EI) calcd for C26H22O3+ [M]+: 382.1569; Found: 382.1558.
+
intensity): 256 (M+, 100), 197 (98). HRMS (EI) calcd for C17H20O2
[M]+: 256.1463; Found: 256.1459.
(2E,4E)-Benzhydryl 2,5-diphenylpenta-2,4-dienoate (5i). Yield
60% (75 mg, purified by silica gel column chromatography using
PE:EA = 30:1 as eluent, Rf = 0.45); white solid; IR (neat) 1706, 1223
(2E,4E)-Methyl 2,5-diphenylpenta-2,4-dienoate (5d). Yield 66%
(53 mg, purified by silica gel column chromatography using PE:EA
= 30:1 as eluent, Rf = 0.45); white solid; IR (neat) 1707, 1616, 1434,
1232 cm-1; 1H NMR (300 MHz, CDCl3) s, 3Hdd, J =
11.4, 15.6 Hz, 1Hd, J = 15.6 Hz, 1H7.25-7.44 (m, 10H),
d, J = 11.1 Hz, 1H13C NMR (75 MHz, CDCl3) 52.2, 124.7,
127.2, 127.7, 128.0, 128.7, 128.9, 130.3, 132.2, 135.1, 136.2, 140.6,
140.7, 167.9; EI-MS (m/z, relative intensity): 264 (M+, 57), 205
1
cm-1; H NMR (300 MHz, CDCl3) dd, J = 11.4, 15.6 Hz,
1H6.97-7.02 (m, 2H), -m, 20Hd, J = 11.1 Hz,
1H13C NMR (75 MHz, CDCl3) 77.3, 124.7, 126.9, 127.2, 127.7,
128.0, 128.4, 128.7, 128.9, 130.4, 132.4, 135.0, 136.2, 140.4, 140.8,
140.9, 166.2; EI-MS (m/z, relative intensity): 416 (M+, 3), 167 (100).
HRMS (EI) calcd for C30H24O2+ [M]+: 416.1776; Found: 416.1762.
+
(100). HRMS (EI) calcd for C18H16O2 [M]+: 264.1150; Found:
264.1142.
(2E,4E)-Cinnamyl 2,5-diphenylpenta-2,4-dienoate (5j). Yield 58%
(64 mg, purified by silica gel column chromatography using PE:EA
= 30:1 as eluent, Rf = 0.40); white solid; IR (neat) 1703, 1223 cm-1;
1H NMR (300 MHz, CDCl3) d, J = 6.0 Hz, 2Htd, J =
6.0, 15.9 Hz, 1Hd, J = 15.9 Hz, 1Hdd, J = 11.4, 15.6
Hz, 1Hd, J = 15.6 Hz, 1H7.26-7.47 (m, 15H),d, J =
11.1 Hz, 1H13C NMR (75 MHz, CDCl3) 65.5, 123.3, 124.7,
126.6, 127.2, 127.8, 128.0, 128.1, 128.6, 128.7, 128.9, 130.4, 132.3,
(2E,4E)-Methyl 2-phenyl-5-p-tolylpenta-2,4-dienoate (5e). Yield
57% (48 mg, purified by silica gel column chromatography using
PE:EA = 30:1 as eluent, Rf = 0.35); white solid; IR (neat) 1708, 1603,
1434, 1233 cm-1; 1H NMR (300 MHz, CDCl3) s, 3Hs,
3Hdd, J = 11.4, 15.6 Hz, 1Hd, J = 15.6 Hz,
1Hd, J = 7.8 Hz, 2H7.23-7.31 (m, 4H), 7.36-7.45 (m, 3H),
d, J = 11.1 Hz, 1H13C NMR (75 MHz, CDCl3) 21.3, 52.1,
6 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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ARTICLE
133.8, 135.0, 136.2, 140.7, 140.8, 167.1; EI-MS (m/z, relative HRMS (ESI) calcd for C16H19N2O2S+ (M+H)+: 303V.1ie1w6A7r;ticFleoOunnlinde:
+
intensity): 366 (M+, 3), 117 (100). HRMS (EI) calcd for C26H22O2
[M]+: 366.1620; Found: 366.1628.
303.1160; Anal. Calcd for C16H18N2O2S: C, 63.55; H, 6.00; N, 9.26.
Found: C, 63.49; H, 6.08; N, 9.25.
DOI: 10.1039/C6OB00454G
N-(Bis(4-chlorophenyl)methylene)methanesulfonohydrazide (6d).
(2E,4E)-allyl 2,5-diphenylpenta-2,4-dienoate (5k). Yield 51%
(45 mg, purified by silica gel column chromatography using PE:EA
= 30:1 as eluent, Rf = 0.45); white solid; IR (neat) 1707, 1224 cm-1;
1H NMR (300 MHz, CDCl3) d, J = 5.4 Hz, 2Hdd, J =
0.9, 10.5 Hz, 1Hdd, J = 1.2, 17.1 Hz, 1Hddd, J = 5.4,
10.8, 15.9 Hz, 1Hdd, J = 11.4, 15.6 Hz, 1H6.99 (d, J =
15.6 Hz, 1H),m, 10Hd, J = 11.1 Hz, 1H13C
NMR (75 MHz, CDCl3) 65.5, 117.9, 124.7, 127.2, 127.7, 128.0,
128.7, 128.9, 130.4, 132.2, 135.0, 136.2, 140.7, 140.8, 167.0; EI-MS
(m/z, relative intensity): 290 (M+, 55), 205 (100). HRMS (EI) calcd
for C20H18O2+ [M]+: 290.1307; Found: 290.1318.
o
Yield 46 % (1.53 g); white solid; mp: 145-146 C; IR (film): 3198,
1
1386, 1159, 984, 829 cm-1; H NMR (400 MHz, CDCl3) δ 3.19 (s,
3H), 7.22-7.24 (m, 2H), 7.30-7.33 (m, 2H), 7.41 (broad, 1H), 7.45-
7.49 (m, 2H), 7.56-7.58 (m, 2H); 13C NMR (100 MHz, CDCl3) δ
39.2, 128.7, 128.8, 128.9, 129.8, 130.4, 134.4, 136.5, 136.8, 151.8;
HRMS (ESI) calcd for C14H13Cl2N2O2S+ (M+H)+: 343.0075; Found:
343.0048; Anal. Calcd for C14H12Cl2N2O2S: C, 48.99; H, 3.52; N,
8.16. Found: C, 48.59; H, 3.47; N, 8.25.
N-(Bis(4-fluorophenyl)methylene)methanesulfonohydrazide (6e).
o
Yield 44 % (1.37 g); white solid; mp: 141-142 C; IR (film): 3190,
1
1606, 1507, 1392, 1312, 1224, 1165, 1063, 987, 842, 767 cm-1; H
General procedure for the preparation of N-mesylhydrazones.
NMR (400 MHz, CDCl3) δ 3.18 (s, 3H), 7.01-7.05 (m, 2H), 7.26-
7.29 (m, 4H), 7.40 (broad, 1H), 7.51-7.55 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 39.1, 115.6, 117.2, 126.7, 129.6, 130.6, 132.4, 152.2,
162.8, 165.3; HRMS (ESI) calcd for C14H13F2N2O2S+ (M+H)+:
311.0666; Found: 311.0654; Anal. Calcd for C14H12F2N2O2S: C,
54.19; H, 3.90; N, 9.03. Found: C, 54.26; H, 3.87; N, 9.07.
Methanesulfonyl chloride (1.15 g, 10 mmol) was added slowly to a
stirred ice-cold solution of hydrazine hydrate (0.5 g, 10 mmol) in
water (1.5 mL), followed by 2 M NaOH (aq, 5 mL), such that the
N-(Di-m-tolylmethylene)methanesulfonohydrazide (6f). Yield 25 %
(0.73 g); white solid; mp: 160-161 C; IR (film): 3209, 1585, 1380,
o
1340, 1316, 1163, 1062, 969, 873 cm-1; 1H NMR (400 MHz, CDCl3)
δ 2.34 (s, 3H), 2.42 (s, 3H), 3.16 (s, 3H), 7.04-7.05 (m, 2H), 7.18-
7.23 (m, 2H), 7.28-7.30 (m, 1H), 7.32-7.33 (m, NH), 7.42-7.46 (m,
3H); 13C NMR (100 MHz, CDCl3) δ 21.4, 21.5, 39.1, 125.1, 125.2,
127.9, 128.2, 128.6, 129.7, 130.9, 130.9, 131.2, 136.3, 138.1, 139.9,
154.7; HRMS (ESI) calcd for C16H19N2O2S+ (M+H)+: 303.1167;
Found: 303.1160; Anal. Calcd for C16H18N2O2S: C, 63.55; H, 6.00;
o
temperature did not exceed 8 C. On completion, the mixture was
added into a solution of ketone (10 mmol) in a minimum amount of
o
MeOH. The reaction mixture was heated at 50 C and monitored by
TLC analysis. After completion of the reaction, the product was
collected by filtration and washed thoroughly with cold Et2O or
recrystallized with EtOH (10 mL).
N-(Diphenylmethylene)methanesulfonohydrazide (6a). Yield 64 % N, 9.26. Found: C, 63.47; H, 6.03; N, 9.23.
o
(1.73 g); white solid; mp: 207-208 C; IR (film): 3203, 1396, 1337,
1160, 990, 882, 785, 705 cm-1; H NMR (400 MHz, CDCl3) δ 3.19
(s, 3H), 7.26-7.29 (m, 2H), 7.32-7.8 (m, 3H), 7.44 (broad, 1H), 7.54-
7.58 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 39.1, 127.7, 128.3,
128.4, 129.9, 130.1, 130.3, 131.1, 136.3, 154.2; HRMS (ESI) calcd
for C14H15N2O2S+ (M+H)+: 275.0854; Found: 275.0854; Anal. Calcd
for C14H14N2O2S: C, 61.29; H, 5.14; N, 10.21. Found: C, 61.29; H,
5.12; N, 10.35.
1
N-(Bis(3-methoxyphenyl)methylene)methanesulfonohydrazide (6g).
o
Yield 25 % (0.84 g); white solid; mp: 100-101 C; IR (film): 3195,
1
1577, 1464, 1310, 1173, 1002, 969, 871, 703 cm-1; H NMR (400
MHz, CDCl3) δ 3.18 (s, 3H), 3.80 (s, 3H), 3.83 (s, 3H), 6.75-6.83 (m,
2H), 6.92-6.94 (m, 1H), 7.03-7.05 (m, 1H), 7.10-7.12 (m, 1H), 7.18
(broad, 1H), 7.25-7.26 (m, 1H), 7.45-7.49 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 39.1, 55.4, 55.5, 113.0, 113.6, 115.6, 115.8, 120.1,
120.5, 129.3, 131.1, 132.3, 137.5, 153.8, 159.6, 160.6; HRMS (ESI)
N-(Bis(4-methoxyphenyl)methylene)methanesulfonohydrazide (6b). calcd for C16H19N2O4S+ (M+H)+: 335.1066; Found: 335.1063.
o
Yield 38 % (1.28 g); white solid; mp: 103-105 C; IR (film): 3208,
1
1609, 1512, 1318, 1159, 1030, 983, 839 cm-1; H NMR (400 MHz,
N-(Bis(3-fluorophenyl)methylene)methanesulfonohydrazide (6h).
o
Yield 35 % (1.06 g); white solid; mp: 165-167 C; IR (film): 3202,
CDCl3) δ 3.17 (s, 3H), 3.82 (s, 3H), 3.89 (s, 3H), 6.84-6.87 (m, 2H),
7.04-7.07 (m, 2H), 7.19-7.23 (m, 2H), 7.38 (broad, 1H), 7.40-7.52
(m, 2H); 13C NMR (100 MHz, CDCl3) δ 38.9, 55.4, 55.5, 113.7,
115.1, 123.1, 129.3, 129.4, 130.0, 154.2, 160.8, 161.2; HRMS (ESI)
calcd for C16H19N2O4S+ (M+H)+: 335.1066; Found: 335.1064.
1
1583, 1442, 1340, 1271, 1176, 1016, 977, 893 cm-1; H NMR (400
MHz, CDCl3) δ 3.20 (s, 3H), 6.98-7.01 (m, 1H), 7.07-7.12 (m, 2H),
7.26-7.34 (m, 4H), 7.48 (broad, 1H), 7.56-7.61 (m, 1H); 13C NMR
(100 MHz, CDCl3) δ 39.2, 114.3, 115.7, 117.4, 117.9, 123.4, 124.1,
130.0, 132.0, 132.5, 138.0, 151.2, 162.2, 164.7; HRMS (ESI) calcd
N-(Di-p-tolylmethylene)methanesulfonohydrazide (6c). Yield 32 % for C14H13F2N2O2S+ (M+H)+: 311.0666; Found: 311.0652.
o
(1.12 g); white solid; mp: 151-152 C; IR (film): 3200, 1392, 1340,
1160, 983 cm-1; 1H NMR (400 MHz, CDCl3) δ 2.36 (s, 3H), 2.44 (s,
N-(Bis(2-fluorophenyl)methylene)methanesulfonohydrazide
(6i).
o
Yield 36 % (1.12 g); white solid; mp: 201-202 C; IR (film): 3206,
3H), 3.17 (s, 3H), 7.12-7.16 (m, 4H), 7.34-7.36 (m, 2H), 7.41 (broad,
1H), 7.45-7.47 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 21.4, 21.5,
39.0, 127.7, 128.1, 128.3, 129.0, 130.4, 133.7, 140.3, 140.4, 154.6;
1
1614, 1488, 1451, 1319, 1220, 1108, 990, 764 cm-1; H NMR (400
MHz, CDCl3) δ 3.20 (s, 3H), 7.00-7.05 (m, 1H), 7.16-7.32 (m, 4H),
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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Organic & Biomolecular Chemistry
Page 8 of 11
ARTICLE
Journal Name
7.37-7.41 (m, 1H), 7.50-7.55 (m, 1H), 7.62 (broad, 1H), 7.64-7.64
N-((4-chlorophenyl)(phenyl)methylene)methanesulfoVnioewhyAdrtricalezOidneline
o
(m, 1H); 13C NMR (100 MHz, CDCl3) δ 39.2, 116.6, 117.0, 124.2, (6o). Yield 41 % (1.27 mg); white solid; mp: 180-183 C; IR (film):
DOI: 10.1039/C6OB00454G
124.6, 125.5, 129.6, 130.2, 131.8, 132.6, 145.3, 157.4, 159.9, 162.0; 3200, 2363, 1485, 1393, 1335, 1314, 1145, 1092, 990, 830 cm-1; H
HRMS (ESI) calcd for C14H13F2N2O2S+ (M+H)+: 311.0666; Found: NMR (400 MHz, CDCl3) δ 3.19 (s, 3H), 7.25-7.32 (m, 4H), 7.46
1
311.0662.
(broad, 1H), 7.49-7.51(m, 2H), 7.56-7.58 (m, 3H); 13C NMR (100
MHz, CDCl3) δ 39.2, 128.3, 128.6, 128.9, 130.0, 130.5, 130.6, 134.7,
136.2, 153.0; HRMS (ESI) calcd for C14H14ClN2O2S+ (M+H)+:
309.0465; Found: 309.0451; Anal. Calcd for C14H13ClN2O2S: C,
54.46; H, 4.24; N, 9.07. Found: C, 54.54; H, 4.22; N, 9.19.
N-((2-Fluorophenyl)(phenyl)methylene)methanesulfonohydrazide
(6j). Yield 91 % (2.65 g); white solid; mp: 196-198 C; IR (film):
2926, 2351, 1590, 1519, 1317, 1159, 982, 836 cm-1; H NMR (400
o
1
MHz, CDCl3) δ 3.19 (s, 3H), 7.26-7.46 (m, 4H), 7.51-7.41 (m, 4H),
7.67-7.69 (m, 1H), 7.84-7.86 (m, 1H); 13C NMR (100 MHz, CDCl3)
N-((3,4-
δ 31.2, 117.0, 118.6, 125.7, 127.2, 127.9, 128.5, 129.7, 130.3, 131.5, dimethylphenyl)(phenyl)methylene)methanesulfonohydrazide (6p).
o
132.7, 135.6, 148.9; HRMS (ESI) calcd for C14H14FN2O2S+ (M+H)+: Yield 25 % (0.73 g); white solid; mp: 193-195 C; IR (film): 3200,
1
293.0760; Found: 293.0758.
1354, 1442, 1396, 1338, 1311, 1145, 1029, 989, 910, 822 cm-1; H
NMR (400 MHz, CDCl3) δ 2.24 (s, 3H), 2.27 (s, 3H), 3.18 (s, 3H),
7.07-7.09 (m, 1H), 7.19-7.21 (dd, J = 7.9 Hz, 1.8 Hz, 1H), 7.24-7.35
(m, 3H), 7.40 (broad, 1H), 7.52-7.57(m, 3H); 13C NMR (100 MHz,
CDCl3) δ 19.8, 19.8, 39.0, 125.5, 128.3, 128.4, 129.6, 129.8, 130.1,
131.3, 133.9, 136.7, 139.2, 154.6; HRMS (ESI) calcd for
C16H19N2O2S+ (M+H)+: 303.1167; Found: 303.1154; Anal. Calcd for
C16H18N2O2S: C, 63.55; H, 6.00; N, 9.26. Found: C, 63.50; H, 5.99;
N, 9.31.
N-((3-
(Methylthio)phenyl)(phenyl)methylene)methanesulfonohydrazide
(6k). Yield 59 % (1.35 g); white solid; mp: 168-170 C; IR (film):
o
3211, 1335, 1319, 1159, 785, 705 cm-1; 1H NMR (400 MHz, CDCl3)
δ 2.45 (m, 3H), 3.19 (s, 3H), 7.27 (m, 5H), 7.45 (s, NH), 7.48 (s, 1H),
7.56-7.57 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 15.8, 39.1, 124.6,
125.6, 127.9, 128.3, 128.8, 129.9, 130.4, 130.8, 136.9, 139.0, 153.6;
HRMS (ESI) calcd for C15H17N2O2S2 (M+H)+: 321.0731; Found:
+
321.0726.
N-((4-Chlorophenyl)(4-
methoxyphenyl)methylene)methanesulfonohydrazide (6q). Yield 25 %
o
N-(Phenyl(4-
(0.85 g); white solid; mp: 144-145 C; IR (film): 3208, 1609, 1485,
1
1381, 1340, 1316, 1159, 1091, 983, 824 cm-1; H NMR (400 MHz,
(trifluoromethyl)phenyl)methylene)methanesulfonohydrazide
Yield 67 % (1.67 g); white solid; mp: 129-131 C; IR (film): 3195,
1612, 1409, 1312, 1162, 1067, 983, 849, 776 cm-1; H NMR (400
(6l).
o
CDCl3) δ 2.37-2.47 (m, 3H), 3.18 (s, 3H), 7.14-7.16 (m, 2H), 7.22-
7.26 (m. 2H), 7.29-7.32 (m, 2H), 7.41-7.43 (m, NH), 7.49-7.56 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 21.4, 21.5, 39.0, 39.1, 127.5,
127.6, 128.2, 128.6, 128.9, 129.2, 129.5, 129.9, 130.2, 130.6, 133.2,
135.0, 136.1, 136.5, 140.7, 140.7, 153.2, 153,2; HRMS (ESI) calcd
for C15H16ClN2O3S+ (M+H)+: 339.0570; Found: 339.0556.
1
MHz, CDCl3) δ 3.19 (m, 3H), 7.26-7.61 (m, 8H), 7.67-7.69 (m, 1H),
7.84-7.86 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 39.1, 39.2, 122.2,
122.5, 124.9, 125.3, 125.3, 125.3, 126.9, 126.9, 127.5, 127.9, 128.3,
128.5, 129.1, 130.1, 130.3, 130.5, 130.6, 131.5, 131.8, 132.2, 132.6,
134.9, 134.9, 135.6, 139.6, 152.4, 152.6; HRMS (ESI) calcd for
C15H14F3N2O2S+ (M+H)+: 343.0728; Found: 343.0715; Anal. Calcd
for C15H13F3N2O2S: C, 52.63; H, 3.83; N, 8.18. Found: C, 52.45; H,
3.83; N, 8.22.
General procedure for the synthesis of 1,1’-diaryl butadienes
from N-mesylhydrazones and allyl bromides.
A 10 mL Schlenk tube was charged with Pd2(dba)3 (4.6 mg, 2.5
mol%), tris(2,6-dimethoxyphenyl)phosphine (17.7 mg, 20 mol%)
and LiOtBu (80.0 mg, 5.0 equiv). After degassed and filled with N2
for 4 times, the tube was charged with 1 mL of THF. The allyl
halides (1.5 equiv) was then added into the mixture. After that, the
N-mesylhydrazone was dissolved in THF (4 mL) and the solution
N-((4-Methoxyphenyl)(phenyl)methylene)methanesulfonohydrazide
(6m). Yield 31 % (0.94 g); white solid; mp: 173-175 C; IR (film):
o
3189, 2357, 1609, 1511, 1317, 1251, 1140, 1029, 989 cm-1; 1H NMR
(400 MHz, CDCl3) δ 3.18 (s, 3H), 3.82 (s, 3H), 6.84-6.86 (m, 2H),
7.25-7.28 (m, 2H), 7.31 (broad, 1H), 7.49-7.58(m, 5H); 13C NMR
(100 MHz, CDCl3) δ 39.0, 55.4, 113.7, 128.3, 129.0, 129.2, 129.8,
130.2, 131.3, 154.2, 161.2; HRMS (ESI) calcd for C15H17N2O3S+
(M+H)+: 305.0960; Found: 305.0959; Anal. Calcd for C15H16N2O3S:
C, 59.19; H, 5.30; N, 9.20. Found: C, 59.23; H, 5.24; N, 9.37.
o
was added dropwise to the reaction via peristaltic pump at 80 C for
o
1 h. The reaction mixture was stirred at 80 C for another 4 h. Then
the mixture was filtrated through a pad of silica gel and washed with
Et2O. Solvent was evaporated under reduced pressure to leave a
crude mixture, which is purified by silica gel column
chromatography to afford the product.
N-([1,1'-Biphenyl]-4-
Buta-1,3-diene-1,1-diyldibenzene (7a).20 Yield 73% (30 mg,
purified by silica gel column chromatography using PE as eluent, Rf
= 0.75); colorless oil; 1H NMR (400 MHz, CDCl3) δ 5.12 (dd, J =
1.8, 10.1 Hz, 1H), 5.41 (dd, J = 1.8, 16.8 Hz, 1H), 6.44 (ddd, J =
16.9, 10.2, 10.8 Hz, 1H), 6.72 (d, J = 11.0 Hz, 1H), 7.21-7.40
(m ,10H); 13C NMR (100 MHz, CDCl3) δ 118.6, 127.4, 127.5, 127.6,
128.2, 128.2, 128.5, 130.4, 135.0, 139.7, 142.1, 143.2.
yl(phenyl)methylene)methanesulfonohydrazide (6n). Yield 12 %
o
(0.36 g); white solid; mp: 204-205 C; IR (film): 3198, 2926, 1606,
1
1485, 1385, 1318, 1162, 983, 844, 769 cm-1; H NMR (400 MHz,
CDCl3) δ 3.21 (s, 3H), 7.26 (broad, 1H), 7.30-7.39 (m, 3H), 7.43-
7.47(m, 3H), 7.56-7.85 (m, 8H); 13C NMR (100 MHz, CDCl3) δ 39.1,
127.0, 127.1, 127.8, 128.1, 128.3, 128.9, 129.9, 130.3, 131.1, 135.2,
140.2, 142.8, 153.9; HRMS (ESI) calcd for C20H19N2O2S+ (M+H)+:
351.1167; Found: 351.1158.
8 | J. Name., 2012, 00, 1-3
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Page 9 of 11
Organic & Biomolecular Chemistry
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Journal Name
ARTICLE
4,4'-(Buta-1,3-diene-1,1-diyl)bis(methoxybenzene) (7b).20 Yield 79 % 3,3'-(Buta-1,3-diene-1,1-diyl)bis(fluorobenzene) (7h)V.2ie2wYAireticldle 5O6nlin%e
DOI: 10.1039/C6OB00454G
(42 mg, purified by silica gel column chromatography using PE:EA (27 mg, purified by silica gel column chromatography using PE as
1
1
= 10:1 as eluent, Rf = 0.38); yellow oil; H NMR (400 MHz, CDCl3) eluent, Rf = 0.66); colorless oil; H NMR (400 MHz, CDCl3) δ 5.21
δ 3.81 (s, 3H), 3.85 (s, 3H), 5.07 (dd, J = 1.6, 9.9 Hz, 1H), 5.34 (dd, (dd, J = 1.1, 10.1 Hz, 1H), 5.45 (dd, J = 0.9, 16.8 Hz, 1H), 6.40 (ddd,
J = 1.6, 16.6 Hz, 1H), 6.45 (ddd, J = 16.7, 10.8, 10.1 Hz, 1H), 6.69 J = 16.8, 10.8, 10.3 Hz, 1H), 6.72 (d, J = 11.0 Hz, 1H), 6.96-7.09 (m,
(d, J = 11.0 Hz, 1H), 6.81-6.83 (m, 2H), 6.90-6.92 (m, 2H), 7.13- 6H), 7.22-7.28 (m, 1H), 7.34-7.39 (m, 1H); 13C NMR (100 MHz,
7.15 (m, 2H), 7.20-7.23 (m, 2H); 13C NMR (100 MHz, CDCl3) δ CDCl3) δ 114.1, 117.1, 120.2, 123.0, 126.1, 129.8, 134.1, 140.5,
55.3, 113.5, 113.6, 117.3, 126.7, 128.9, 131.6, 132.2, 135.1, 135.3, 141.1, 143.7, 161.5, 161.6, 163.9, 164.0.
142.4, 158.9, 159.2.
2,2'-(Buta-1,3-diene-1,1-diyl)bis(fluorobenzene) (7i). Yield 36 %
4,4'-(Buta-1,3-diene-1,1-diyl)bis(methylbenzene) (7c).21 Yield 66 % (18 mg, purified by silica gel column chromatography using PE as
(31 mg, purified by silica gel column chromatography using PE as eluent, Rf = 0.55); yellow oil; IR (film): 1488, 1453, 1248, 1224,
eluent, Rf = 0.70); colorless oil; H NMR (400 MHz, CDCl3) δ 2.22 1065 cm-1; 1H NMR (400 MHz, CDCl3) δ 5.22 (dd, J = 1.2, 10.1 Hz,
1
(s, 3H), 2.39 (s, 3H), 5.08 (dd, J = 1.5, 10.1 Hz, 1H), 5.33 (dd, J = 1H), 5.44 (dd, J = 1.1, 16.9 Hz, 1H), 6.34 (ddd, J = 16.9, 10.8, 10.3
1.9, 17.3 Hz, 1H), 6.45 (ddd, J = 16.8, 10.9, 10.1 Hz, 1H), 6.65 (d, J Hz, 1H), 6.78 (d, J = 11.0 Hz, 1H), 7.00-7.25 (m, 7H), 7.29-7.35 (m,
= 11.0 Hz, 1H), 7.07-7.14 (m, 4H), 7.16-7.24 (m, 4H); 13C NMR 1H); 13C NMR (100 MHz, CDCl3) δ 115.7, 115.9, 115.9, 116.1,
(100 MHz, CDCl3) δ 21.1, 21.3, 117.8, 127.5, 127.6, 128.8, 128.9, 120.3, 123.9, 123.9, 123.9, 126.9, 127.0, 128.9, 129.0, 129.5, 129.5,
130.3, 135.2, 136.8, 137.0, 137.3, 139.5, 143.1.
130.5, 130.5, 131.3, 132.0, 132.1, 134.2, 134.2, 134.3, 158.7, 159.0,
+
161.2, 161.5; HRMS (ESI) calcd for C16H19F2 (M+H)+: 243.0985;
4,4'-(Buta-1,3-diene-1,1-diyl)bis(chlorobenzene) (7d).20 Yield 69 %
(38 mg, purified by silica gel column chromatography using PE as
eluent, Rf = 0.61); yellow oil; 1H NMR (400 MHz, CDCl3) δ 5.17 (dd,
found: 243.0979.
(Z/E)-1-Fluoro-2-(1-phenylbuta-1,3-dien-1-yl)benzene (7j). Yield
J = 1.1, 10.1 Hz, 1H), 5.42 (dd, J = 1.0, 16.7 Hz, 1H), 6.37 (ddd, J = 55 % (25 mg, purified by silica gel column chromatography using
16.8, 10.9, 10.2 Hz, 1H), 6.67 (d, J = 11.0 Hz, 1H), 7.11-7.19 (m, PE as eluent, Rf = 0.60); yellow oil; IR (film): 1487, 1448, 1222, 996,
1
4H), 7.23-7.26 (m, 2H), 7.34-7.38 (m, 2H); 13C NMR (100 MHz, 907 cm-1; H NMR (400 MHz, CDCl3) δ 5.17 (dd, J = 1.1, 10.1 Hz,
CDCl3) δ 119.9, 128.5, 128.6, 128.8, 129.3, 131.7, 133.6, 133.6, 1H), 5.43 (dd, J = 1.0, 16.9 Hz, 1H), 6.22-6.32 (m, 1H), 6.84 (d, J =
134.2, 137.6, 140.2, 140.7.
11.0 Hz, 1H), 7.10-7.38 (m, 9H); 13C NMR (100 MHz, CDCl3) δ
115.7, 116.0, 119.4, 124.0, 124.0, 126.6, 126.7, 126.9, 127.7, 128.4,
129.5, 129.6, 130.0, 132.5, 132.5, 134.5, 136.6, 140.6, 158.9, 161.4;
HRMS (ESI) calcd for C16H14F+ (M+H)+: 225.1080; Found:
225.1074.
4,4'-(Buta-1,3-diene-1,1-diyl)bis(fluorobenzene) (7e).21 Yield 51 %
(25 mg, purified by silica gel column chromatography using PE as
1
eluent, Rf = 0.65); colorless oil; H NMR (400 MHz, CDCl3) δ 5.15
(dd, J = 1.2, 10.0 Hz, 1H), 5.40 (dd, J = 1.1, 16.8 Hz, 1H), 6.38 (ddd,
J = 16.8, 10.9, 10.2 Hz, 1H), 6.63 (d, J = 11.0 Hz, 1H), 6.95-7.02 (m,
(Z/E)-Methyl(3-(1-phenylbuta-1,3-dien-1-yl)phenyl)sulfane
(7k).
2H), 7.05-7.10 (m, 2H), 7.14-7.25 (m, 4H); 13C NMR (100 MHz, Yield 82 % (41 mg, purified by silica gel column chromatography
CDCl3) δ 115.1, 115.3, 119.1, 128.7, 129.2, 132.0, 134.5, 135.3, using PE:EA = 20:1 as eluent, Rf = 0.60); yellow oil; Z/E = 50:50,
138.1, 141.1, 161.2, 163.7.
two sets of resonance signals were observed for the (Z/E)-isomers in
the NMR spectra. 1H NMR (400 MHz, CDCl3) δ 2.44 and 2.46 (s
each, 3:3H), 5.14 and 5.40 (d each, J = 10.1 and 16.9 Hz, 1:1H),
6.43 (m, 2H), 6.70 (m, 2H), 6.97-7.02 (m, 2H), 7.10-7.23 (m, 8H),
7.28-7.40 (m, 8H); 13C NMR (100 MHz, CDCl3) δ 15.7, 15.9, 119.0,
119.0, 124.7, 125.4, 125.6, 125.8, 127.2, 127.5, 127.6, 128.1, 128.2,
128.3, 128.6, 128.8, 129.0, 130.3, 134.8, 134.8, 138.4, 138.5, 139.3,
140.3, 141.76, 142.6, 142.7, 142.8; HRMS (ESI) calcd for C17H17S+
(M+H)+: 253.1051; Found: 253.1045.
3,3'-(Buta-1,3-diene-1,1-diyl)bis(methylbenzene) (7f). Yield 62 %
(29 mg, purified by silica gel column chromatography using PE as
eluent, Rf = 0.68); colorless oil; IR (film): 1604, 1510, 1463, 1285,
1
1246, 1173, 1035 cm-1; H NMR (400 MHz, CDCl3) δ 2.31 (s, 3H),
2.35 (s, 3H), 5.10 (dd, J = 1.9, 10.1 Hz, 1H), 5.37 (dd, J = 1.8, 16.8
Hz, 1H), 6.45 (ddd, J = 16.8, 11.0, 10.1 Hz, 1H), 6.67 (d, J = 11.0
Hz, 1H), 7.01-7.29 (m, 8H); 13C NMR (100 MHz, CDCl3) δ 21.4,
21.5, 118.2, 124.9, 127.5, 128.0, 128.1, 128.1, 128.2, 128.3, 130.9,
135.1, 137.1, 139.7, 132.2, 143.4; HRMS (ESI) calcd for C18H19
(M+H)+: 235.1487; Found: 235.1481.
+
(Z/E)-1-(1-Phenylbuta-1,3-dien-1-yl)-4-(trifluoromethyl)benzene
(7l). Yield 73 % (40 mg, purified by silica gel column
chromatography using PE:EA = 40:1 as eluent, Rf = 0.70); yellow oil;
IR (film): 1326, 1167, 1127, 1068, 1017, 911, 842 cm-1; Z/E = 51:49,
Two sets of resonance signals were observed for the (Z/E)-isomers in
3,3'-(Buta-1,3-diene-1,1-diyl)bis(methoxybenzene) (7g). Yield 66 %
(35 mg, purified by silica gel column chromatography using PE:EA
= 10:1 as eluent, Rf = 0.35); yellow oil; IR (film): 1596, 1576, 1486,
1463, 1432, 1285, 1159 cm-1; 1H NMR (400 MHz, CDCl3) δ 3.77 (s,
3H), 3.79 (s, 3H), 5.13 (dd, J = 1.6, 10.1 Hz, 1H), 5.39 (dd, J = 1.5,
16.8 Hz, 1H), 6.45 (ddd, J = 16.9, 10.8, 10.2 Hz, 1H), 6.70 (d, J =
11.0 Hz, 1H), 6.75-6.89 (m, 6H), 7.18-7.31 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 55.3, 112.9, 113.1, 115.8, 118.8, 120.2, 122.9, 128.7,
129.1, 129.2, 134.9, 140.9, 142.8, 143.3, 159.4, 159.5; HRMS (ESI)
calcd for C18H19O2+ (M+H)+: 267.1385; Found: 267.1379.
1
the NMR spectra. H NMR (400 MHz, CDCl3) δ 5.20 (m, 2H), 5.43
and 5.47 (dd each, J = 1.0 and 5.9 Hz, 1:1H), 6.32-6.50 (m, 2H),
6.74 and 6.77 (d each, J = 11.1 Hz, 1:1H), 7.19-7.66 (m, 18H); 13C
NMR (100 MHz, CDCl3) δ 119.9, 120.1, 125.1, 125.2, 125.2, 125.2,
127.5, 127.8, 127.9, 128.4, 129.1, 129.4, 129.7, 130.3, 130.3, 130.8,
134.2, 134.6, 138.9, 141.3, 141.6, 141.8, 143.5, 145.6; HRMS (ESI)
calcd for C17H14F3+ (M+H)+: 275.1048; Found: 275.1042.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
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Organic & Biomolecular Chemistry
Page 10 of 11
ARTICLE
(Z/E)-1-Methoxy-4-(1-phenylbuta-1,3-dien-1-yl)benzene
Journal Name
(7m).20
(E)-Penta-1,3-diene-1,1-diyldibenzene (7r).24 Yield 77 % (34 mg,
View Article Online
DOI: 10.1039/C6OB00454G
Yield 66 % (31 mg, purified by silica gel column chromatography purified by silica gel column chromatography using PE as eluent, Rf
using PE:EA = 20:1 as eluent, Rf = 0.70); yellow oil; Z/E = 51:49, = 0.68); colorless oil; 1H NMR (400 MHz, CDCl3) δ 1.74 (d, J = 6.8
Two sets of resonance signals were observed for the (Z/E)-isomers in Hz, 3H), 5.86-5.95 (m, 1H), 6.12-6.18 (m, 1H), 6.67 (d, J = 10.9 Hz,
1
the NMR spectra. H NMR (400 MHz, CDCl3) δ 2.44 and 2.47 (s 1H), 7.21-7.28 (m, 8H), 7.33-7.41 (m, 2H); 13C NMR (100 MHz,
each, 3:3H), 5.13 and 5.16 (m each, 2H), 5.38 and 5.42 (m each, 2H), CDCl3) δ 18.5, 127.0, 127.1, 127.4, 128.1, 128.2, 128.3, 129.7,
6.38-6.48 (m, 2H), 6.68 and 6.73 (d each, J = 11.0 Hz, 1:1H), 6.97- 130.5, 131.7, 140.0, 140.0, 142.5.
7.40 (m, 18H); 13C NMR (100 MHz, CDCl3) δ 55.3, 113.5, 113.6,
(4-Methylpenta-1,3-diene-1,1-diyl)dibenzene (7s).20 Yield 65% (30
117.6, 118.2, 126.9, 127.3 127.5, 127.7, 128.2, 128.3, 128.7, 120.4,
mg, purified by silica gel column chromatography using PE as eluent,
Rf = 0.70); colorless oil; IR (film): 1602, 1485, 997, 787, 773 cm-1;
1H NMR (400 MHz, CDCl3) δ 1.76 (s, 3H), 1.89 (s, 3H), 5.90 (d, J =
131.7, 131.9, 135.1, 139.9, 142.5, 142.8, 158.9; HRMS (ESI) calcd
for C17H17O+ (M+H)+: 237.1279; Found: 237.1274.
(Z/E)-4-(1-Phenylbuta-1,3-dien-1-yl)-1,1'-biphenyl (7n).21 Yield 11.4 Hz, 1H), 6.87 (d, J = 11.4 Hz, 1H), 7.21-7.40 (m, 10H); 13C
57 % (32 mg, purified by silica gel column chromatography using NMR (100 MHz, CDCl3) δ 18.7, 26.6, 123.2, 124.5, 126.9, 127.0,
1
PE as eluent, Rf = 0.66); white solid; H NMR (400 MHz, CDCl3) δ 127.5, 128.1, 128.2, 130.6, 137.8, 139.7, 140.2, 143.1; HRMS (ESI)
5.15 (m, 1H), 5.42 (m, 1H), 6.40-6.58 (m, 1H), 6.72-6.80 (m, 1H), calcd for C19H19+ (M+H)+: 247.1487; Found: 247.1481.
7.25-7.66 (m, 14H); 13C NMR (100 MHz, CDCl3) δ 118.7, 118.8,
(Cyclohex-2-en-1-ylidenemethylene)dibenzene (7t). Yield 48% (24
mg, purified by silica gel column chromatography using PE as eluent,
Rf = 0.60); yellow oil; IR (film): 1490, 1442, 1074, 1030, 761, 680
126.9, 126.9, 127.0, 127.1, 127.4, 127.4, 127.5, 127.6, 128.4, 128.7,
128.7, 127.8, 128.0, 128.3, 128.5, 128.8, 128.9, 130.5, 130.9, 135.0,
138.7, 139.6, 140.2, 140.3, 140.7, 140.8, 141.0, 142.2, 142.7, 142.8.
1
cm-1; H NMR (400 MHz, CDCl3) δ 1.74 (q, J = 6.1 Hz, 2H), 2.18
(Z/E)-1-Chloro-4-(1-phenylbuta-1,3-dien-1-yl)benzene
(7o).23 (m, 2H), 2.46 (t, J = 6.2 Hz, 2H), 5.83 (dt, J = 10.1, 4.1 Hz, 1H),
Yield 45 % (22 mg, purified by silica gel column chromatography 6.25 (dt, J = 10.1, 2.1 Hz, 1H), 7.13-7.30 (m, 10H); 13C NMR (100
using PE as eluent, Rf = 0.68); yellow oil; Z/E = 50:50, Two sets of MHz, CDCl3) δ 23.3, 26.0, 29.1, 126.4, 126.5, 127.7, 127.8, 130.3,
resonance signals were observed for the (Z/E)-isomers in the NMR 130.6, 130.9, 133.0, 136.9, 142.2, 142.4.
1
spectra. H NMR (400 MHz, CDCl3) δ 5.14-5.18 (m, 2H), 5.39 and
(3-Methylbuta-1,3-diene-1,1-diyl)dibenzene (7u).24 Yield 49% (22
5.43 (m each,1:1H), 6.36-6.47 (m, 2H), 6.67-6.72 (m, 2H), 7.14-7.41
(m, 18H); 13C NMR (100 MHz, CDCl3) δ 119.2, 119.3, 127.6, 127.6,
127.7, 128.2, 128.3, 128.4, 128.5, 128.8, 128.8, 129.0, 130.4, 131.8,
133.3, 133.4, 134.5, 134.8, 138.1, 139.2, 140.6, 141.7, 141.8, 141.9.
mg, purified by silica gel column chromatography using PE as eluent,
1
Rf = 0.65); white oil; H NMR (400 MHz, CDCl3) δ 1.47 (s, 3H),
4.97 (s, 1H), 5.19 (m, 1H), 6.86 (s, 1H), 7.19-7.26 (m, 6H), 7.31-
7.35 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 22.1, 114.3, 119.1,
(Z/E)-1,2-Dimethyl-4-(1-phenylbuta-1,3-dien-1-yl)benzene (7p).21 127.2, 127.5, 128.0, 128.1, 130.3, 130.8, 140.7, 141.5, 142.5, 143.3.
Yield 46 % (22 mg, purified by silica gel column chromatography
using PE as eluent, Rf = 0.75); colorless oil; Z/E = 51:50, Two sets of
Acknowledgements
resonance signals were observed for the (Z/E)-isomers in the NMR
spectra. 1H NMR (400 MHz, CDCl3) δ 2.22-2.25 (s each, 3:3H),
This project was supported by the National Basic Research
2.26-2.30 (s each, 3:3H), 5.11 (m, 2H), 5.35 and 5.38 (m each, 1:1H),
Program of China (973 Program, 2012CB821600) and the
6.37-6.52 (m, 2H), 6.67-6.68 (d each, J = 11.0 Hz, 1:1H), 6.95-7.00
(m, 3H), 7.04-7.22 (m, 6H), 7.28-7.40 (m, 7H); 13C NMR (100 MHz,
CDCl3) δ 19.5, 19.6, 19.8, 19.9, 118.0, 118,1, 125.2, 127.3, 127.7,
127.9, 128.1, 128.2, 128.7, 129.5, 129.5, 130.4, 131.5, 135.1, 135.3,
135.8, 136.2, 136.3, 137.1, 139.7, 139.9, 142.4, 143.2, 143.3.
National Natural Science Foundation of China (Grant
21472004 and 21332002)
.
Notes and references
1
(a) G. Wang, S. Mohan, E. Negishi, Proc. Natl. Acad. Sci. U. S. A. 2011,
108, 11344. (b) Biermann, U. Bornscheuer, M. A. R. Meier, J. O.
Metzger, H. J. Schäfer, Angew. Chem., Int. Ed., 2011, 50, 3854. (c) W.
Erb, J. P. Zhu, Nat. Prod. Rep. 2013, 30, 161.
For recent examples of 1,3-dienes in organic Synthesis, see: (a) B. Maji,
H. Yamamoto, J. Am. Chem. Soc., 2015, 137, 15957. (b) P. Yu, A. Patel,
K. Houk, J. Am. Chem. Soc., 2015, 137, 13518. (c) E. Mackay, M.
Nörret, L. S. Wong, I. Louis, A. Lawrence, A. Willis, M. Sherburn, Org.
Lett., 2015, 17, 5517. (d) J. Ishihara, S. Nakadachi, Y. Watanabe, S.
Hatakeyama, J. Org. Chem., 2015, 80, 2037. (e) V. Eschenbrenner-Lux,
K. Kumar, H. Waldmann, Angew. Chem., Int. Ed., 2014, 53, 11146. (f)
R. Patel, N. Argade, Org. Lett., 2013, 15, 14.
For reviews, see: (a) G. Mehta, R. Uma, Acc. Chem. Res., 2000, 33, 278.
(b) B. M. Trost, F. D.Toste, A. B. Pinkerton, Chem. Rev., 2001, 101,
2067. (c) C. Aubert, O. Buisine, M. Malacria, Chem. Rev., 2002, 102,
813. (d) S. T. Diver, A. J. Giessert, Chem. Rev., 2004, 104, 1317. (e) B.
M. Trost, M. U. Frederiksen, M. T. Rudd, Angew. Chem., Int. Ed., 2005,
(Z/E)-1-Chloro-4-(1-(4-methoxyphenyl)buta-1,3-dien-1-yl)benzene
(7q). Yield 52
% (28 mg, purified by silica gel column
chromatography using PE:EA = 10:1 as eluent, Rf = 0.36); yellow oil;
IR (film): 1511, 1489, 1419, 1394, 1090, 1015, 909 cm-1; Z/E =
50:50, Two sets of resonance signals were observed for the (Z/E)-
isomers in the NMR spectra. 1H NMR (400 MHz, CDCl3) δ 2.34 and
2.39 (s each, 3:3H), 5.12 and 5.15 (s each, 1:1H), 5.37 and 5.41 (s
each, 1:1H), 6.37-6.49 (m, 2H), 6.84-6.70 (m, 2H), 7.07-7.16 (m,
8H), 7.19-7.26 (m, 6H), 7.34-7.36 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 21.2, 21.3, 118.8, 118.9, 127.4, 128.1, 128.2, 128.3, 128.4,
128.7, 128.9, 129.0, 129.0, 129.6, 130.3, 131.8, 133.3, 134.6, 134.9,
136.2, 137.4, 137.7, 138.2, 138.8, 140.8, 141.8, 142.0; HRMS (ESI)
calcd for C17H16ClO+ (M+H)+: 271.0890; Found: 271.0884.
2
3
10 | J. Name., 2012, 00, 1-3
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Page 11 of 11
Organic & Biomolecular Chemistry
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Journal Name
ARTICLE
44, 6630. (c) E. Negishi, Z. H. Huang, G. W. Wang, S. Mohan, C.
C. Valdés, Chem. – Eur. J., 2015, 21, 16463. (h) Ò. Torres, T. Parella,
Wang, H. Hattori, Acc. Chem. Res., 2008, 41, 1474. For selected
examples, see: (f) T. Mitsudo, S.-W. Zhang, M. Nagao, Y. Watanabe, J.
Chem. Soc., Chem. Commun., 1991, 598. (g) M. Murakami, M.
Ubukata, Y. Ito, Tetrahedron Lett., 1998, 39, 7361. (h) A. T. Lindhardt,
M. L. H. Mantel, T. Skrydstrup, Angew. Chem., Int. Ed., 2008, 47, 2668.
(i) Y. Shibata, M. Hirano, K. Tanaka, Org. Lett., 2008, 10, 2829. (j) S.
Mannathan, C.-H. Cheng, Chem. Commun., 2010, 1923.
M. Solà, A. Roglans, A. Pla-Quintana, Chem. – EuVr.iewJ.A, rt2ic0l1e5O,nl2in1e,
DOI: 10.1039/C6OB00454G
16240. (i) P. Xu, F.-S. Han, Y.-H. Wang, Adv. Synth. Catal., 2015, 357,
3441. (j) M. Roche, S. M. Salim, J. Bignon, H. Levaique, J.-D. Brion,
M. Alami, A. Hamze, J. Org. Chem., 2015, 80, 6715. (k) M. Kitamura,
R. Yuasa, D. L. Van Vranken, Tetrahedron Lett., 2015, 56, 3027. (l) X.
S. Shang, N. T. Li, X. H. Siyang, P. N. Liu, J. Org. Chem., 2015, 80,
4808.
4
5
(a) B. E. Maryanoff, A. B. Reitz, Chem. Rev., 1989, 89, 863. (b) M. 14 (a) X. Feng, J. Wang, J. Zhang, J. Yang, N. Wang, X. Yu, Org. Lett.,
Julia, J. M. Paris, Tetrahedron Lett., 1973, 29, 4833. (c) J. Pospisil, T.
Pospisil, I. E. Marko, Org. Lett., 2005, 7, 2373. (d) L. F. van Staden, D.
Gravestock, D. J. Ager, Chem. Soc. Rev., 2002, 31, 195. (e) H. Cui, Y.
Li, S. Zhang, Org. Biomol. Chem., 2012, 10, 2862.
2010, 12, 4408. (b) J. Barluenga, M. Tomás-Gamasa, F. Aznar, C.
Valdés, Eur. J. Org. Chem., 2011, 1520. In these reports, sulfones were
obtained via nucleophilic attack of sulfinate group upon the metal
carbene. Results showed that the yield of methyl sulfone were lower
than that of tolyl sulfones, presumably due to the weak nucleophilicity
of the mesyl anion as compared with the corresponding tosyl anion.
(a) X. Shang, Z. Q. Liu, Chem. Soc. Rev., 2013, 42, 3253. (b) J. K.
Stille, Angew. Chem., Int. Ed. Engl., 1986, 25, 508. (c) W. Cabri, I.
Candiani, Acc. Chem. Res., 1995, 28, 2. (d) C. Zheng, D. Wang, S. 15 For reports on the migratory insertion of stable palladium carbene
Stahl, J. Am. Chem. Soc., 2012, 134, 16496. (e) E. Negishi, Angew.
Chem., Int. Ed., 2011, 50, 6738. (f) Y. Zhang, Z. Cui, Z. Li, Z.-Q. Liu,
Org. Lett., 2012, 14, 1838.
(a) C. Aubert, O. Buisine, M. Malacria, Chem. Rev., 2002, 102, 813. (b)
B. M. Trost, F. D. Toste, A. B. Pinkerton, Chem. Rev., 2001, 101, 2067.
(c) Y. Shibata, M. Hirano, K. Tanaka, Org. Lett., 2008, 10, 2829. (d) N.
Saito, K. Saito, M. Shiro, Y. Sato, Org. Lett., 2011, 13, 2718.
(a) K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem., Int. Ed.,
2005, 44, 4442. (b) E. Negishi, Z. Huang, G. Wang, S. Mohan, C.
Wang, H. Hattori, Acc. Chem. Res., 2008, 41, 1474. (c) A. Deagostino,
C. Prandi, C. Zavattaro, P. Venturello, Eur. J. Org. Chem., 2006, 2463.
(d) M. Lemhadri, A. Battace, F. Berthiol, T. Zair, H. Doucet, M.
Santelli, Synthesis, 2008, 1142. (e) J. Huang, Y. Dong, X. -X. Wang, H.
-C. Luo, Chem. Commun., 2010, 46, 1035.
For reviews, see: (a) Q. Xiao, Y. Zhang, J. Wang, Acc. Chem. Res.,
2013, 46, 236. (b) Y. Zhang, J. Wang, Eur. J. Org. Chem., 2011, 6,
1015. (c) Z. Shao, H. Zhang, Chem. Soc. Rev., 2012, 41, 560. (d) J.
Barluenga, C. Valdés, Angew. Chem., Int. Ed., 2011, 50, 7486. (e) Z.
Liu, J. Wang, J. Org. Chem., 2013, 78, 10024. (f) Y. Xia, Y. Zhang, J.
Wang, ACS Catal., 2013, 3, 2586.
species, see: (a) A. C. Albéniz, P. Espinet, R. Manrique, A. Pérez-
Mateo, Angew. Chem., Int. Ed., 2002, 41, 2363. (b) M. Bröring, C. D.
Brandt, S. Stellwag, Chem. Commun., 2003, 2344. (c) D. Solé, L.
Vallverdú, X. Solans, M. Font-Bardia, J. Bonjoch, Organometallics,
2004, 23, 1438. (d) A. C. Albéniz, P. Espinet, R. Manrique, A. Pérez-
Mateo, Chem. – Eur. J., 2005, 11, 1565. (e) A. C. Albéniz, P. Espinet,
A. Pérez-Mateo, A. Nova, G. Ujaque, Organometallics, 2006, 25, 1293.
(f) V. É. Trépanier, E. Fillion, Organometallics, 2007, 26, 30. (g) J. M.
Goll, E. Fillion, Organometallics, 2008, 27, 3622. (h) I. Meana, A. C.
Albéniz, P. Espinet, Organometallics, 2012, 31, 5494. For
computational studies on palladium-catalyzed reactions involving
carbene species, see: (i) Y. Xia, S. Qu, Q. Xiao, Z.-X. Wang, P. Qu, L.
Chen, Z. Liu, L. Tian, Z. Huang, Y. Zhang, J. Wang, J. Am. Chem. Soc.,
2013, 135, 13502. (j) F. Ye, S. Qu, L. Zhou, C. Peng, C. Wang, J.
Cheng, M. L. Hossain, Y. Liu, Y. Zhang, Z.-X. Wang, J. Wang, J. Am.
Chem. Soc., 2015, 137, 4435.
6
7
8
9
16 A stoichiometric reaction of -allylic nickel complex with ethyl
diazoacetate to give 1,3-diene compounds was reported previously, see:
I. Moritani, Y. Yamamoto, H. Konishi, J. Chem. Soc. D: Chem.
Commun., 1969, 1457.
For selected recent examples: (a) G. Qin, L. Li, J. Li, H. Huang, J. Am.
Chem. Soc., 2015, 137, 12490. (b) M. Kitamura, R. Yuasa, D. L. Van
Vranken, Tetrahedron Lett., 2015, 56, 3027. (c) P.-X. Zhou, Y.-Y. Ye,
L.-B. Zhao, J.-Y. Hou, X. Kang, D.-Q. Chen, Q. Tang, J.-Y. Zhang, Q.-
X. Huang, L. Zheng, J.-W. Ma, P.-F. Xu, Y.-M. Liang, Chem. – Eur. J.,
2014, 20, 16093. (d) J. Aziz, G. Frison, M. Gómez, J.-D. Brion, A.
Hamze, M. Alami, ACS Catal., 2014, 4, 4498. (e) P.-S. Wang, H.-C.
Lin, X.-L. Zhou, L.-Z. Gong, Org. Lett., 2014, 16, 3332. (f) P.-X. Zhou,
Y.-Y. Ye, J.-W. Ma, L. Zheng, Q. Tang, Y.-F. Qiu, B. Song, Z.-H. Qiu,
P.-F. Xu, Y.-M. Liang, J. Org. Chem., 2014, 79, 6627. (g) P.-X. Zhou,
L. Zheng, J.-W. Ma, Y.-Y. Ye, X.-Y. Liu, P.-F. Xu, Y.-M. Liang, Chem.
– Eur. J., 2014, 20, 6745. (h) R. Barroso, R. A. Valencia, M.-P. Cabal,
C. Valdés, Org. Lett., 2014, 16, 2264. (i) Y. Xia, Z. Liu, Y. Zhang, J.
Wang, J. Org. Chem., 2014, 79, 7711.
17 N. S. Mani, C. M. Mapes, J. Wu, X. Deng, T. K. Jones, J. Org. Chem.,
2006, 71, 5039.
18 A. Llebaria, F. Camps, J. M. Moretó, Tetrahedron, 1993, 49, 1283.
19 F. G. Stakem, R. F. Heck, J. Org. Chem., 1980, 45, 3584.
20 H. Cui, Y. Li, S. Zhang, Org. Biomol. Chem., 2012, 10, 2862.
21 L. Zhou, F. Ye, Y. Zhang, J. Wang, Org. Lett., 2012, 14, 922.
22 J. Drexler, R. Lindermayer, M. A. Hassan, J. Sauer, Tetrahedron Lett.,
1985, 26, 2559.
23 Q. Yang, H. Chai, T. Liu, Z. Yu, Tetrahedron Lett., 2013, 54, 6485.
24 T. Mitsudo, M. Kadokura, Y. Watanabe, J. Org. Chem., 1987, 52, 1695.
10 S. Chen, J. Wang, Chem. Commun., 2008, 4198.
11 Q. Xiao, B. Wang, L. Tian, Y. Yang, J. Ma, Y. Zhang, S. Chen, J.
Wang, Angew. Chem., Int. Ed., 2013, 52, 9305.
12 For the details, see Electronic Supplementary Information.
13 For the review on the use of N-tosylhydrazones as carbene precursors,
see: (a) J. R. Fulton, V. K. Aggarwal, J. de Vicente, Eur. J. Org. Chem.,
2005, 1479. For selected recent examples of transition-metal-catalyzed
cross-coupling with N-tosylhydrazones, see: (b) X. Li, X. Liu, H. Chen,
W. Wu, C. Qi, H. Jiang, Angew. Chem., Int. Ed., 2014, 53, 14485. (c) A.
Yada, S. Fujita, M. Murakami, J. Am. Chem. Soc., 2014, 136, 7217. (d)
P.-X. Zhou, Y.-Y. Ye, J.-W. Ma, L. Zheng, Q. Tang, Y. F. Qiu, B. Song,
Z. H. Qiu, P. F. Xu, Y.-M. Liang, J. Org. Chem., 2014, 79, 6627. (e) Z.
Liu, H. Tan, T. Fu, Y. Xia, D. Qiu, Y. Zhang, J. Wang, J. Am. Chem.
Soc., 2015, 137, 12800. (f) D. Arunprasath, P. Muthupandi, G. Sekar,
Org. Lett., 2015, 17, 5448. (g) R. Barroso, M.-P. Cabal, R. Badía-Laiño,
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