Palladium-catalyzed, ligand-free SN2’ substitution reactions of organoaluminum with propargyl acetates for the synthesis of multi-substituted allenes

Article abstract of DOI:10.1016/j.jorganchem.2018.06.020

We describe a convenient method for the synthesis of multi-substituted allenes from S_N2′ substitution reactions organoaluminum with propargyl acetates: The S_N2′ substitution reaction of organoaluminum (0.4 mmol) with propargyl acetat

Full text of DOI:10.1016/j.jorganchem.2018.06.020

Accepted Manuscript
Palladium-catalyzed, ligand-free S 2’ substitution reactions of organoaluminum with
N
propargyl acetates for the synthesis of multi-substituted allenes
Xuebei Shao, Chang Wen, Gang Zhang, Kangping Cao, Ling Wu, Qinghan Li
PII:
S0022-328X(18)30516-3
10.1016/j.jorganchem.2018.06.020
JOM 20479
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 25 February 2018
Revised Date: 17 June 2018
Accepted Date: 24 June 2018
Please cite this article as: X. Shao, C. Wen, G. Zhang, K. Cao, L. Wu, Q. Li, Palladium-catalyzed,
ligand-free S 2’ substitution reactions of organoaluminum with propargyl acetates for the
N
synthesis of multi-substituted allenes, Journal of Organometallic Chemistry (2018), doi: 10.1016/
j.jorganchem.2018.06.020.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Palladium-catalyzed, ligand free SN2’
substitution reactions of organoaluminum
with propargyl acetates for the synthesis of
multi-substituted allenes
Leave this area blank for abstract info.
Xuebei Shao, Chang Wen, Gang Zhang, Kangping Cao, Ling Wu, Qinghan Li
R3
R
OAc
Pd(dppf)Cl2 (1 mol%)
K2CO3 (1.0 equiv)
R1
•
R
R1
R1
+ AlR3
R2
R3
R3
THF (2 mL), 4 h, 60 oC
R2
R2
1
2 or 4
3 or 5
R = CH3
2:3 = 99:1
58-98% yield
50-94% yield
R = CH3, C2H5
R1 = alkyl, aryl
4:5 = 95:5~99:1
R = C2H5
R2 = (hetero)aryl
R3 = H, CH3, C2H5

1
ACCEPTED MANUSCRIPT
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com
Palladium-catalyzed, ligand-free SN2’ substitution reactions of organoaluminum with
propargyl acetates for the synthesis of multi-substituted allenes
Xuebei Shao, Chang Wen, Gang Zhang, Kangping Cao, Ling Wu, Qinghan Li
College of Chemistry and Environmental Protection Engineering, Southwest University for Nationalities,Chengdu, 610041, China.
ARTICLE INFO
ABSTRACT
We describe a convenient method for the synthesis of multi-substituted allenes from SN2’
substitution reactions organoaluminum with propargyl acetates: The SN2’ substitution reaction
of organoaluminum (0.4 mmol) with propargyl acetates (0.5 mmol) mediated by PdCl2(dppf) (1
Article history:
Received
Received in revised form
Accepted
o
mol%) at 60 C in THF without ligand could produce multi-substituted allenes in moderate to
good yields(up to 98%) and high selectivities (up to 99%). Their structures have been
Available online
determined by HRMS and 1H(13C)NMR data.
2009 Elsevier Ltd. All rights reserved
.
Keywords:
allenes
palladium
propargyl acetate
organoaluminum reagent
SN2’ substitution reaction
o
1. Introduction
reagent at 60 C in short reaction time with good yields for tri-
and tetra-substituted allenes. The process was simple and easily
performed, and it provides an efficient method for the synthesis
of multi-substituted allene derivatives. Notably, in our procedure
palladium is used as the single catalyst and ligands free.
Allenes are very useful building blocks and functional groups
that are widely applied for many transformations in organic
synthesis[1-9]. Allene moieties have also been found in natural
products [10-11], pharmaceuticals[10-11], and molecular
materials [12]. Because of these, the synthesis of allenes has
inspired ample interest of organic and medical chemistry.
Developing efficient reactions for the synthesis of allenes from
simple and readily available organic compounds is very
important[13-36]. Until now numerous synthetic methodologies
have been developed to access allenes[37-47]. Among these
methods hitherto developed, the metal-catalyzed SN2’-type
displacement of propargyl alcohol derivatives with organometal
species is one of the most generally useful ones (Scheme 1) [43-
46]. However, this type of reactions has been less explored due to
a complication of two competitive pathways. A key success of
this reaction relies mainly on suitable catalytic systems and/or
appropriate organometallic reagents that can selectively produce
either compound 2 or 3. Therefore, the development of rapid and
more efficient procedures for the synthesis of allenes still
remains a challenge.
R2
R2
R1
Nu.
R1
Nu
2
LnM
SN2'
LnM
R2
X
R2
R2
X
LnM
SN2
R1
Nu.
MLn
Nu
R1
R1
X
3
Scheme 1. SN2’ and SN2 processes of metal-catalyzed coupling
reactions of propargyl derivatives with organometallic nucleophiles.
2. Results and Discussion
Our initial studies used 1,3-diphenylprop-2-ynyl acetate (1a)
[33,59] and trimethylaluminum(AlMe3) as model substrates.
According to our previous studied results, in preliminary study,
treatment of propargyl acetate (1a) with AlMe3 use various
palladium salt as catalyst and K2CO3 (1.0 equiv.) as base without
ligand in THF at 60 oC for 6 h. The results showed that Pd(OAc)2,
Pd(PPh3)4, Pd(PPh3)2Cl2 and PdCl2(dppf) were all effective in
catalyzing the SN2’ substitution reaction of AlMe3 with propargyl
acetate (1a) (Table 1, entries 1-4). However, the catalytic system
Our previous studies show that organoaluminium reagents are
highly efficient nucleophiles for cross-coupling reactions with
aromatic halides[48-50] or benzylic halides[51], and the
investigations have demonstrated that palladium is a good
catalytic metal[52-53]. To continue our effort to develop coupling
reactions using reactive organometallic reagents[33-34, 54-58],
we herein report a palladium(II)-catalyzed, ligand free SN2’-
substitution reactions of propargyl acetates with organoaluminum
———
Corresponding author. Tel.: +0086-28-8592-8015; fax: +86-28-8552-4382; e-mail: lqhchem@163.com, lqhchem@swun.cn

2
Journal of Organometallic Chemistry
higheAst CCEPTED MANUSCRIPT
of PdCl2(dppf)/K2CO3 showed the
capability of
conditions, and the results are summarized in Table 2 (entries 1-
conversion (100%) among metals/ K2CO3 combinations (Table 1,
entry 6). While using K3PO4 as base, the PdCl2(dppf)-catalyzed
the SN2’ substitution reaction of propargyl acetate (1a) with
AlMe3 produced the product 1-methyl-1,3-diphenyl-allene (2a)13
and 1,3-diphenylbutyne (3a) only in 45% conversion (Table 1,
entry 7). When treatment of propargyl acetate (1a) with AlMe3 in
2). A brief examination of the influence of solvent on the
conversion of the product 2a and 3a revealed that THF was the
solvent of choice. In toluene or hexane, the conversion was less
efficient (Table 2, entries 1-2). Further studies indicated that the
reaction time influenced the conversion of the product 2a and 3a.
It was found that the most favorable reaction time is 4 h (Table 2,
entry 4). Extensive screening showed that the optimized the SN2’
substitution reaction conditions were 1 mol % Pd(PPh3)2Cl2, 1.0
mmol K2CO3, 0.4 mmol AlMe3, 0.5 mmol propargyl acetate in
THF at 60 oC for 4 h.
o
THF at 60 C in the absence of K2CO3 to afford both 1-methyl-
1,3-diphenyl-allene (2a) and 1,3-diphenylbutyne (3a) with only a
81% conversion and a ratio of 28: 72 in favor of the alkyne 3a
(Table 1, entry 8). Compared with the results of Entry 6, it can be
seen that potassium carbonate plays an important role in the
reaction, which may be the result of the formation of aluminum
carbonate adducts.
Table 3. PdCl2(dppf)-catalyzed the SN2’ substitution reaction of propargyl
a
acetates with AlMe3
.
R
Me
OAc
Table 1 Effect of the palladium source, the loading of Me3Al and the base on
PdCl2(dppf)(1 mol%)
R2
a
R2
AlMe3
+
Me
+
R2
THF (2 mL), 4 h, 60 o
K2CO3(1.0equiv.)
C
the SN2’ substitution reaction.
R
R
R1
R1
R1
Me
OAc
1
2
3
1 mol% PdLn
Me
Ph
Entry
1
2
3
4
5
6
7
8
1
R
H
H
H
H
H
H
H
H
H
R1
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
R2
Ph
2-MePh
3-MePh
4-MePh
2-MeOPh
2-ClPh
Prod.
2a
2b
2c
2d
2e
2f
2g
2h
2i
2j
2k
2l
2m
2n
2o
2p
2q
2r
2s
2:3b 2Yield(%)c
99/1 97
99/1 85
99/1 97
99/1 98
99/1 97
99/1 95
99/1 66
99/1 87
99/1 80
99/1 89
99/1 91
99/1 73
99/1 66
99/1 95
99/1 91
99/1 97
99/1 80
99/1 89
99/1 63(66)d
99/1 92
99/1 70
99/1 58
99/1 84
99/1 74
Ph
+
AlMe3
+
Ph
THF, 60 oC, 6 h
Base (1.0equiv.)
Ph
Ph
1a
1b
1c
1d
1e
1f
1g
1h
1i
Ph
1a
2a
3a
Entry PdLn
Base
K2CO3
K2CO3
Conv. (%)b
5
11
2a/3a(%)c
99/1
99/1
1
PdCl2
2
Pd(acac)2
3
4
5
6
7
8
Pd(PPh3)2Cl2
Pd(OAc)2
Pd(PPh3)4
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
K2CO3
K2CO3
K2CO3
K2CO3
K3PO4
-
K2CO3
K2CO3
K2CO3
K2CO3
35
21
53
100
45
99/1
99/1
99/1
99/1
4-BrPh
1- naphthyl
2- naphthyl
Me
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
1j Me Ph
99/1
1k Me 2-FPh Me
1l Me 3-BrPh Me
1m Me 2-thienyl Me
1n Me Ph
1o Me 2-FPh
1p Me 3-FPh Et
1q Me 4-FPh Et
1r Me 3-ClPh Et
1s Me 3-BrPh Et
1t Me 4-MePh Et
1u Me 2-thienyl Et
1v Me Ph
1w Me Ph
1x Me Ph
81
28/72
64/36
99/1
99/1
99/1
9d
10e
11f
12g
100
100
100
40
Et
Et
a1a/AlMe3/PdLn = 0.5/0.5/0.005mmol. b Conversion of 2a+3a was determined
1
c
1
d
by H NMR spectra. The ratio of 2a/3a was determined by HNMR. 1a
e
f
/AlMe3/PdLn = 0.5/0.3/0.005mmol. 1a/AlMe3/PdLn = 0.5/0.4/0.005mmol.
1a/AlMe3/PdLn = 0.5/0.6/0.005mmol. g1a/AlMe3/PdCl2(dppf)/K2CO3 = 0.5/
2t
2u
2v
2w
2x
0.4/0.005/0.5 mmol, R.T.
Ph
4-ClPh
4-FPh
Subsequently, the effect of the amount of AlMe3 was also
investigated. When the AlMe3 loading was decreased from 0.5
mmol to 0.4 mmol or increased from 0.5 mmol to 0.6 mmol, the
reaction conversation and selectivity remained unchanged (Table
1, entries 10 and 11). While the AlMe3 loading was decreased
from 0.5 mmol to 0.3 mmol, the reaction selectivity decreased
from 99:1 to 64:36 (Table 1, entry 9). Furthermore, when the
reaction temperature was decreased from 60 oC to room
temperature, the conversion of the product 2a and 3a was
decreased from 100% to 40% (Table 1, entries 10 and 12).
a1/AlMe3/PdCl2(dppf)/PPh3/ K2CO3 = 0.5/0.4/0.005/0.5 mmol, 4h, 60 oC. b
The ratio of 2/3 was determined by 1HNMR. c Isolated yield, two runs. d 5h.
With the optimized conditions in hand, the scope of this reaction
was studied by using various propargyl acetates, and results are
presented in Table 3 (entries 1-24). The corresponding products
tri- and tetra-substituted allenes (i.e., 2a–2x) were obtained in
good yields with high selectivities. Reactions of aromatic
propargyl acetates with either electron-donating or electron-
withdrawing groups on the aromatic ring furnished tri- and tetra-
substituted allenes (i.e., 2b–2g, 2k-2l, 2o-2t and 2w, 2x) in good
isolated yields from 66% to 98% (Table 3, entries 2-7, 11,12, 15-
20, 23 and 24). Aromatic propargyl acetates containing 1-
naphthyl and 2-naphthyl substituents also produced the tri-
substituted allene products (i.e., 2h and 2i) with 99% selectivity
in yields of 80% and 87% (Table 3, entries 8 and 9). The SN2’
substitution reactions of AlMe3 with heteroaromatic propargyl
acetates containing thienyl group was also explored, and after 4 h,
tetra-substituted allenes 2m and 2u were formed with 99%
selectivity in yields of 66% and 70%, respectively (Table 3,
entries 13 and 21). More importantly, the tetra-substituted allenes
bearing biaryl group 2v-2x resulting from propargyl acetates 1w-
1x were obtained in 99% selectivity with isolated yields of 58-
84% (Table 3, entries 22-24).
Table 2 Effect of the solvent, the reaction time and the reaction temperature
a
on SN2’ substitution reaction.
1 mol%
PdCl2(dppf)
Me
OAc
Me
Ph
+
AlMe3
+
Ph
Ph
Solvent, Temp.,
Time, K2CO3
Ph
Ph
Ph
1a
3a
2a
Entry
Solvent
Toluene
n-Hexane
THF
THF
THF
Time (h)
Conv.(%)b 2a/3a(%)c
1
2
3
4
5
6
6
3
4
5
71
99/1
99/1
99/1
99/1
99/1
55
95d
100(97)d
100(97)d
a1a /AlMe3/ PdCl2(dppf)/K2CO3
Conversion of 2a+3a was determined by 1H NMR spectra. The ratio of
2a/3a was determined by 1HNMR. d Isolated yield.
=
0.5/0.4/0.005/0.5 mmol, 60 oC.
b
c
To further study the reactivity and selectivity, the reaction of 1a
with AlMe3 under others conditions were investigated. Firstly,
various solvents were screened under the model reaction
To broaden the reaction scope, we subsequently examined the
SN2’ substitution reactions of AlEt3. Results showed that the

3
4.2 General Procedures for the Synthesis of Propargyl Acetates
1(a-i)
reactions of the secondary propargyl acetates 1(b, c, d, y, z) or
the tertiary propargyl acetates 1(m, t, o, r, aa) underwent the
coupling reactions smoothly to give the tri- or tetra-substituted
allenes (i.e., 4b, 4c, 4d, 4y, 4z, 4aa, 4m, 4t, 4o, 4r) with high
selectivity (up to 99:1) and good isolated yields (50-94%, Table 4,
entries 1-10). Under the same conditions, aliphatic propargyl
acetates bearing TMS group 1z reacted with AlEt3 to provide the
tri-substituted allenes 4z with good isolated yields (83%) and
high selectivity (99%) (Table 4, entry 5). In addition, the tetra-
substituted allenes bearing a thienyl group 4m resulting from
propargyl acetate 1m was obtained with isolated yield of 50%
and 99% selectivity (Table 4, entry 7).
ACCEPTED MANUSCRIPT
To a solution of the alkyne (16.5 mmol) in anhydrous THF (25ml)
at -78ºC under nitrogen atmosphere was added n-BuLi 1.6 M
(16.5 mmol). The reaction was stirred at this temperature for 20
minutes then at room temperature for 1h. After cooling to -78 oC,
the aldehyde (15.0 mmol) was added and the reaction was stirred
at room temperature for 1h. After addition of acetate anhydrous
(30.0 mmol) at 0oC, the reaction mixture was warmed to room
temperature and stirred for 2h before quenched with a saturated
aqueous NH4Cl solution . The mixture was extracted with diethyl
ether (3 × 30 mL). The combined organic layers were washed
with brine, dried over magnesium sulfate, filtered and evaporated
to give the crude products. The crude product was subjected to
flash column chromatography on silica gel (hexane or ethyl
acetate and hexane) to afford the corresponding propargylic
acetate 1(a-i).
Table 4. PdCl2(dppf) -catalyzed the SN2’ substitution reaction of propargyl
a
acetates with AlEt3
.
R
Et
OAc
PdCl2(dppf)(1 mol%)
R2
R2
AlEt3
Et
+
+
R2
THF (2 mL), 4 h, 60 o
K2CO3(1.0equiv.)
C
R
R1
R
R1
R1
1,3-Diphenylprop-2-ynyl acetate (1a) [59]: Yield:1.06g (85
%),Yellow oil. H NMR (400 MHz, CDCl3) δ: 7.60 (dd, J1 = 8.4
Hz, J2 = 1.6 Hz, 2H), 7.48-7.46 (m, 2 H), 7.42- 7.34 (m, 3 H),
7.32-7.27 (m, 3 H), 6.70 (s, 1H), 2.11 (s, 3H) ppm. 13C NMR
(100 MHz, CDCl3) δ: 169.9, 137.3, 132.0, 129.1, 128.9, 128.8,
128.4, 127.9, 122.2, 87.2, 85.7, 66.2, 21.2 ppm.
1
1
4
5
Entry
1
2
3
4
5
6
7
1
R
H
H
H
H
H
R1
Ph
Ph
Ph
Ph
TMS
R2
Prod.
4b
4c
4d
4y
4:5b 4 Yield(%)c
98/2 86
95/5 83
95/5 81
98/2 79
99/1 83
98/2 79
99/1 50
98/2 83
99/1 74
99/1 94
1b
1c
1d
1y
1z
2-MePh
3-MePh
4-MePh
3-BrPh
4-ClPh
3-Phenyl-1-o-tolylprop-2-ynyl acetate (1b) [33]: Yield:1.66
4z
1
1aa Me 4-MePh Me
1m Me 2-thienyl Me
1t Me 4-MePh Et
1o Me 2-FPh
1r Me 3-ClPh
4aa
4m
4t
4o
4r
g, 84%, yellow oil. H NMR (400 MHz, CDCl3)
δ
: 7.69-7.65
(m, 1H), 7.50-7.46 (m, 2H), 7.35-7.28 (m, 5H), 7.24-7.18 (m,
1H), 6.77 (s, 1H), 2.46 (s, 3H), 2.15 (s, 3H) ppm. 13C NMR
8
9
10
Et
Et
(100 MHz, CDCl3)
δ: 169.8, 136.4, 135.3, 131.9, 130.7,
128.9, 128.7, 128.3, 128.1, 126.4, 122.3, 86.9, 85.5, 64.2,
21.0, 19.2 ppm.
a1/AlMe3/PdCl2(dppf)/PPh3/ K2CO3 = 0.5/0.4/0.005/0.5 mmol, 4h, 60 oC. b
The ratio of 4/5 was determined by 1HNMR. c Isolated yield, two runs.
3-Phenyl-1-m-tolylprop-2-ynyl acetate (1c) [33]: Yield:1.68
3. Conclusion
1
g, 85%, yellow oil. H NMR (400 MHz, CDCl3)
δ
: 7.51-7.45
(m, 2H), 7.44-7.38 (m, 2H), 7.35-7.29 (m, 4H), 7.18 (d, J =
In conclusion, a palladium-catalyzed cross-coupling reaction of
substituted propargyl acetates with trimethylaluminum reagents
is reported. The SN2’ substitution reactions of aromatic propargyl
acetates with trimethylaluminum or triethylaluminum afford tri-
and tetra-substituted allenes in good to excellent yields with high
selectivities. The SN2’ substitution reactions of aromatic
propargyl acetates containing 1/2-naphthyl substituents
producing the tri-substituted allenes products of 2h and 2i in 87%
and 80% yields with 99% selectivity. The SN2’ substitution
reactions of 2-methyl-4-arylbut-3-yn-2-yl acetate with
trimethylaluminum or triethylaluminum can smoothly to give the
tetra-substituted allenes product of 2(j-x) and 4(aa, m, t, o, r) in
excellent yields (up to 97%) with high selectivities (up to 99%).
This methodology provides useful procedure for the synthesis of
tri- and tetra-substituted allenes. Further studies on the
application of this catalyst to other organoaluminum reagents are
currently under way.
7.6 Hz, 1H), 6.67 (s, 1H), 2.38 (s, 3H), 2.14 (s, 3H) ppm.
13C{1H} NMR (100 MHz, CDCl3)
δ: 169.9, 138.6, 137.1,
131.9, 129.9, 128.8, 128.6, 128.5, 128.2, 124.9, 122.2, 86.8,
85.7, 66.1, 21.5, 21.2 ppm.
3-Phenyl-1-p-tolylprop-2-ynyl acetate (1d) [33]: Yield:1.53
1
g, 78%, yellow oil. H NMR (400 MHz, CDCl3)
δ
: 7.51-7.44
(m, 4H), 7.37-7.28 (m, 3H), 7.24-7.20 (m, 2H), 6.67 (s, 1H),
2.39 (s, 3H), 2.14 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3)
δ
: 169.9, 138.9, 134.3, 131.9, 129.3, 128.8, 128.2, 127.8,
122.1, 86.9, 85.7, 65.9, 21.2, 21.0 ppm.
1-(2-Methoxyphenyl)-3-phenylprop-2-ynyl acetate (1e)
1
[33]: Yield: 1.74 g, 83%, yellow oil. H NMR (400 MHz,
CDCl3) δ: 7.76 (dd, J1 = 1.6, J2 = 7.6 Hz, 1H), 7.51-7.43 (m,
2H), 7.39-7.33 (m, 1H), 7.32-7.27 (m, 3H), 7.05 (s, 1H), 7.04-
7.01 (m, 1H), 6.92 (dd, J = 1.2, 8.4 Hz, 1H), 3.83 (s, 3H), 2.13
(s, 3H) ppm. 13C NMR (100 MHz, CDCl3)
δ: 169.8, 156.8,
4. Experimental Section:
131.9, 130.4, 129.1, 128.6, 128.2, 125.2, 122.5, 120.6, 110.8,
86.5, 85.7, 61.0, 55.6, 21.1 ppm.
4.1. Materials and instruments
1H NMR and 13C NMR spectra were recorded on a Varian 400
MHz spectrometer. The chemical shifts are reported relative to
TMS. Analytical thin-layer chromatography (TLC) was
performed on silica 60F-254 plates. Flash column
chromatography was carried out on silica gel (200–400 mesh).
All reactions were carried out under nitrogen atmosphere.
Chemical reagents and solvents were purchased from Damas-
beta and Aldrich, and were used without further purification with
the exception of these reagents: THF, Et2O, Hexane and Toluene
were distilled from Sodium under Nitrogen. Compounds of
propargyl acetates 1a-1z and 1aa were prepared according to
literature procedures[33,59]. Purification of the reaction products
was carried out by flash chromatography.
1-(2-Chlorophenyl)-3-phenylprop-2-ynyl acetate (1f) [33]:
Yield: 1.81 g, 85%, yellow oil. 1H NMR (400 MHz, CDCl3)
δ:
7.86-7.83 (m, 1H), 7.51-7.44 (m, 2H), 7.43-7.39 (m, 1H),
7.38-7.29 (m, 5H), 6.96 (s, 1H), 2.15 (s, 3H) ppm. 13C NMR
(100 MHz, CDCl3)
δ: 169.6, 134.6, 133.5, 132.1, 130.3,
129.8, 129.5, 128.8, 128.3, 127.2, 122.1, 87.5, 84.6, 63.3, 21.0
ppm.
1-(4-Bromophenyl)-3-phenylprop-2-ynyl acetate (1g) [58]:
Yield: 2.06 g, 84%, yellow oil. 1H NMR (400 MHz, CDCl3)
δ:
7.56-7.50 (m, 2H), 7.49-7.44 (m, 2H), 7.42-7.38(m, 2H),
7.36-7.33 (m, 3H), 6.67 (s, 1H), 2.14 (s, 3H) ppm.13C NMR
(100 MHz, CDCl3)
δ: 169.5, 143.4, 131.9, 131.8, 128.5,
128.3, 128.2, 122.8, 119.8, 90.3, 84.1, 72.6, 22.1 ppm.

4
Journal of Organometallic Chemistry
ACCEPTED MANUSCRIPT
1-(Naphthalen-1-yl)-3-phenylprop-2-ynyl Acetate (1h)[33]:
Yield: 1.185g (75 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
8.29 (d, J = 8.4 Hz, 1H), 7.88 (d, J= 7.2 Hz, 1H) 7.82(t, J = 7.0
Hz, 2H), 7.54 (t , J = 7.6 Hz, 1H), 7.48- 7.41 (m, 4 H), 7.33 (s,
1H), 7.22 (t, J = 3.0Hz, 3H), 2.08 (s, 3H) ppm. 13C NMR (100
MHz, CDCl3) δ: 170.0, 134.1, 132.5, 132.0, 130.7, 130.1,
128.9(d, J = 5.7Hz), 128.4,126.7(d, J = 3.1Hz), 126.1, 125.3,
123.9, 122.2, 87.7, 85.8, 64.7, 21.2.ppm.
7.45-7.41 (m, 1H), 7.30-7.24 (m, 1H), 7.08-7.01 (m, 2H), 2.12-
2.07 (m, 1H), 2.05 (s, 3H), 1.97-1.88 (m, 1H), 1.75 (s, 3H), 1.10
(t, J = 3.8 Hz, 3H)ppm. 13C NMR (100 MHz, CDCl3) δ: 169.4,
163.0 (d, J = 250.2 Hz), 133.8 (d, J = 1.3 Hz), 130.1 (d, J = 7.9
Hz), 123. 9 (d, J = 3.8 Hz), 115.5 (d, J = 20.7Hz), 111.5 (d, J =
15.6Hz), 94.6 (d, J = 3.4Hz), 78.6, 76.2, 34.7, 26.1, 22.0,
8.7ppm.
3-Methyl-1-(3-fluorophenyl)pent-1-yn-3-yl Acetate (1p) [58]:
Yield: 0.588g (47 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
7.27-7.20 (m, 2H), 7.15-7.11 (m, 1H), 7.02-6.97 (m, 1H), 2.10-
2.01 (m, 4H), 1.96-1.87 (m, 1H), 1.73 (s, 3H), 1.07 (t, J = 3.0
Hz,3H) ppm. 13C NMR (100 MHz, CDCl3) δ: 169.4, 163.6 (d, J =
244.8 Hz), 129.8 (d, J = 8.6 Hz), 127.8 (d, J = 3.0 Hz), 124.7 (d,
J = 9.4 Hz) 118.7 (d, J = 22.6 Hz), 115.7 (d, J = 21.0 Hz), 90.35,
83.9 (d, J = 3.4 Hz), 76.0, 34.6, 26.0, 21.9, 8.7 ppm.
1-(Naphthalen-2-yl)-3-phenylprop-2-ynyl Acetate(1i) [33]:
Yield: 1.343g (85 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
8.04 (s, 1H), 7.86-7.79 (m, 3 H), 7.69 (dd, J1 = 8.4 Hz, J2 = 1.2
Hz, 1H), 7.50-7.45 (m, 4 H), 7.28(t, J = 2.6 Hz, 3H), 6.88(s, 1H),
2.11(s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ: 169.8, 134.5,
133.5, 133.1, 132.0, 128.9, 128.7, 128.3, 128.3 (d, J = 1.8Hz),
127.7, 127.2, 126.7, 126.5, 125.2, 122.1, 87.4, 85.7, 66.3, 21.2
ppm.
3-Methyl-1-(4-fluorophenyl)pent-1-yn-3-yl Acetate (1q) [58]:
Yield: 0.400g (32 %), Yellow oil. 1H NMR (400 MHz, CDCl3)δ:
7.38 (q, J = 3.2 Hz, 2H), 6.94 (t, J = 8.0Hz, 2H), 2.06-1.97 (m,
4H), 1.92-1.83 (m, 1H), 1.69 (s, 3H), 1.04 (t, J = 7.4 Hz, 3H)
ppm. 13C NMR (100 MHz, CDCl3) δ: 169.4, 162.6 (d, J = 247.9
Hz), 133.8 (d, J = 8.3Hz), 118.9 (d, J = 3.4 Hz), 115.5 (d, J =
21.9Hz), 89.1, 84.1, 76.1, 34.6, 26.1, 22.0, 8.7 ppm..
4.3 General procedures for the synthesis of propargyl acetates
1(j-x)
n-BuLi (9.5 mL, 15.2mmol, 1.6M in hexane) was added to
anhydrous THF (30 mL) under an argon atmosphere and the flask
was cooled to –78°C. Then, alkyne (12.2mmol) was added
dropwise and stirred for 30 minutes at –78oC. Subsequently,
acetone (0.92 g, 1.16 mL, 15.85mmol) was added dropwise. The
reaction mixture was stirred for 2 h at room temperature. Then,
acetate anhydrous (1.68 g, 1.56 mL, 16.5mmol) was added
dropwise at 0 °C. The mixture was stirred overnight at room
temperature and. After completion, sat. aq. NH4Cl (15 mL) was
added and the mixture was extracted with diethyl ether (3 × 15
mL), washed with sat. NaHCO3 (10 mL), H2O (10 mL) and dried
over Na2SO4. The crude product was chromatographed on silica
gel (ethyl acetate/hexane) to afford the corresponding propargyl
acetate 1(j-x).
3-Methyl-1-(3-chlorophenyl)pent-1-yn-3-yl Acetate (1r) [58]:
Yield: 0.746g (56 %), Yellow oil. 1H NMR (400 MHz, CDCl3)δ:
7.43-7.39 (m, 1H), 7.33-7.26 (m, 1H), 7.24-7.22 (m, 1H), 7.20-
7.15 (m, 1H), 2.06-1.97 (m, 4H), 1.92-1.83 (m, 1H), 1.70 (s, 3H),
1.04 (t, J = 7.4Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ:
169.3, 133.9, 131.6, 129.9, 129.4, 128.5, 124.4, 90.5, 83.6, 75.8,
34.5, 25.9, 21.9, 8.6 ppm.
3-Methyl-1-(3-bromophenyl)pent-1-yn-3-yl Acetate (1s) [58]:
Yield: 0.715g (46 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
7.58 (t, J = 1.8 Hz, 1H), 7.45-7.41 (m, 1H), 7.29-7.26 (m, 1H),
7.15 (t, J = 7.8 Hz, 1H), 2.11-2.00 (m, 4H), 1.97-1.86 (m, 1H),
1.73 (d, J = 6.8 Hz, 3H), 1.10-1.05 (m, 3H) ppm. 13C NMR (100
MHz, CDCl3) δ: 169.5, 134.7, 131.8(d, J = 39.8Hz), 130.1(d, J =
76.2 Hz), 128.3 (d, J = 12.6 Hz), 124.9, 122.5 (d, J= 77.9 Hz),
90.1 (d, J = 136.7 Hz), 84.4(d, J = 147.6 Hz), 76.2(d, J = 33.0
Hz), 34.7(d, J = 7.1 Hz), 26.1 (d, J = 12.5 Hz), 22.1(d, J = 6.8
Hz), 8.8(d, J = 4.1 Hz) ppm.
2-Methyl-4-phenylbut-3-yn-2-yl acetate (1j)[57]: Yield: 0.654g
(60 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.43-7.41 (m,
2H), 7.24-7.28 (m, 3H), 2.02 (s, 3H), 1.74 (s, 6H) ppm. 13C NMR
(100 MHz, CDCl3) δ: 169.1, 131.7, 128.2, 128.1, 122.6, 90.1,
83.9, 72.3, 28.9, 21.8 ppm.
2-Methyl-4-(2-fluorophenyl)but -3-yn-2-yl Acetate (1k) [58]:
1
Yield: 0.791g (67 %), Yellow oil. H NMR (400 MHz, CDCl3)
δ:7.44-7.40 (m, 1H), 7.30-7.24 (m, 1H), 7.08-7.01 (m, 2H), 2.05
(s, 3H), 1.76 (s, 6H)ppm. 13C NMR (100 MHz, CDCl3) δ: 169.4,
162.8 (d, J = 250.0 Hz), 133.8 (d, J = 1.1 Hz), 130.2 (d, J =
7.9Hz), 123.8 (d, J = 3.8 Hz), 115.4 (d, J = 20.8 Hz), 111.3 (d, J
= 15.5 Hz), 95.5 (d, J = 3.3Hz), 72.4, 29.0, 22.0ppm.
3-Methyl-1-(4-methylphenyl)pent-1-yn-3-yl Acetate (1t) [58]:
Yield: 0.812g (66 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
7.31 (d, J = 7.6 Hz, 2H), 7.07 (d, J = 8.0 Hz, 2H), 2.31 (s, 3H),
2.09-2.00 (m, 4H),1.94-1.85 (m, 1H), 1.72 (s, 3H), 1.06 (t, J =
7.2 Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ: 169.5, 138.4,
131.8, 129.0, 119.8, 88.7, 85.2, 76.4, 34.7, 26.2, 22.1, 21.5, 8.8
ppm.
2-Methyl-4-(3-bromophenyl)but-3-yn-2-yl Acetate (1l) [58]:
1
Yield: 0.743g (50 %), Yellow oil. H NMR (400 MHz, CDCl3)
δ:7.59 (s, 1H), 7.44-7.29 (m, 3H), 7.17-7.14 (m, 1H), 2.06 (d, J =
1.6Hz, 3H), 1.75 (d, J = 2.0Hz, 6H) ppm, 13C NMR (100 MHz,
CDCl3) δ: 169.3, 134.6, 131.5, 130.4, 129.7, 128.2, 124.7, 122.0,
91.6, 82.5, 72.2, 29.0, 22.0 ppm.
3-methyl-1-(thiophen-2-yl)pent-1-yn-3-yl acetate (1u) Yield:
0.952g (80 %), Yellow oil. H NMR (400 MHz, CDCl3) δ: 7.24-
1
7.20 (m, 2H), 6.96- 6.94 (m, 1H), 2.08-2.03 (m, 4H), 1.96-1.89
(m, 1H), 1.73 (s, 3H), 1.07 (t, J = 7.2 Hz,3H) ppm. 13C NMR
(100 MHz, CDCl3) δ: 169.4, 132.4, 127.3, 126.9, 93.2, 78.4,
76.2, 34.6, 26.0, 22.0, 8.8 ppm. HRMS(ESI):m/z calcd for
C12H15O2S+ (M + H)+ 223.07145, found 223.07132.
2-Methyl-4-(2-thienyl)but-3-yn-2-yl Acetate (1m) [58]: Yield:
1
0.907g (81 %), Yellow oil. H NMR (400 MHz, CDCl3) δ: 7.21-
7.19 (m, 1H), 7.18-7.17 (m, 1H), 6.92-6.90 (m, 1H), 2.00 (t, J =
2.2Hz, 3H), 1.71 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ:
169.3, 132.4, 127.3, 126.9, 122.5, 94.0, 77.4, 72.4, 29.0, 22.0
ppm.
2,4-Diphenylbut-3-yn-2-yl Acetate (1v) [58]: Yield: 0.770g (77
1
%), Yellow oil. H NMR (400 MHz, CDCl3) δ: 7.63 (d, J = 7.6
Hz, 2 H), 7.52-7.50 ( m, 2 H), 7.36 (t, J = 7.6 Hz, 2H), 7.30-7.27
( m, 4H ), 2.06 (s, 3H), 1.96 (s, 3H) ppm. 13C NMR (100 MHz,
CDCl3) δ: 168.6, 142.8, 132.0, 128.6, 128.4, 128.3, 127.9, 125.0,
122.5, 88.6, 87.2, 76.1, 32.2, 21.9 ppm.
3-Methyl-1-phenylpent -1-yn-3-yl Acetate (1n) [58]: Yield:
1
0.684g (59 %), Yellow oil. H NMR (400 MHz, CDCl3) δ: 7.43
(t, J = 3.6 Hz, 2H), 7.29-7.25 (m, 3H), 2.11-2.04 (m, 4H), 1.96-
1.87 (m, 1H), 1.74 (s, 3H), 1.08 (t, J = 7.4 Hz, 3H) ppm, 13C
NMR (100 MHz, CDCl3) δ: 169.4, 131.9, 128.3, 128.2, 122.8,
89.3, 85.1, 76.2, 34.7, 26.1, 22.0, 8.8 ppm.
4-(4-Chlorophenyl)-2-phenylbut-3-yn-2-yl Acetate (1w) [58]:
Yield: 1.101 g (70 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
7.59-7.55 (m, 2H), 7.52-7.49 (m, 2H), 7.34-7.29 (m, 5H), 2.07 (s,
3H), 1.94 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ: 168.6,
141.5, 133.7, 132.0, 128.8, 128.6, 128.4, 126.6, 122.3, 88.1, 87.5,
75.6, 32.1, 21.8 ppm
3-Methyl-1-(2-fluorophenyl)pent-1-yn-3-yl Acetate (1o) [58]:
Yield: 0.838g (67 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:

5
4-(4-Fluorophenyl)-2-phenylbut-3-yn-2-yl Acetate (1x) [58]:
Yield: 0.715 g (48 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
7.64-7.60 (m, 2H), 7.52-7.50 (m, 2H), 7.33-7.30 (m, 3H), 7.06-
7.02 (m, 2H), 2.07 (s, 3H), 1.96 (s, 3H) ppm. 13C NMR (100
MHz, CDCl3) δ: 168.7, 162.4 (d, J = 245.1 Hz), 138.7, 132.0,
128.8, 128.4, 127.1 (d, J = 8.2 Hz), 122.4, 115.3 (d, J = 20.5 Hz),
88.3, 87.5, 75.7, 32.2, 21.9 ppm.
1-(2-Methoxyphenyl)-3-phenylbuta-1,2-diene
(2e) [33]:
ACCEPTED MANUSCRIPT
1
Yield: 0.114 g, 97%, yellow oil. H NMR (400 MHz, CDCl3) δ:
7.47-7.44 (m, 2H), 7.38-7.31 (m, 3H), 7.25-7.18 (m, 2H), 6.91-
6.86 (m, 3H), 3.86 (s, 3H), 2.22 (d, J = 3.3 Hz, 3H) ppm. 13C
NMR (100 MHz, CDCl3) δ: 207.3, 156.1, 136.5, 128.4, 128.1,
127.8, 126.8, 125.7, 122.8, 120.7, 111.1, 103.8, 90.5, 55.6, 16.8
ppm.
1-(3-bromophenyl)-3-phenylprop-2-ynyl acetate (1y): 2.18 g,
83%, yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.74 (s, 1H),
7.52-7.46 (m, 4H), 7.31-7.23(m, 4H), 6.65 (s, 1H), 2.12 (s,
3H)ppm. 13C NMR (100 MHz, CDCl3) δ: 169.6, 139.4, 132.1,
131.9, 130.8, 130.3, 129.0, 128.4, 126.4, 122.7, 121.8, 87.5, 85.0,
65.2, 21.1ppm.
1-(2-Chlorophneyl)-3-phenylbuta-1,2-diene (2f) [33]: Yield:
0.116 g, 96%, yellow oil. H NMR (400 MHz, CDCl3) δ: 7.47-
7.40 (m, 3H), 7.37-7.33 (m, 3H), 7.25-7.22 (m, 1H), 7.18-7.12
(m, 2H), 6.91 (q, J = 2.8 Hz, 1H), 2.23 (d, J = 2.6 Hz, 3H) ppm.
13C NMR (100 MHz, CDCl3): δ = 207.8, 135.8, 132.2, 129.8,
128.5, 128.4, 128.1, 127.2, 126.8, 125.7, 104.8, 93.1, 16.7 ppm.
1
1-(4-Chlorophenyl)-3-(trimethylsilyl)prop-2-ynyl acetate (1z)
[58]: 1.56 g, 74%, yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.45
(d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.45 (s, 1H), 2.06
(s, 3H), 1.24 (s, 9H) ppm. 13C NMR (100 MHz, CDCl3) δ: 169.6,
135.4, 134.5, 129.2, 128.7, 96.5, 74.9, 65.1, 30.7, 27.5, 21.1, -0.4
ppm.
1-(4-bromophneyl)-3-phenylbuta-1,2-diene (2h) [58]: Yield:
0.094g, 66%, yellow oil. H NMR (400 MHz, CDCl3) δ: 7.45-
7.43 (m, 2H), 7.35-7.32 (m, 2H), 7.31-7.21 (m, 5H), 6.44 (q, J =
2.7 Hz, 1H), 2.23 (d, J = 2.6 Hz, 3H) ppm. 13C NMR (100 MHz,
CDCl3) δ: 206.9, 136.1, 133.1, 132.6, 128.8, 128.5, 128.2, 127.1,
125.8, 105.1, 95.7, 16.8 ppm.
1
2-Methyl-4-(4-methylphenyl)but-3-yn-2-yl acetate (1aa) [58]:
2.19 g, 83%, yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.31 (d, J
= 8.0 Hz, 2H), 7.07 (d, J = 8.0 Hz, 2H), 2.30 (s, 3H), 2.01 (s,
3H), 1.72 (s, 6H) ppm. 13CNMR (100 MHz, CDCl3) δ: 169.5,
138.4, 131.8, 129.1, 119.7, 89.6, 84.2, 72.6, 29.2, 22.0, 21.5 ppm.
1-(Naphthylen-1-yl)-3-phenylbuta-1,2-diene (2h) [58]: Yield:
0.111g (87 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
8.26(d, J = 7.6Hz,1H), 7.82 (d, J = 7.2 Hz, 1H), 7.71 (d, J = 8.0
Hz,1H), 7.56(d, J = 7.2 Hz, 1H), 7.51-7.44 (m, 4H), 7.39 (t, J =
7.6 Hz, 1H), 7.33-7.30 (t, J = 7.4 Hz, 2H), 7.21 (t, J = 7.2 Hz,
1H), 7.15 (d, J = 2.0 Hz, 1H), 2.26 (d, J = 2.4 Hz,1H) ppm. 13C
NMR (100 MHz, CDCl3) δ: 208.3, 136.5, 134.1, 131.1, 130.8,
128.8, 128.6, 127.8, 127.1, 126.3, 126.0, 125.8, 125.8, 125.7,
123.8, 103.5, 93.5, 17.0 ppm.
4.4 General Procedures for the Coupling Reaction of Propargyl
acetates with Trimethylaluminum or Triethylaluminum
Under a dry nitrogen atmosphere, a mixture of PdCl2(dppf)
(0.0037 g, 0.005 mmol), and K2CO3 ( 0.0691 g, 0.50 mmol) in a
reaction vessel was added an trimethylaluminum or
triethylaluminum (0.4 mmol) in 2 mL THF followed by an
addition of propargyl acetate (0.50 mmol). The resulted solution
1-(Naphthylen-2-yl)-3-phenylbuta-1,2-diene (2i) [57]: Yield:
0.102g (80 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.76, -
7.69(m, 4H), 7.48 (d, J = 8.0 Hz, 3H), 7.44-7.37 (m, 2H), 7.32(t,
J = 7.6 Hz, 2H), 7.21 (t, J = 7.2 Hz, 1H), 6.63 (d, J = 2.0 Hz,
1H), 2.25 (d, J = 2.4 Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3)
δ: 207.5, 136.4, 133.9, 132.8, 132.2, 128.6, 128.4, 127.84,
127.82, 127.2, 126.4, 126.0, 125.79, 125.76, 124.9, 104.9,
97.1,17.0 ppm.
o
was stirred at 60 C for 4 h. After completion the reaction, the
mixture was diluted with saturated ammonium chloride solution
(5 mL) and extracted with ethyl acetate (3× 15 mL). The
combined organic layers were dried over anhydrous Na2SO4,
filtered and evaporated in vacuum. The residue was subjected to
flash column chromatography on silica gel (hexane or ethyl
acetate and hexane) to afford the corresponding allene products 2.
1-(4-methylpenta-2,3-dien-2-yl)benzene (2j) [58]: Yield:
0.070g (89 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
7.37(d, J = 8.0 Hz, 2H), 7.30(t, J = 6.0Hz, 2H), 7.16 (t, J =
8.0Hz, 1H), 2.05(s, 3H), 1.79(s, 6H) ppm. 13C NMR (100 MHz,
CDCl3) δ: 202.1, 138.9, 128.3, 126.2, 125.8, 98.2, 97.0, 20.6,
17.4 ppm.
1,3-Diphenylbuta-1,2-diene (2a) [33]: Yield: 0.100g (97 %),
1
Yellow oil. H NMR (400 MHz, CDCl3) δ: 7.48–7.44 (m, 2 H),
7.36–7.28 (m, 6 H), 7.25–7.20 (m, 2 H), 6.48 (q, J = 2.8 Hz, 1
H), 2.23 (d, J = 2.8 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3) δ:
206.9, 136.4, 134.6, 128.8, 128.6, 127.2(d, J = 1.4Hz),127.0,
126.0, 104.7, 96.7, 16.9 ppm.
1-Fluoro-2-(4-methylpenta-2,3-dien-2-yl)benzene (2k) [58]:
Yield: 0.080g (91 %), Yellow oil. 1H NMR (400 MHz. CDC13) δ:
7.17-7.13 (m ,1H), 7.02-6.99 (d, J = 4 Hz, 1H), 6.96-6.85 (m
,2H), 1.97 (q, J1 = J2 = 4 Hz , 3H), 1.66 (t, J = 3.2 Hz, 6H) ppm,
13C NMR (100 MHz, CDCl3) δ: 203.7 (d, J = 1.5 Hz), 160.2 (d, J
= 247.5 Hz), 129.4 (d, J = 3.8 Hz), 127.9 ( d, J = 8.2 Hz ), 127.4
(d, J = 11.7 Hz), 123.8 (d, J = 3.6 Hz), 116.0 (d, J = 22.7 Hz),
95.1 (d, J = 1.5 Hz), 93.8, 20.6, 19.4 (d, J = 2.8 Hz) ppm.
1-(2-Methylphenyl)-3-pethylbuta-1,2-diene (2b) [33]: Yield:
0.095 g, 85%, yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.46 (d,
J = 7.6 Hz, 2H), 7.36-7.31 (m, 3H), 7.25-7.20 (m, 1H), 7.17-7.11
(m, 3H), 6.66 (q, J = 3.2 Hz, 1H), 2.40 (s, 3H), 2.23 (d, J = 3.2
Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 207.5, 136.6,
135.3, 132.7, 130.8, 128.5, 127.5, 126.95, 126.91, 126.2, 125.8,
103.5, 94.1, 20.1, 16.9 ppm.
1-Bromo-3-(4-methylpenta-2,3-dien-2-yl)benzene (2l) [58]:
Yield: 0.070g (73 %), Yellow oil. 1H NMR (400 MHz. CDC13) δ:
7.44-7.41 (m, 1H),7.35 (dd, J1 = 7.6 Hz, J2 = 0.8 Hz, 1H), 7.29-
7.27 (m, 1H), 7.18-7.11 (m, 1H), 2.05 (s, 3H), 1.75 (d, J = 4 Hz,
6H) ppm. 13C NMR (100 MHz, CDCl3) δ: 202.1, 138.8, 137.8,
128.3, 127.0, 125.8, 123.0, 98.2, 96.8, 21.7, 20.6, 17.5 ppm.
1-(3-Methylphenyl)-3-phenylbuta-1,2-diene (2c) [33]: Yield:
1
0.106 g, 97 %, yellow oil. H NMR (400 MHz, CDCl3) δ: 7.45
(d, J = 8.0 Hz, 2H), 7.35 (t, J = 7.2 Hz, 2H), 7.23 (dd, J = 8.4,
16.4 Hz, 2H), 7.21-7.12 (m, 2H), 7.02 (d, J = 7.2 Hz, 1H), 6.45
(q, J = 2.8 Hz, 1H), 2.33 (s, 3H), 2.23 (d, J = 2.8 Hz, 3H) ppm.
13C NMR (100 MHz, CDCl3) δ: 206.8, 138.2, 136.4, 134.4,
128.6, 128.4, 127.9, 127.5, 127.1, 125.8, 124.1, 104.3, 96.6, 21.5,
16.8 ppm.
2-(4-methylpenta-2,3-dien-2-yl)thiophene (2m) [58]: Yield:
0.054g (66 %), Yellow oil. 1H NMR (400 MHz,CDCl3) δ: 7.11
(d, J = 5.2 Hz, 1H), 6.95-6.93 (m, 1H), 6.84 (t, J = 3.6 Hz, 1H),
2.04 (d, J = 0.8 Hz, 3H), 1.78 (d, J = 0.8 Hz, 6H) ppm. 13C NMR
(100 MHz, CDCl3) δ: 201.1, 145.1, 127.5, 124.0, 122.4, 98.0,
94.4, 77.5, 77.2, 76.8, 20.6, 18.3 ppm.
1-(4-Methylphenyl)-3-phenylbuta-1,2-diene (2d) [33]: Yield:
1
0.107g, 98%, yellow oil. H NMR (400 MHz, CDCl3) δ: 7.46-
7.43 (m, 2H), 7.34-7.31 (m, 2H), 7.25-7.20 (m, 3H), 7.13 (d, J =
8.0 Hz, 2H), 6.46 (q, J = 2.8 Hz, 1H), 2.33 (s, 3H), 2.22 (d, J =
2.8 Hz, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ: 206.5,
136.6, 136.5, 131.6, 129.5, 128.3, 126.9, 126.8, 125.7, 104.5,
96.4, 21.2, 16.9 ppm.
1-(4-methylhexa-2,3-dien-2-yl)benzene (2n) [58]: Yield: 0.082g
(95 %), Yellow oil. 1H NMR (400 MHz. CDC13) δ: 7.38 (d, J = 8
Hz, 2H), 7.30 (t, J = 8 Hz, 2H), 7.16 (t, J = 6 Hz,1H), 2.11-

6
Journal of Organometallic Chemistry
13
ACCEPTED MANUSCRIPT
2.04(m , 5H) , 1.78 (s, 3H), 1.05-1.01 (m, 3H) ppm. C NMR
(100 MHz, CDCl3) δ: 201.3, 138.9, 129.1, 128.3, 126.1, 125.7,
103.4, 100.1, 27.6, 19.0, 17.5, 12.5 ppm.
7.41 (m, 2H), 7.38-7.35 (m, 2H), 7.34-7.30 (m, 2H), 7.23-7.19
(m, 1H), 7.02-6.97 (m, 2H), 2.19 (s, 3H), 2.18 (s, 3H) ppm. 13
C
NMR (100 MHz, CDCl3) δ: 205.6 (d, J = 2.1 Hz), 205.63, 162.0
(d, J = 244.3 Hz), 137.2, 133.3 (d, J = 3.2 Hz), 128.6, 127.4 (d, J
= 7.9 Hz), 127.0, 125.9, 115.4 (d, J = 21.4Hz), 102.7, 101.7,
17.2, 17.0 ppm.
1-Fluoro-2-(4-methylhexa-2,3-dien-2-yl)benzene (2o) [58]:
Yield: 0.086g (91 %), Yellow oil. 1H NMR (400 MHz,CDCl3) δ:
7.20- 7.15 (m ,1H), 7.03- 7.00 (m ,1H), 6.97- 6.85 (m ,2H), 1.98
(t, J = 2.4Hz ,3H), 1.94-1.91 (m ,2H), 1.66 (d, J = 3.6 Hz ,3H),
0.97- 0.92 (m ,3H)ppm. 13C NMR (100 MHz, CDCl3) δ: 202.9
(d, J = 2.0 Hz), 160.4 (d, J = 247.6Hz), 129.6 (d, J = 3.9Hz),
127.8 (d, J =8.2 Hz), 127.5 (d, J = 13.7 Hz), 123.8 (d, J = 3.6
Hz), 116.1 (d, J = 22.7 Hz), 101.4 (d, J = 1.3 Hz), 95.7, 27.3
,19.6 (d, J = 2.8 Hz) 19.0, 12.3ppm.
1-methyl-2-(3-phenylpenta-1,2-dien-1-yl)benzene (4b):Yield:
0.1014g (87%), yellow oil. H NMR (400 MHz, CDCl3) δ: 7.45-
1
7.38 (m, 3H), 7.30-7.27 (m, 2H), 7.19-7.08 (m, 4H), 6.74-6.73
(m, 1H), 2.57-2.53 (m, 2H), 2.38 (s, 3H), 1.21-1.17 (m, 3H) ppm
ppm. 13C NMR (100 MHz, CDCl3) δ: 206.5, 136.5, 135.8, 132.6,
130.7, 128.8, 127.3, 127.00, 126.7, 126.3, 126.1, 110.6, 96.9,
23.6, 20.1, 12.7 ppm. HRMS (ESI) m/z calcd for C18H19+ (M+H)+
235.14813, found 235.14836.
1-Fluoro-3-(3-methylhexa-2,3-dien-2-yl)benzene (2p) [58]:
Yield: 0.092g (97 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
7.25-7.21 (m, 1H), 7.14 (d, J = 8Hz, 1H), 7.09-7.05 (m, 1H),
6.87-6.83 (m, 1H), 2.11-2.04 (m, 5H), 1.79 (s, 3H), 1.02 (t, J =
8Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ: 201.6, 163.3 (d, J
= 242.5Hz), 141.7 (d, J = 7.4Hz), 129.6 (d, J =8.3Hz), 121.2(d, J
= 2.6Hz), 112.7 (dd, J1 = 21.4, J2 = 38.2 Hz), 104.0, 99.6 (d, J =
2.5Hz), 27.5, 18.9, 17.4, 12.4 ppm.
1-methyl-3-(3-phenylpenta-1,2-dien-1-yl)benzene (4c): Yield:
0.0972g (83%), yellow oil..1H NMR (400 MHz, CDCl3) δ: 7.71-
7.68 (m, 2H), 7.55-7.51 (m, 2H), 7.45-7.38 (m, 4H), 7.25 (m,
1H), 6.78-6.76 (m, 1H), 2.85-2.79 (m, 2H), 2.55 (d, J = 4.0 Hz
,3H), 1.47-1.42 (m, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ:
206.4, 138.4, 136.4, 134.7, 128.7, 128.6, 128.0, 127.5, 127.1,
126.2, 124.0, 111.6, 98.8, 23.3, 21.5, 12.7 ppm. HRMS (ESI) m/z
calcd for C18H19+ (M+H)+ 235.14813, found 235.14827.
1-Fluoro-4-(4-methylhexa-2,3-dien-2-yl)benzene (2q) [58]:
Yield: 0.076g (80 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
7.34- 7.30 (m, 2H), 6.98 (t, J = 8.0 Hz ,2H), 2.04 (s, 5H), 1.78 (s,
3H), 1.04-1.00 (m, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ:
201.0, 161.6 (d, J = 241.2Hz), 127.0 (d, J = 7.8Hz), 115.1, 114.9,
103.6, 99.3, 27.6, 9.0, 17.7, 12.4 ppm.
1-methyl-4-(3-phenylpenta-1,2-dien-1-yl)benzene (4d): Yield:
0.095g (81 %), yellow oil. H NMR (400 MHz, CDCl3) δ: 7.64
(d, J = 7.6 Hz ,2H), 7.49 (t, J = 7.6Hz ,2H), 7.44-7.36 (m, 3H),
7.30(d, J = 8.0 Hz ,2H), 6.74 (t, J = 3.2Hz ,1H), 2.78-2.74 (m,
2H), 2.51 (s, 3H), 1.38 (t, J = 7.2Hz ,3H)ppm. 13C NMR (100
MHz, CDCl3) δ: 206.0, 136.8, 136.2, 131.9, 129.5, 128.5, 127.0,
126.9, 126.1, 121.4, 98.4, 23.9, 21.5, 12.8 ppm.
1
1-Chloro-3-(4-methylhexa-2,3-dien-2-yl)benzene (2r) [58]:
Yield: 0.092g (89 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ:
7.33 (s, 1H), 7.26- 7.19 (m, 2H), 7.14- 7.12 (m, 1H), 2.11-2.04
(m, 5H), 1.79 (s, 3H), 1.02 (t, J = 8.0 Hz ,3H) ppm. 13C NMR
(100 MHz, CDCl3) δ: 201.6, 141.1, 134.3, 129.4, 126.1, 125.7,
123.7, 104.1, 99.4, 27.5, 18.9, 17.5, 12.4 ppm.
2-(5-methylhexa-3,4-dien-3-yl)thiophene (4m): Yield: 0.044g
(50%), yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.15(d, J = 4.8
Hz, 1H), 7.00-6.96(m, 1H), 6.92-6.90(m, 1H), 2.43(q, J = 7.2 Hz,
2H), 1.85(s, 6H), 1.16(t, J = 7.2 Hz ,3H) ppm. 13C NMR (100
MHz, CDCl3) δ: 200.5, 144.5, 127.4, 123.6, 122.0, 101.3, 100.1,
24.6, 20.6, 20.5, 12.6ppm. HRMS (ESI) m/z calcd for C11H15S+
(M+H)+ 179.08890, found 179.08853.
1-Bromo-3-(3-methylhexa-2,3-dien-2-yl)benzene (2s) [58]:
Yield: 0.079g (63 %), Yellow oil. H NMR (400 MHz, CDCl3) δ:
7.40-7.27 (m, 1H), 7.21-7.19 (m, 2H), 6.99-6.98 (m, 1H), 2.34 (s,
1H), 2.07-2.05 (m, 4H), 1.78 (s, 3H), 1.05-1.01 (m, 3H) ppm. 13C
NMR (100 MHz, CDCl3) δ: 201.3, 138.9, 137.8, 128.3, 127.0,
126.4, 125.6, 122.8, 103.2, 100.1, 27.6, 19.0, 17.6, 12.5 ppm.
1
1-methyl-4-(5-methylhepta-3,4-dien-3-yl)benzene (4t): Yield:
0.083g (83%), yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.27 (d,
J = 8.4 Hz, 2H ), 7.08 (d, J = 7.6 Hz, 2H), 2.39 (q, J = 7.2 Hz,
2H ), 2.30 (s, 3H), 2.13-2.01(m, 2H), 1.78 (s, 3H), 1.09 (t, J = 7.6
Hz, 3H), 1.03 (t, J = 7.2 Hz, 3H)ppm. 13C NMR (100 MHz,
CDCl3) δ: 200.4, 135.7, 129.3, 129.0, 126.5, 125.8, 107.2, 105.3,
94.4, 27.7, 23.4, 21.1, 19.2, 12.9, 12.6ppm. HRMS (ESI) m/z
calcd for C15H21+(M+H)+ 201.16378, found 201.16356.
1-Methyl-4-(4-methylpenta-2,3-dien-2-yl)benzene (2t) [58]:
Yield: 0.085g (92 %), Yellow oil. H NMR (400 MHz, CDCl3) δ:
7.27 (d, J = 8.4 Hz, 2H), 7.10(d, J = 8.0 Hz, 2H), 2.32 (s, 3H),
2.09-2.03 (m, 5H), 1.77 (s, 3H), 1.02 (t, J = 7.4 Hz, 3H) ppm. 13C
NMR (100 MHz, CDCl3) δ: 201.0, 136.0, 135.8, 129.0, 125.6,
103.2, 100.0, 27.7, 21.2, 19.0, 17.6, 12.5 ppm.
1
1-fluoro-2-(5-methylhepta-3,4-dien-3-yl)benzene (4o): Yield:
0.075g (74%), yellow oil. H NMR (400 MHz, CDCl3) δ: 7.36-
2-(4-methylhexa-2,3-dien-2-yl)thiophene (2u) Yield: 0.062g
(70 %), Yellow oil. H NMR (400 MHz, CDCl3) δ: 7.09 (d, J =
1
1
7.25 (m, 1H), 7.17-7.09 (m, 1H), 7.07-6.96(m, 2H), 2.40 (q, J =
7.2 Hz, 2H ), 2.09-1.98 (m, 2H), 1.79 (m, 3H), 1.07-1.03 (m,
6H). 13C NMR (100 MHz, CDCl3) δ: 201.8, 160.3 (d, J = 246.7
Hz), 129.7 (d, J = 4.1 Hz) 127.8 (d, J = 8.0 Hz), 123.8 (d, J = 3.5
Hz), 115.1(d, J = 22.8 Hz), 105.6, 103.1 (d, J = 72.4 Hz), 86.9 (d,
J = 6.5 Hz), 27.5, 25.6, 19.2, 12.9, 12.4ppm. HRMS (ESI) m/z
calcd for C14H18F+(M+H)+ 205.13871, found 205.13860.
4.8 Hz, 1H), 6.94 (t, J = 4.2 Hz, 1H), 6.84 (d, J = 2.8 Hz, 1H),
2.08-2.03 (m, 5H), 1.77 (m, 3H), 1.04 (t, J = 7.2 Hz, 3H) ppm.
13C NMR (100 MHz, CDCl3) δ: 200.3, 145.2, 127.4, 123.8,
122.2, 104.4, 96.5, 27.8, 19.0, 18.3, 12.4 ppm. HRMS(ESI):m/z
calcd for C11H15S+ (M + H)+ 178.08162, found 178.08138.
2,4-Diphenylpenta-2,3-diene (2v) [58]: Yield: 0.064g (58 %),
Yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.44-7.42 (m, 4H),
7.33-7.29 (m, 4H), 7.22-7.20 (m, 2H), 2.20 (s, 6H) ppm. 13C
NMR (100 MHz, CDCl3) δ: 206.0, 137.4, 128.6, 126.9, 125.9,
102.5, 16.9 ppm.
1-chloro-3-(5-methylhepta-3,4-dien-3-yl)benzene (4r): Yield:
0.103g (94%), yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.34 (t,
J = 2.0 Hz, 1H), 7.26-7.17 (m, 2H), 7.13-7.10 (m, 1H), 2.37 (q, J
= 7.2 Hz, 2H ), 2.15-2.03 (m, 2H), 1.80 (s, 3H), 1.09 (t, J = 7.2
Hz, 3H), 1.03 (t, J = 7.6 Hz, 3H)ppm. 13C NMR (100 MHz,
CDCl3) δ: 201.0, 140.9, 134.4, 129.5, 126.1 (d, J = 15.7 Hz),
124.0, 106.6, 106.3, 93.7, 27.6, 23.3, 19.0, 12.7, 12.5ppm.
HRMS (ESI) m/z calcd for C14H18Cl+ (M+H)+ 221.10915, found
221.10960.
2-phenyl-4-(4-chlorophenyl)penta-2,3-diene (2w) [58]: Yield:
0.107g (84 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.42-
7.39 (m, 2H), 7.35-7.27 (m, 6H), 7.25-7.19 (m, 2H), 2.19 (s, 3H),
2.17 (s, 2H) ppm. 13C NMR (100 MHz, CDCl3) δ: 206.0, 137.0,
135.9, 132.6, 128.6 (d, J = 2.8 Hz), 127.2, 127.0, 125.9, 102.9,
101.8, 16.9, 16.9 ppm.
1-bromo-3-(3-phenylpenta-1,2-dienyl)benzene (4y): Yield:
0.117g (79%), yellow oil. H NMR (400 MHz, CDCl3) δ: 7.47-
2-phenyl-4-(4-fluorophenyl)penta-2,3-diene (2x) [58]: Yield:
0.088g (74 %), Yellow oil. 1H NMR (400 MHz, CDCl3) δ: 7.43-
1

7
[22] V. Lavallo.; G. D. Frey.; S. Kousar.; B. Donnadieu.; G. Bertrand.
7.42 (m, 3H), 7.34-7.30 (m, 3H), 7.25-7.21 (m, 2H), 7.15 (t, J =
7.6 Hz, 1H), 6.49 (t, J = 3.2 Hz, 1H), 2.65-2.52 (m, 2H), 1.19 (t,
J = 7.2 Hz, 3H)ppm. 13C NMR (100 MHz, CDCl3) δ: 206.7,
137.3, 135.9, 130.3, 130.0, 129.6, 128.7, 127.4, 126.2, 125.4,
123.1, 112.4, 97.7, 23.3, 12.7ppm. HRMS (ESI) m/z calcd for
C17H16Br+ (M+H)+ 299.04299, found 299.04373.
ACCEPTED MANUSCRIPT
Proc. Natl. Acad. Sci. USA, 104(2007)13569–13573.
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1-(1-(4-chlorophenyl)penta-1,2-dien-3-yl)trimethylsilane (4z):
Yield: 0.103g (83%), yellow oil. H NMR (400 MHz, CDCl3) δ:
7.26-7.16 (m, 4H), 6.15-6.12 (m, 1H), 2.20-2.01(m, 2H), 1.11 (s,
9H), 1.00 (t, J = 7.2 Hz, 3H)ppm. 13C NMR (100 MHz, CDCl3) δ:
201.5, 135.2, 131.8, 128.8, 127.7, 127.4, 120.6, 107.4, 96.4, 34.6,
30.4, 29.6, 20.6, 12.8ppm. HRMS (ESI) m/z calcd for
C14H20ClSi+(M+H)+ 251.10173, found 251.10179.
1
1-methyl-4-(5-methylhexa-3,4-dien-3-yl)benzene (4aa): Yield:
1
0.073g (79%), yellow oil. H NMR (400 MHz, CDCl3) δ: 7.27-
7.24 (m, 2H), 7.10-7.08 (m, 2H), 2.40-2.34 (m, 2H), 2.30 (d, J =
2.0 Hz, 3H), 1.79 (d, J = 2.4 Hz, 6H), 1.11-1.07 (m, 3H). 13
C
NMR (100 MHz, CDCl3) δ: 201.3, 135.8, 135.7, 129.0, 125.9,
105.2, 98.9, 23.4, 21.1, 20.7, 12.8ppm. HRMS (ESI) m/z calcd
for C14H19+ (M+H)+ 187.14813, found 187.14801.
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Acknowledgments
We thank the Sichuan Provincial Department of science and
technology support program (No. 2015NZ0033) and the graduate
student innovation funds of Southwest University for
Nationalities (No. CX2017SZ010).
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ACCEPTED MANUSCRIPT
Highlights
Palladium-catalyzed, ligand-free SN2’ substitution reactions of organoaluminum with
propargyl acetates for the synthesis of multi-substituted allenes
Xuebei Shao, Chang Wen, Gang Zhang, Kangping Cao, Ling Wu, Qinghan Li
1. 1 mol% Pd(dppf)Cl2 complexes showed high activity in SN2’ substitution
reactions of organoaluminum with propargyl acetates.
2. The multi-substituted allenes derivatives were obtained in good to excellent yields
(50-98 %) with high selectivities (up to 99%).
3. Both aromatic and heteroaromatic propargyl acetates are tolerated in the reactions.
4. This catalyst system provided one of the most convenient approaches to the
construction of multi-substituted allenes.
Corresponding author. Tel.: +86-28-8592-8015; fax: +86-28-8552-4382; e-mail: lqhchem@163.com,
lqhchem@swun.cn