Synthesis of multi-substituted allenes from organoalane reagents and propargyl esters by using a nickel catalyst

Article abstract of DOI:10.1039/c8ob00781k

A highly efficient and simple route for the synthesis of multi-substituted allenes has been developed by a nickel catalyzed S_N2′ substitution reaction of propargyl esters with organic aluminium reagents under mild conditions, which gave the corresponding multi-substituted allenes in good to excellent yields (up to 92%) and high selectivities (up to 99%) at 60 °C for 6 h in THF. Aryls bearing electron-donating or electron-withdrawing groups in propargyl esters gave products in good yields. In addition, the multi-substituted allenes bearing a thienyl or a pyridyl group were obtained in 95-97% selectivities with isolated yields of 72-83%. Furthermore, the S_N2′ substitution reaction worked efficiently with propargyl carbonate compounds as well. On the basis of the experimental results, a possible catalytic cycle has been proposed.

Full text of DOI:10.1039/c8ob00781k

View Article Online
View Journal
Organic &
Biomolecular
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. shao, Z. Zhang,
Q. Li and Z. Zhao, Org. Biomol. Chem., 2018, DOI: 10.1039/C8OB00781K.
This is an Accepted Manuscript, which has been through the
Volume 14 Number
1 7 January 2016 Pages 1–372
Royal Society of Chemistry peer review process and has been
accepted for publication.
Organic &
Biomolecular
Chemistry
www.rsc.org/obc
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-0520
COMMUNICATION
Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
rsc.li/obc

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 1 of 10
View Article Online
DOI: 10.1039/C8OB00781K
Organic & Biomolecular Chemistry
ARTICLE
Synthesis of multi-substituted allenes from organoalane reagents
and propargyl esters by using a nickel catalyst
Received 00th January 20xx,
Accepted 00th January 20xx
Xue Bei Shao, Zhen Zhang, Qing Han Li* and Zhi Gang Zhao
DOI: 10.1039/x0xx00000x
A highly efficient and simple route for the synthesis of multi-substituted allenes has been developed by nickel catalyzed
the SN2’ substitution reaction of propargyl esters with organic aluminium reagents under mild conditions, giving the
corresponding multi-substituted allenes in good to excellent yields (up to 92%) and high selectivities (up to 99%) at 60 oC
for 6h in THF. The aryls bearing electron-donating or electron-withdrawing groups in propargyl esters gave products in
good yields. In addition, the multi-substituted allenes bearing a thienyl, or pyridyl group were obtained in 95-97%
selectivities with isolated yields of 72-83%. Furthermore, the SN2’ substitution reaction worked efficiently with propargyl
carbonate compounds as well. On the basis of the experimental results, a possible catalytic cycle has been proposed.
www.rsc.org/
multi-substituted allene derivatives.
Introduction
R2
R3
R2
R3
R1
R1
Nu-
Nu-
Allenes are important structural scaffolds found in many natural
and pharmaceutical products,1 and in addition, they serve as
building blocks for many organic transforamtion.2 Thus, their
synthesis and applications have attracted considerable attention
over the past decades. Developing some simple and efficient
method for the synthesis of multi-substituted allenes from simple
and easily available organic compounds is very important. Until now
numerous effective synthetic methodologies of synthesis allenes
have been reported.3,4 Synthetic protocols for substituted allenes
include elimination of allylic compounds,5 isomerization of alkynes,6
a reaction of aldehyde and terminal alkynes,7 and a few cases of
metal-catalyzed reactions of propargylic compounds.8,9 Among
them, the metal-catalyzed SN2’-type substitution reactions of
propargylic derivatives with organometal reagents is one of the
most generally useful (Scheme 1).2b 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.
LnM
R2
R3
Nu
LnM
2
X
SN2'
LnM
R2
R2
MLn
X
R3
Nu
R1
1
R1
R1
SN2
R3
3
X
Scheme 1 SN2’ and SN2 Processes of Metal-catalyzed Coupling Reactions of
Propargyl Derivatives with Organometallic Nucleophiles.
Results and discussion
To optimize the reaction conditions, effects of nickel source,
phosphine ligand, solvent, reaction time, the amount of
organoaluminum reagent, and the molar ratio of metal to ligand on
the SN2’ substitution reaction were investigated using propargyl
acetate (1a) (Table 1 and Table 2). In a preliminary study, use of
only NiCl2 as the catalyst, the SN2’ substitution reaction of propargyl
acetate (1a) with trimethylaluminum (AlMe3) afforded the 1-
methyl-1,3-diphenyl-allene (2a) with 15% yield and a ratio of 75:25
in favor of the allene 2a (Table 1,entry 1). When 8 mol % PPh3 was
used as ligand, the NiCl2-catalyzed the SN2’ substitution reaction of
propargyl acetate (1a) with AlMe3 produced the product 2a with
20% yield (Table 1, entry 2). The product ratio was about 88:12 in
favor of the allene 2a. To our delight, when 2.0 equive K2CO3 were
used as additive, the NiCl2/ PPh3 catalyzed the SN2’ substitution
reaction of propargyl acetate (1a) with AlMe3 produced the product
2a with 45% yield and a ratio of 90:10 in favor of the allene 2a
(Table 1, entry 3). While, the SN2’ substitution reaction of propargyl
acetate (1a) with AlMe3 produced the product 2a with 70% yield
and a ratio of 90:10 in favor of the allene 2a at 60oC (Table 1, entry
5). Other phosphine ligands were further examined (Table 1, entries
6-8). It was found that the PPh3 ligand was the best effective for the
reactivity and selectivity (Table 1, entry 5). Other phosphine ligands
did not provide satisfactory results. Solvents were then screened
To continue our effort to develop efficient coupling reactions using
reactive organometallic reagents to synthesis of tri- and tetra-
substituted allenes,10 we herein report a Ni(PhP3)2Cl2 (4 mol%)/PPh3
(8 mol%)/K2CO3(2.0 equive.) catalyzed the SN2’ substitution
reactions of propargyl acetates with organoaluminum reagents at
60 oC in short reaction time with good yields for the synthesis of tri-
and tetra-substituted allenes. The process was simple and easily
performed, and it provides an efficient method for the synthesis of
Address: College of Chemistry and Environmental Protection Engineering,
Southwest University for Nationalities, Chengdu 610041, P. R. China. Fax: 86-28-
85524382;E-mail: lqhchem@163.com,lqhchem@swun.cn.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-10 | 1
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 2 of 10
View Article Online
DOI: 10.1039/C8OB00781K
ARTICLE
Journal Name
under the model reaction conditions, and the results are PPh3 was altered to 1:1 or 1:3, low yield of 2a is obtained (Table 2,
summarized in Table 1 (entries 9-11). Solvents such as toluene, entries 10 and 11). Therefore, the optimal SN2’ substitution reaction
diethyl ether and hexane were unsuitable for this reaction since conditions was 4 mol % Ni(PPh3)2Cl2, 8 mol % PPh3, 1.0 mmol K2CO3,
they gave lower yields and selectivity.
0.3 mmol AlMe3, 0.5 mmol propargyl acetate in THF (1 mL) at 60oC
for 6 h.
Table 1. Effect of the ligand and solvent in the cross-coupling of propargyl
acetates (1a) with AlMe3.a
Table 2. Effect of the of metal and the loading of AlMe3 in the cross-
coupling of propargyl acetates (1a) with AlMe3.a
AlMe3
Me
Ph
NiCl2(4 mol%)
Me
AlMe3
Ph
NiX2(4 mol%)
PPh3 (8 mol%)
+
OAc
2a
Ligand (8 mol%)
Ph
+
2a
+
OAc
THF (1 mL), 60oC, 3 h
additives (2.0equiv.)
(eq.1)
Ph
+
Me
THF (1 mL), 60oC, time
K2CO3 (2.0equiv.)
(eq.2)
Me
Ph
3a
Ph
Ph
Ph
3a
Ph
1a
Ph
Ph
Ph
1a
Entry
Ligand
Additives
Solvent
2a:3a
2a Yield
AlMe3
(mmol)
0.6
Time
(h)
3
2a:3a
2a Yield
(%)c
25
(%)b
(%)c
15
20
45
15
68
50
20
65
20
30
10
Entry
NiX2
(%)b
1d
2d
3d
4
-
-
THF
75:25
88:12
90:10
50:50
90:10
90:10
50:50
90:10
50:50
1:99
1
NiBr2
89:11
50:50
50:50
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
PPh3
PPh3
PPh3
PPh3
PCy3
dppe
P(2-furyl)3
PPh3
PPh3
PPh3
-
THF
2
Ni(OAc)2
0.6
3
10
K2CO3
K3PO4
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
THF
3
Ni(acac)2
0.6
3
10
THF
4
Ni(PPh3)2Cl2
Ni(PPh3)2Cl2
Ni(PPh3)2Cl2
Ni(PPh3)2Cl2
Ni(PPh3)2Cl2
Ni(PPh3)2Cl2
Ni(PPh3)2Cl2
Ni(PPh3)2Cl2
0.6
3
70
5
THF
5
0.7
3
30
6
THF
6
0.3
3
75
7
THF
7
0.3
6
86
8
THF
8d
9e
10f
11g
0.3
6
38
9
Hexane
Et2O
Toluene
0.3
6
60
10
11
0.3
6
50
50:50
0.3
6
30
a1a /AlMe3/NiCl2/Ligand = 0.5/0.6/0.02/0.04 mmol. b The ratio of 2a/3a was
determined by 1HNMR. c Isolated yield of 2a. d RT.
a 1a /AlMe3/NiX2/ PPh3= 0.5/0.6/0.02/0.04 mmol. b The ratio of 2a/3a was
determined by 1HNMR. c Isolated yield of 2a. d 1a /AlMe3/Ni(PPh3)2Cl2/ PPh3
To further study the reactivity and product selectivity, other
parameters of the reaction conditions were optimized (eq. 2, Table
2). Other nickel sources with PPh3 were subsequently surveyed.
Although NiBr2, Ni(OAc)2 and Ni(acac)2 can effectively catalyzed the
the SN2’ substitution reaction, the product selectivity and yield of 2a
e
=
0.5/0.3/0.01/0.02 mmol.
1a /AlMe3 /Ni(PPh3)2Cl2/PPh3
=
0.5/0.3/
f
g
0.025/0.05 mmol. 1a/AlMe3/ Ni(PPh3)2Cl2/PPh3 = 0.5/0.6/0.02/0.02 mmol.
1a /AlMe3 /Ni(PPh3)2Cl2/PPh3 = 0.5 /0.6/0.02/0.06 mmol.
Under the optimized reaction conditions, the scope of catalytic SN2’
were low (Table 2, entries 1-3). Gratifyingly, excellent selectivity substitution reactions of propargyl acetates with AlMe3 was then
(2a:3a>99%) and good yield of 2a (70%) were obtained using
Ni(PPh3)2Cl2 (Table 2, entry 4). The effect of the amount of AlMe3
was also investigated. When the AlMe3 loading was decreased from
0.6 mmol to 0.3 mmol, the yield of 2a increased from 70% to 75%
(Table 2, entries 4 and 6). However, when the AlMe3 loading was
increased from 0.6 mmol to 0.7 mmol, the yield of 2a decreased
from 70% to 30% (Table 2, entries 4 and 5). While, excellent
explored (eq. 3), and results are presented in Table 3. In all the
cases, high yield and excellent selectivity were obtained for all
evaluated substrates (Table 3, 2a-2q). The SN2’ substitution
reactions of secondary propargyl acetates 1(a-q) with AlMe3 gave
tri-substituted allenes 2(a-q) in >97% selectivity with excellent
isolated yields (71-91%, Table 3, entries 1-17). Reactions of
aromatic propargyl acetate reagents bearing electron-donating
selectivity (2a:3a>99%) and good yield of 2a (86%) were obtained substituents (Table 3, entries 2-5) or electron-withdrawing
when the reaction time extended to 6h (Table 2, entry 7). When
increasing or decreasing the amount of Ni(PPh3)2Cl2, affording 2a in
low yield (Table 2, entries 8, 9). When the ratio of Ni(PPh3)2Cl2 and
substituents (Table 3, entries 6-9) on the aromatic ring furnished tri-
substituted allenes 2(b-i) in good to excellent isolated yields from
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 3 of 10
View Article Online
DOI: 10.1039/C8OB00781K
Journal Name
ARTICLE
81 to 91% and high selectivity (>99%) (Table 3, entries 2-9).
Furthermore, the propargyl acetate bearing a bulky 1-naphthyl
group was also produced the tri-substituted allene 2j with 99%
selectivity in isolated yield of 80% (Table 3, entry 10). The propargyl
17
18
1q Me3Si 2-naphthyl
1r Pentyl TMS
98: 2
71(2q)
0(2r)
-
acetate bearing n-pentyl and benzyl group were also explored, and a1/AlMe3/Ni(PPh3)2Cl2/PPh3 = 0.5/0.3/0.02/0.04 mmol. The ratio of 2/3 was
b
determined by 1H NMR. cIsolated yield of 2, two runs.
after 6 h, 2k and 2l were formed with 97-99% selectivity in isolated
yields of 81-87% (Table 3, entries 11 and 12). For aromatic
The SN2’ substitution reactions of the tertiary propargyl acetates
propargyl acetate containing pyridyl group, the catalytic system was
4(a-r) with AlMe3 gave tetra-substituted allenes 5(a-r) in >97%
still effective enough to furnish 2m in a 72% yield with 95%
selectivity with excellent isolated yields (83-92%, Table 4, entries 1-
selectivity (Table 3, entry 13). Under the same conditions, aliphatic
18). The results indicate that the reactions of aromatic propargyl
propargyl acetates bearing TMS group 1(n-q), also reacted with
acetates with electron-donating groups (4b, 4p) or electron-
AlMe3 to provide the tri-substituted allenes 2(n-q) with good
withdrawing groups (4c-4h, 4k-4o) on the aromatic rings underwent
isolated yields (71-86%) and high selectivity (up to 99%) (Table 3,
the SN2’ substitution reactions smoothly to give the tetra-
entries 14-17). However, the SN2’ substitution reactions of 1-
substituted allenes (i.e., 5b, 5p, 5c-5h, 5k-5o) with high selectivity
(trimethylsilyl)oct-1-yn-3-yl acetate (1r) with AlMe3 couldn’t
(up to 99%) and good to excellent isolated yields (83-92%, Table 4,
produced the trimethyl(nona-2,3-dien-2-yl)silane (2r).
entries 2, 16, 3-8, 11-15). In addition, the tetra-substituted allenes
bearing a thienyl group 5i resulting from propargyl acetate 4i was
obtained with isolated yield of 83% and 97% selectivity (Table 4,
entry 9). More importantly, the tetra-substituted allenes bearing
biaryl group 5q-5r resulting from propargyl acetates 4q-4r were
obtained in 97-98% selectivity with isolated yields of 83-85% (Table
4, entries 17,18).
Table 3. Tri-substituted allenes from the SN2’ substitution reactions of
,
propargyl acetates (1) with AlMe3.a
AlMe3
R2
Me
Ni(PPh3)2Cl2(4 mol%)
PPh3 (8 mol%)
+
OAc
R1
2
+
Me
THF (1 mL), 6 h, 60oC
K2CO3 (2.0equiv.)
(eq.3)
R2
Table 4. Tetra-substituted allenes from the SN2’ substitution reactions of
propargyl acetates (4) with AlMe3.a
R2
R1
3
R1
2Yield(%)c
1
Me
Entry
1
R1
R2
2:3 (%)b
99: 1
99: 1
99: 1
99: 1
99: 1
99: 1
99: 1
99: 1
99: 1
99: 1
97: 3
99:1
R2
Me
Ni(PPh3)2Cl2(4 mol%)
PPh3 (8 mol%)
THF (1 mL), 6 h, 60oC
K2CO3 (2.0equiv.)
AlMe3
+
OAc
1
1a Ph
1b Ph
1c Ph
1d Ph
1e Ph
1f Ph
1g Ph
1h Ph
1i Ph
1j Ph
1k Ph
1l Ph
1m Ph
Ph
85(2a)
83(2b)
83(2c)
83(2d)
81(2e)
87(2f)
91(2g)
88(2h)
87(2i)
80(2j)
81(2k)
87(2l)
72(2m)
84(2n)
82(2o)
86(2p)
R1
5
+
Me
2
o-MePh
m-MePh
p-MePh
o-MeOPh
o-ClPh
(eq.4)
R2
R2
6
R1
Me
4
3
R1
Me
4
Entry
4
R1
R2
5:6 (%)b
5 Yield (%)c
84(5a)
88(5b)
91(5c)
92(5d)
92(5e)
92(5f)
5
1
4a Ph
Me
99: 1
98: 2
99: 1
99: 1
99: 1
99: 1
99: 1
99: 1
97: 3
99: 1
99: 1
99: 1
6
2
4b p-MePh Me
4c m-ClPh Me
4d o-FPh Me
4e m-FPh Me
4f p-FPh Me
4g m-BrPh Me
4h p-BrPh Me
4i 2-thienyl Me
7
p-ClPh
3
8
p-BrPh
p-CF3Ph
1-naphthyl
n-pentyl
benzyl
4
9
5
10
11
12
13
14
15
16
6
7
86(5g)
91(5h)
83(5i)
8
3-pyridyl
95:5
9
1n Me3Si Ph
99: 1
98: 2
98: 2
10
11
12
4j Ph
Et
Et
83(5j)
1o Me3Si p-MePh
1p Me3Si p-ClPh
4k o-FPh
90(5k)
90(5l)
4l m-FPh Et
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 4 of 10
View Article Online
DOI: 10.1039/C8OB00781K
ARTICLE
Journal Name
propargyl acetates with organometallic nucleophiles, is shown in
Scheme 2. The first reaction involves replacements of both chloride
ions in Ni(PPh3)2Cl2 with two alkyl groups of AlR3 followed by
reductive elimination of two alkyl groups and coordination of PR3 to
furnish a Ni(0) active species of Ni(PPh3)2 (8). Then, the Ni(0) is
attacked by the triple bond of propargyl acetates to form a л-
complex (9), which is then converted to the corresponding complex
10 or complex 11. Complex 11 could isomerize to complex 10.
Complex 10 is more stable than the complex 11, so complex 10 is
major. Transmetalation of 10 or 11 with AlR3 gives
alkyl(allenyl)nickel(II) intermediate 12 or alkyl(propargyl) nickel(II)
intermediate 13 and R2Al(OAc). Finally complex 12 or 13 undergoes
reductive elimination to afford the desired product of an allene 2/5
or an alkyne 3/6 and regenerates the active Ni(0) species for the
next catalytic cycle.
13
14
15
16
17
18
4m p-FPh
Et
99: 1
99: 1
99: 1
98: 2
98: 2
97:3
92(5m)
88(5n)
87(5o)
84(5p)
83(5q)
85(5r)
4n m-ClPh Et
4o m-BrPh Et
4p p-MePh Et
4q Ph
4r Ph
4-FPh
4-ClPh
a4/AlMe3/Ni(PPh3)2Cl2/PPh3 = 0.5/0.3/0.02/0.04 mmol. The ratio of 5/6 was
determined by 1HNMR. cIsolated yield of 5, two runs.
b
For comparison, coupling reactions of other propargyl esters
7(a,b) with AlMe3 catalyzed by the same catalytic system were
Me3Al (4 mol%)
Ni(PPh3)2Cl2(4 mol%)
PPh3 (8 mol%)
THF (1 mL), 60oC, 2 h
H
conducted (eq. 5). Results showed that the reactions of
propargyl carbonate underwent the coupling reactions
OAc
OAc
Ni(PPh3)2
(eq. 6)
Ph
Ph
smoothly to give the tri- and tetra-substituted allenes (i.e., 2a
,
Ph
Ph
1a
5a) with high selectivity (up to 98:2) and good isolated yields
(81-83%, Table 5, entries 1-2). This study demonstrates that
the synthesis of allene method for different propargyl esters
have good tolerance.
Ni(PPh3)2Cl2
AlMe3
R3
R1
Me
Me
R2
MeAlCl2
(PPh3)2NiMe2
PPh3
R1 R3 3 or 6
R2
2 or 5
Table 5. Ni(PPh3)2Cl2/Ph3P-catalyzed the SN2’ substitution reactions of
propargyl carbonate (7) with AlMe3.a
Me
R3
Me-Me
Me
R3
(Ph3P)2Ni
R1
R2
(Ph3P)2Ni
(Ph3P)2Ni
OAc
R1
R3
13
8
R2
R1
Me2Al(OAc)
12
AlMe3
R2
Me2Al(OAc)
AlMe3
Ni(PPh3)2Cl2(4 mol%)
R2
Me
1 or 4
R1
(Ph3P)2Ni
R2
+
R2
PPh3 (8 mol%)
AlMe3
OAc
OAc
R3
R3
2 or 5
Ph
+
OCOOMe
(Ph3P)2Ni
R1
(Ph3P)2Ni
THF (1 mL), 6 h, 60oC
K2CO3 (2.0equiv.)
Me
R2
R3
R1
(eq.5)
10
R2
R1 OAc
R2
R1
Ph
11
9
R1
3 or 6
Ph
7
Scheme 2. The proposed catalytic cycle for the formation of 2 or 5 and 3 or 6.
Entry
7
R1 R2
2:3/5:6 (%)b
2 or 5 Yield (%)c
Conclusions
1
2
7a Ph
H
97:3
98:2
81 (2a)
A nickel-catalyzed the SN2’ substitution reactions of substituted
propargyl acetates or carbonate with organoaluminum reagents is
reported. The SN2’ substitution reactions of aromatic propargyl
acetates and aliphatic propargyl acetates with organoaluminum
reagents afford tri- and tetra-substituted allenes in good to
excellent yields (up to 92%) with high selectivity (up to 99%). The
SN2’ substitution reactions of propargyl acetates bearing n-pentyl
group and TMS group producing the tri-substituted allenes in 71-
86% yields with 98-99% selectivities. SN2’ substitution reactions of
aromatic propargyl acetate containing pyridyl group also produce
the allene product of 2m in a 72% yield with selectivity of up to 95%.
The SN2’ substitution reactions of 2-methyl-4-arylbut-3-yn-2-yl
acetate with AlMe3 can smoothly to give the tetra-substituted
allenes in excellent yields (up to 92%) with high selectivity (up to
99%). The SN2’ substitution reaction of 2-methyl-4-thienyl but-3-yn-
2-yl acetate (4i) with AlMe3 can smoothly to give the tetra-
substituted allenes product of 5i in 83% yield with 97% selectivity.
More importantly, the tetra-substituted allenes bearing biaryl group
were obtained in 97-98% selectivities with isolated yields of 83-85%.
Furthermore, the SN2’ substitution reactions worked efficiently with
propargyl carbonate as well. The methodology provides useful
procedure for the synthesis of tri- and tetra-substituted allenes.
Further studies on the application of this catalyst to other
7b Me Me
83 (5a)
a 7/AlMe3/Ni(PPh3)2Cl2/PPh3 = 0.5/0.3/0.02/0.04 mmol. b The ratio of 2:3/5:6
was determined by 1HNMR. c Isolated yield of 2 or 5, two runs.
In order to further explore the reaction mechanism, control
experiments were carried out (eq. 6; for details see the Supporting
Information). Under the above conditions, 4 mol% Ni(PPh3)2Cl2 and
4mol% AlMe3 were added to the reaction system with 1,3-
diphenylprop-2-ynyl acetate as the substrate(eq. 6). After 2 hour,
the reaction mixture was analyzed by infrared spectroscopy, it was
found that the characteristic peak of allylene structure appeared
around 1967cm-1. At the same time, the reaction mixture was
analyzed by 1HNMR, and it was found that the characteristic peak of
allylene appeared in 6.46ppm. However, the same results were not
obtained when only 4 mol% Ni(PPh3)2Cl2 was used to react with 1,3-
diphenylprop-2-ynyl acetate. The results show that the
transmetalation and reduction of Ni(PPh3)2Cl2 with AlMe3 gives Ni(0)
active species of Ni(PPh3)2, and then Ni(0) activates the tri-bond of
propargyl acetates to form a л-complex and then isomerizes to
form the metallene structure. Thus, a proposed possible reaction
mechanism for the coupling reaction, based on known nickel
chemistry and the above results on the coupling reaction of
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 5 of 10
View Article Online
DOI: 10.1039/C8OB00781K
Journal Name
ARTICLE
MHz, CDCl3): δ = 169.9, 138.5, 137.2, 132.0, 129.8, 128.9, 128.7,
organoaluminum reagents and propargyl ester are currently under
way.
128.5, 128.4, 125.0, 122.3, 87.0, 85.84, 66.2, 21.5, 21.2ppm.
3-Phenyl-1-p-tolylprop-2-ynyl acetate (1d): [4h] Eluent: PE/EA = 10/1,
1.50 g, 76%, yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.49-7.45 (m,
4H), 7.30-7.26 (m, 3H), 7.20-7.18 (d, J = 8.0 Hz, 2H), 6.67 (s, 1H),
Experimental Section
General Procedures: 1H NMR and 13CNMR 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).
2.34 (s, 3H), 2.08 (s, 3H)ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ =
169.9, 138.9, 134.4, 131.9, 129.4, 128.8, 128.3, 127.9, 122.2, 86.9,
85.9, 66.0, 21.3, 21.2 ppm.
HRMS were recorded on
a
Bruker Micro TOF spectrometer
[4h]
1-(2-Methoxyphenyl)-3-phenylprop-2-ynyl acetate (1e):
Eluent:
equipped with an ESI ion source. FT-IR169 infrared spectrometer
(The solid is pressed by KBr and the liquid by liquid membrane). All
reactions were carried out under nitrogen atmosphere. Chemical
reagents and solvents were purchased from Adamas-beta and
Aldrich, and were used without further purification with the
exception of these reagents: THF, Ether and Toluene were distilled
from Sodium under Nitrogen. Compounds of propargyl carbonate
7(a, c) were synthesized in literature [12]. Purification of reaction
products was carried out by flash chromatography.
PE/EA = 10/1, 1.76 g, 84%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ =
7.60 (dd, J = 1.6, 7.6 Hz, 1H), 7.49-7.46 (m, 2H), 7.39-7.33 (m, 1H),
7.37-7.27 (m, 3H), 7.03-7.00 (m, 2H), 6.92 (dd, J = 1.2, 8.4 Hz, 1H),
3.85 (s, 3H), 2.11 (s, 3H) ppm.13C{1H} NMR (100 MHz, CDCl3):
δ =
169.8, 156.9, 132.1, 130.5, 129.1, 128.7, 128.3, 125.4, 122.5, 120.8,
111.0, 86.5, 85.9, 61.1, 55.8, 21.2 ppm.
[4h]
1-(2-Chlorophenyl)-3-phenylprop-2-ynyl acetate (1f):
Eluent:
Trimethylaluminum(AlMe3): flammable, explosive reaction in water. PE/EA = 10/1, 1.79 g, 84%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ =
Need of nitrogen protection, with the sealing film sealed bottle to
avoid light and cold storage.
7.85-7.83 (m, 1H), 7.47-7.45 (m, 2H), 7.40-7.37 (m, 1H), 7.34-7.25
(m, 5H), 6.99 (s, 1H), 2.11 (s, 3H) ppm.13C{1H} NMR (100 MHz,
CDCl3):
δ =169.4, 134.6, 133.4, 131.9, 130.3, 129.8, 129.5, 128.9,
General Procedures for the Synthesis of Propargyl Acetates 1(a-q).
128.3, 127.2, 122.0, 87.4, 84.7, 63.3, 20.8 ppm.
n-BuLi (5.16 mL, 8.25 mmol, 1.6 M in hexane) was added to a
solution of the alkyne (8.25 mmol) in anhydrous THF (15ml) at -78oC
under nitrogen atmosphere. The reaction mixture was stirred for 20
minutes at -78oC, then for 1h at room temperature. Aldehyde (7.5
mmol) was added at -78oC, and the mixture was stirred for 1h at
room temperature. After addition of acetate anhydrous (1.53g, 1.42
[4h]
1-(4-Chlorophenyl)-3-phenylprop-2-ynyl acetate (1g):
PE/EA = 10/1, 1.69 g, 79%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ =
7.54-7.52 (m, 2H), 7.47-7.45 (m, 2H), 7.37-7.35 (m, 2H), 7.31-7.29
(m, 3H), 6.66 (s, 1H), 2.11 (s, 3H) ppm. 13C{1H} NMR (100 MHz,
Eluent:
CDCl3):
δ = 169.7, 135.8, 134.9, 131.9, 129.3, 129.0, 128.9, 128.4,
mL, 15.0 mmol) at 0oC, the reaction mixture was warmed to room 121.9, 87.4, 85.2, 65.4, 21.1 ppm
temperature and stirred for 2h. Then a saturated aqueous NH4Cl
[4h]
1-(4-Bromophenyl)-3-phenylprop-2-ynyl acetate (1h):
Eluent:
PE/EA = 10/1, 2.04 g, 83%, yellow oil. 1H NMR (400 MHz, CDCl3):
7.53-7.51 (m, 2H), 7.47-7.45 (m, 4H), 7.34-7.27 (m, 3H), 6.64 (s, 1H),
2.11 (s, 3H) ppm.13C{1H} NMR (100 MHz, CDCl3):
= 169.7, 143.4,
δ =
solution was added. The mixture was extracted with ethyl acetate
(3 × 15 mL). The combined ethyl acetate layers was washed with
brine (20 mL), dried over anhyd Na2SO4, and concentrated in vacuo.
The crude product was chromatographed on silica gel (hexane or
ethyl acetate and hexane) to afford the desired propargyl acetate
1(a-q).
δ
132.0, 131.9, 129.6, 129.0, 128.4, 123.2, 121.9, 87.4, 85.1, 65.47,
22.1 ppm.
[4h]
3-Phenyl-1-(4-(trifluoromethyl)phenyl)prop-2-ynyl acetate (1i):
1,3-Diphenylprop-2-ynyl acetate (1a): [4h] Eluent: PE/EA = 10/1, 1.53
Eluent: PE/EA = 10/1, 1.81 g, 90%, yellow oil. 1H NMR (400 MHz,
g, 82%, yellow oil. 1H NMR (400 MHz, CDCl3):
7.48-7.46 (m, 2H), 7.42-7.35 (m, 3H), 7.32-7.27 (m, 3H), 6.70 (s, 1H),
2.11 (s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
= 169.9, 137.3,
δ = 7.61-7.58 (m, 2H),
CDCl3):
7.36-7.29 (m, 3H), 6.74 (s, 1H), 2.14 (s, 3H) ppm.13C{1H} NMR (100
MHz, CDCl3): = 169.7, 141.1, 132.0, 131.1 ,129.2, 128.5, 128.2,
δ = 7.69 (dd, J = 8.0, 22.4 Hz, 4H), 7.48 (d, J = 6.8 Hz 2H),
δ
δ
132.0, 129.1, 128.9, 128.8, 128.4, 127.9, 122.2, 87.2, 85.7, 66.2,
21.2ppm. IR(KBr) ν: 3075, 2947, 2238, 1762, 1604, 1497, 1456,
1376cm-1.
3-Phenyl-1-o-tolylprop-2-ynyl acetate (1b): [4h] Eluent: PE/EA = 10/1,
1.68 g, 85%, yellow oil. 1H NMR (400 MHz, CDCl3): 1H NMR (400
MHz, CDCl3) δ = 7.69-7.67 (m, 1H), 7.46-7.44 (m, 2H), 7.31-7.24 (m,
5H), 7.21-7.18 (m, 1H), 6.80 (s, 1H), 2.46 (s, 3H), 2.12 (s, 3H). 13C{1H}
NMR (100 MHz, CDCl3): δ = 169.8, 136.4, 135.2, 132.0, 130.9, 129.0,
128.8, 128.3, 128.2, 126.4, 122.2, 86.9, 85.55, 64.4, 21.1, 19.2ppm.
3-Phenyl-1-m-tolylprop-2-ynyl acetate (1c): [4h] Eluent: PE/EA = 10/1,
1.66 g, 84%, yellow oil. 1H NMR (400 MHz, CDCl3): ) δ = 7.48-7.46
(m, 2H), 7.41-7.39 (m, 2H), 7.31-7.28 (m, 4H), 7.18-7.16(d, J = 7.2
Hz, 1H), 6.67(s, 1H), 2.37 (s, 3H), 2.11 (s, 3H)ppm. 13C{1H} NMR (100
125.8 (q, J = 3.8 Hz), 121.8, 87.8, 84.9, 65.4, 21.1 ppm.
[4h]
1-(Naphthalen-1-yl)-3-phenylprop-2-ynyl acetate (1j):
Eluent:
PE/EA = 10/1, 1.85 g, 82%, yellow solid. 1H NMR (400 MHz, CDCl3):
= 8.29 (d, J = 8.4 Hz, 1H), 7.88-7.80 (m, 3H), 7.56-7.41 (m, 5H), 7.33-
7.22 (m, 4H), 2.08 (s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ
δ
=
170.0, 134.1, 132.5, 132.0, 130.7, 130.1, 128.9, 128.8, 128.3, 126.8,
126.7, 126.1, 125.3, 123.9, 122.3, 87.7, 85.8, 64.6, 21.2 ppm.
1-Phenyloct-1-yn-3-yl acetate (1k): [4h] Eluent: PE/EA = 10/1, 1.47 g,
1
85%, colorless oil. H NMR (400 MHz, CDCl3):
δ = 7.41-7.40 (m, 2H),
7.25-7.24 (m, 3H), 5.59 (t, J = 6.8 Hz, 1H), 2.04 (s, 3H), 1.84-1.78 (m,
2H), 1.49-1.46 (m, 2H), 1.32-1.30 (m, 4H), 0.89( t, J = 5.6 Hz, 3H)
ppm.13C{1H} NMR (100 MHz, CDCl3):
122.2, 86.5, 84.9, 64.2, 34.7, 31.1, 24.6, 22.3, 20.7, 13.8 ppm.
δ = 169.5, 131.6, 128.3, 128.0,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 6 of 10
View Article Online
DOI: 10.1039/C8OB00781K
ARTICLE
Journal Name
1,4-diphenylbut-3-yn-2-yl acetate (1l): [4h] Eluent: PE/EA = 10/1, 1.18
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 4(a-r).
1
g, 65 %, yellow oil. H NMR (400 MHz, CDCl3): δ = 7.39-7.37(m, 2H),
7.31-7.23(m, 8H), 5.78(t, J = 6.8Hz, 1H), 3.15(d, J = 6.4Hz, 2H),
2.05(m, 3H)ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ = 169.9, 136.0,
131.8, 129.8, 128.7, 128.4, 128.3, 127.0, 122.2, 86.2, 86.1, 65.1,
41.3, 21.0ppm.
3-Phenyl-1-(pyridin-3-yl)prop-2-ynyl acetate (1m): [4h] Eluent: PE/EA
= 1/1, 1.16 g, 62%, yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.90 (s,
1H), 8.67-8.65 (m, 1H), 7.98-7.95 (m, 1H), 7.53-7.51 (m, 2H), 7.37-
7.34 (m, 4H), 6.77 (s, 1H), 2.17 (s, 3H)ppm. 13C{1H} NMR (100 MHz,
[10d]
2-Methyl-4-phenylbut-3-yn-2-yl acetate (4a):
Eluent: PE/EA =
= 7.41-
7.38 (m, 2H), 7.25-7.22 (m, 3H), 2.02 (s, 3H), 1.73 (s, 6H)
10/1, 2.09 g, 85%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ
ppm.13C{1H} NMR (100 MHz, CDCl3):
122.6, 90.3, 83.9, 72.3, 28.8, 21.9 ppm.
2-Methyl-4-(4-methylphenyl)but-3-yn-2-yl acetate (4b):
δ
= 169.2, 131.8, 128.3, 128.1,
CDCl3):
δ = 169.6, 150.1, 149.3, 135.4, 133.0, 131.9, 129.1, 128.4,
123.5, 121.6, 87.8, 84.5, 64.0, 21.0 ppm.
[10d]
Eluent:
[4h]
PE/EA = 10/1, 2.19 g, 83%, yellow oil. 1H NMR (400 MHz, CDCl3):
7.31 (d, J = 8Hz, 2H), 7.07 (d, J = 8Hz, 2H), 2.30 (s, 3H), 2.01 (s, 3H),
1.72 (s, 6H) ppm.13C{1H} NMR (100 MHz, CDCl3):
= 169.5, 138.4,
131.8, 129.1, 119.7, 89.6, 84.2, 72.6, 29.2, 22.0, 21.5 ppm.
δ
=
1-Phenyl-3-(trimethylsilyl)prop-2-ynyl acetate (1n):
Eluent:
PE/EA = 10/1, 1.47 g, 80%, yellow oil.1H NMR (400 MHz, CDCl3): δ =
7.53-7.50 (m, 2H), 7.40-7.33 (m, 3H), 6.49 (s, 1H), 2.08 (s, 3H), 0.20
(m, 9H) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 169.6, 136.9,
δ
128.9, 128.5, 127.8, 101.2, 92.5, 65.9, 21.1, -0.3 ppm.
[10d]
2-Methyl-4-(3-chlorophenyl)but-3-yn-2-yl acetate (4c):
PE/EA = 10/1, 2.48 g, 86%, yellow oil. 1H NMR (400 MHz, CDCl3):
7.42 (s, 1H), 7.31-7.21 (m, 3H), 2.05 (s, 3H), 1.74 (s, 6H) ppm.13C{1H}
NMR (100 MHz, CDCl3): = 169.6, 134.2, 131.9, 130.2, 129.6, 128.8,
Eluent:
[4h]
1-p-Tolyl-3-(trimethylsilyl)prop-2-ynyl acetate (1o):
Eluent:
δ
=
PE/EA = 10/1, 1.56 g, 80%, yellow oil.1H NMR (400 MHz, CDCl3):
7.41 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 8.0 Hz, 2H), 6.47 (s, 1H), 2.38 (s,
3H), 2.03 (s, 3H), 0.20 (s, 9H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ =
δ
δ
124.6, 91.8, 82.9, 72.5, 29.2, 22.1 ppm.
= 169.4, 138.6, 134.1, 129.2, 127.8, 101.6, 91.1, 65.6, 21.1, 21.1, -
2-Methyl-4-(2-fluorophenyl)but-3-yn-2-yl acetate (4d): Eluent:
0.3 ppm.
PE/EA = 10/1, 2.25 g, 86%, yellow oil. 1H NMR (400 MHz, CDCl3):
7.45-7.41 (m, 1H), 7.28-7.25 (m, 1H), 7.08-7.01 (m, 2H), 2.06 (s, 3H),
1.76 (s, 6H) ppm.13C{1H} NMR (100 MHz, CDCl3):
= 169.5, 162.3(d,
δ =
[4h]
1-(4-Chlorophenyl)-3-(trimethylsilyl)prop-2-ynyl acetate (1p):
Eluent: PE/EA = 10/1, 1.56 g, 74%, yellow oil. 1H NMR (400 MHz,
δ
CDCl3):
δ = 7.45 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.45 (s,
J = 250.2 Hz ), 133.8(d, J = 2.0 Hz ), 130.2 (d, J = 7.9 Hz ), 123.8 (d, J =
1H), 2.06 (s, 3H), 1.24 (s, 9H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ
4.8 Hz ), 115.5 (d, J = 20.1 Hz ), 111.3(d, J = 15.5 Hz), 95.5 (d, J = 3Hz),
+
= 169.6, 135.4, 134.5, 129.2, 128.7, 96.5, 74.9, 65.1, 30.7, 27.5,
77.6, 72.5, 29.1, 22.0 ppm. HRMS (ESI) m/z calcd for C13H14FO2
(M+H)+ 221.09723, found 221.09702.
21.1, -0.4 ppm.
[10d]
[4h]
2-Methyl-4-(3-fluorophenyl)but-3-yn-2-yl acetate (4e):
Eluent:
1-(Naphthalen-2-yl)-3-(trimethylsilyl)prop-2-ynyl acetate (1q):
PE/EA = 10/1, 2.26 g, 84%, yellow oil. 1H NMR (400 MHz, CDCl3):
7.24-7.21 (m, 2H), 7.18-7.12 (m, 1H), 7.01-6.97 (m, 1H), 2.03 (s, 3H),
1.75 (s, 6H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
= 169.3, 163.5,
δ =
Eluent: PE/EA = 10/1, 1.78 g, 80%, white solid; mp =55-57oC. 1H
NMR (400 MHz, CDCl3):
= 8.4 Hz, 1H), 6.57-6.54 (m, 2H), 5.86 (s, 1H), 1.16 (s, 3H), 0.45 (s,
9H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
= 169.5, 135.1, 133.2,
δ = 7.13 (s, 1H), 6.88-6.95 (m, 3H), 6.79 (d, J
δ
161.1, 129.8(d, J = 9 Hz), 127.6 (d, J = 3Hz), 124.6 (d, J = 9Hz), 118.5
δ
(d, J = 22Hz), 115.6 (d, J = 21Hz), 91.3, 82.8, 72.1, 28.9, 21.9 ppm.
132.9, 128.4, 128.1, 127.5, 127.0, 126.4, 126.2, 125.1, 96.3, 75.4,
65.9, 30.7, 27.4, 21.0, -0.3ppm.
[10d]
2-Methyl-4-(4-fluorophenyl)but-3-yn-2-yl acetate (4f):
Eluent:
PE/EA = 10/1, 2.31 g, 86%, yellow oil. 1H NMR (400 MHz, CDCl3):
7.42-7.38 (m, 2H), 7.01-6.96 (m, 2H), 2.05 (s, 3H), 1.74 (s, 6H)
ppm.13C{1H} NMR (100 MHz, CDCl3):
= 169.5, 162.5 (d, J = 247.9
δ =
1-(trimethylsilyl)oct-1-yn-3-yl acetate (1r): Eluent: PE/EA = 10/1,
1
0.99 g, 55%, colorless oil; H NMR (400 MHz, CDCl3):
δ = 5.36 (t, J =
δ
1.6 Hz, 1H), 2.06 (s, 3H), 1.68-1.73 (m, 2H), 1.39-1.43 (m, 2H), 1.28-
1.31 (m, 2H), 0.88 (t, J = 1.7 Hz,3H), 0.55 (s, 9H) ppm. 13C{1H} NMR
Hz), 133.8 (d, J = 8.4Hz), 118.8 (d, J = 3.5Hz), 115.5 (d, J = 22Hz),
90.1, 83.0, 72.5, 29.1, 22.0 ppm.
(100 MHz, CDCl3): δ = 170.0, 102.9, 90.3, 64.5, 34.9, 31.3, 24.7, 22.6,
21.2, 14.0, -0.07ppm. HRMS (ESI) m/z calcd for C13H25O2Si+ (M+H)+
241. 16183, found 241.16157.
2-Methyl-4-(3-bromophenyl)but-3-yn-2-yl acetate (4g): Eluent:
PE/EA = 10/1, 2.74 g, 80%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ =
7.56 (s, 1H), 7.41 (d, J = 2.6Hz, 1H), 7.33 (d, J = 2Hz, 1H), 7.15-7.11
(m, 1H), 2.03 (s, 3H), 1.74 (s, 6H) ppm.13C{1H} NMR (100 MHz,
General procedures for the synthesis of propargyl acetates 4(a-r)
CDCl3):
δ = 169.2, 134.6, 131.5, 130.5, 129.7, 128.2, 124.7, 122.1,
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
91.6, 82.5, 72.2, 29.1, 22.0 ppm. HRMS (ESI) m/z calcd for
C13H14BrO2+ (M+H)+ 281.01717, found 281.01813.
2-Methyl-4-(4-bromophenyl)but-3-yn-2-yl acetate (4h): [10d] Eluent:
PE/EA = 10/1, 2.92 g, 85%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ =
7.32 (d, J = 8Hz, 2H), 7.22 (d, J = 8Hz, 2H), 2.03 (s, 3H), 1.72 (s, 6H)
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 7 of 10
View Article Online
DOI: 10.1039/C8OB00781K
Journal Name
ARTICLE
ppm.13C{1H} NMR (100 MHz, CDCl3):
δ = 169.6, 131.9, 128.5, 128.3,
124.5, 90.6, 83.6, 76.1, 34.6, 26.1, 22.0, 8.8 ppm. HRMS (ESI) m/z
calcd for C14H16BrO2+ (M+H)+ 295.03282, found 295.03207.
122.7, 90.3, 84.1, 72.6, 29.3, 22.2 ppm.
2-methyl-4-(2-thienyl)but-3-yn-2-yl acetate (4i): [10d] Eluent: PE/EA =
3-methyl-1-(4-methylphenyl)pent-1-yn-3-yl acetate (4p): Eluent:
PE/EA = 10/1, 2.11 g, 75%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ =
1
10/1, 2.06 g, 81%, yellow oil. H NMR (400 MHz, CDCl3):
δ = 7.22-
7.17 (m, 2H), 6.92-6.91 (m, 1H), 2.01 (s, 3H), 1.72 (s, 6H)
7.36 (d, J = 2Hz, 2H), 7.12 (d, J = 2 Hz, 2H), 2.36 (s, 3H), 2.12-2.05 (m,
ppm.13C{1H} NMR (100 MHz, CDCl3):
122.5, 94.1, 77.5, 72.4, 28.9, 22.1 ppm.
3-methyl-1-phenylpent-1-yn-3-yl acetate (4j):
δ
= 169.4, 132.4, 127.2, 125.9,
1H), 2.05 (s, 3H), 1.99-1.91 (m, 1H), 1.76 (s, 3H), 1.10 (t, J = 1.8 Hz,
3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ = 168.4, 137.4, 130.8,
[10d]
Eluent: PE/EA =
128.1, 118.8, 87.6, 84.2, 75.5, 33.6, 25.2, 21.1, 20.4, 7.8 ppm. HRMS
10/1, 2.16 g, 82%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ
= 7.45- (ESI) m/z calcd for C15H19O2 (M+H)+ 231.13796, found 231.13725.
+
7.42 (m, 2H), 7.29-7.27(m, 3H), 2.33 (s, 3H), 1.92 (q, J = 3.6 Hz, 2H),
1.73 (s, 3H), 1.06 (t, J = 3.6 Hz, 3H) ppm.13C{1H} NMR (100 MHz,
4-(4-fluorophenyl)-2-phenylbut-3-yn-2-yl acetate (4q): Eluent:
PE/EA = 10/1, 2.15 g, 76%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ
=
CDCl3):
δ = 169.5, 131.9, 128.3, 128.2, 122.8, 89.4, 85.1, 76.2, 34.5,
7.64-7.59 (m, 2H), 7.53-7.51 (m, 2H), 7.33-7.30 (m, 3H), 7.06-7.03
(m, 2H), 2.06 (s, 3H), 1.96 (s, 3H) ppm. 13C{1H} NMR (100 MHz,
26.1, 22.1, 8.8 ppm.
3-methyl-1-(2-fluorophenyl)pent-1-yn-3-yl acetate (4k): Eluent:
CDCl3):
δ = 168.7, 162.3 (d, J = 245.1 Hz), 138.7, 132.1, 128.8, 128.5,
PE/EA = 10/1, 2.32 g, 82%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ =
127.2 (d, J = 8.2 Hz), 122.5, 115.3 (d, J = 20.5 Hz), 88.3, 87.5, 75.6,
7.46-7.41 (m, 1H), 7.31-7.24 (m, 1H), 7.08-7.01 (m, 2H), 2.10-2.02 32.2, 21.8 ppm. HRMS (ESI) m/z calcd for C18H16FO2+(M+H)+
(m, 1H), 2.04 (s, 3H), 1.97-1.91 (m, 1H), 1.75 (s, 3H), 1.09 (t, J = 2 Hz, 283.11288, found 283.11273.
3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ = 169.5, 162.5 (d, J =
4-(4-chlorophenyl)-2-phenylbut-3-yn-2-yl acetate (4r): Eluent: PE/EA
250.2Hz), 133.8 (d, J = 2.0 Hz), 130.1 (d, J = 7.9 Hz), 123.8 (d, J = 3.7
Hz), 115.5 (d, J = 20.8 Hz), 111.4 (d, J = 15.6 Hz), 94.5 (d, J = 3.4 Hz),
78.6, 76.2, 34.6, 26.1, 22.0, 8.7 ppm. HRMS (ESI) m/z calcd for
1
= 10/1, 2.21 g, 74%, yellow oil. H NMR (400 MHz, CDCl3):
7.55 (m, 2H), 7.52-7.48 (m, 2H), 7.35-7.31 (m, 5H), 2.06 (s, 3H), 1.95
(s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
= 168.6, 141.5, 133.6,
δ = 7.58-
δ
C
14H16FO2+ (M+H)+ 235.11288, found 235.11340.
3-methyl-1-(3-fluorophenyl)pent-1-yn-3-yl acetate (4l): [10d] Eluent:
PE/EA = 10/1, 2.46 g, 86%, yellow oil. 1H NMR (400 MHz, CDCl3):
132.1, 128.8, 128.6, 128.4, 126.5, 122.3, 88.1, 87.5, 75.6, 32.1, 21.9
ppm. HRMS (ESI) m/z calcd for C18H16ClO2+ (M+H)+ 299.08333, found
299.08298.
δ
=
7.28-7.15 (m, 2H), 7.14-7.13 (m, 1H), 7.12-6.96 (m, 1H), 2.05 (s, 3H),
General Procedures for the SN2’ Substitution Reaction of Propargyl
Esters with Organoaluminum.
1.92 (q, J = 3.6 Hz, 2H), 1.73 (s, 3H), 1.07 (t, J = 3.6 Hz, 3H)ppm.
13C{1H} NMR (100 MHz, CDCl3):
δ = 169.4, 162.2 (d, J = 244.8Hz),
Under a dry nitrogen atmosphere, a mixture of Ni(PPh3)2Cl2 (0.0131
g, 0.02 mmol), PPh3 (0.0104 g, 0.04 mmol) and K2CO3 (0.138 g, 1.0
mmol) in a reaction vessel was added an organoaluminum (0.3
mmol) in 1 mL THF followed by an addition of propargyl ester (0.50
mmol). The resulted solution was stirred at 60oC for 6 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 or 5.
129.8 (d, J = 8.6 Hz), 127.8 (d, J = 12 Hz), 124.6 (d, J = 9.4 Hz), 118.7
(d, J = 22.6 Hz), 115.6 (d, J = 21Hz), 90.5, 83.9, 76.1, 34.6, 26.1, 22.0,
8.7 ppm.
3-methyl-1-(4-fluorophenyl)pent-1-yn-3-yl acetate (4m): Eluent:
PE/EA = 10/1, 2.29 g, 80%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ =
7.43-7.39 (m, 2H), 6.99-6.95 (m, 2H), 2.07-2.02 (m, 1H), 2.03 (s, 3H),
1.94-1.90 (m, 1H), 1.73(s, 3H), 1.07 (t, J = 3 Hz, 3H) ppm. 13C{1H}
NMR (100 MHz, CDCl3):
δ = 169.4, 162.5 (d, J = 247.9Hz), 133.8 (d, J
= 8.3 Hz), 118.8 (d, J = 3.4 Hz), 115.4 (d, J = 21 Hz), 89.1, 84.0, 76.1,
+
34.6, 26.1, 22.0, 8.7 ppm. HRMS (ESI) m/z calcd for C14H16FO2
(M+H)+ 235.11288, found 235.11250.
3-methyl-1-(3-chlorophenyl)pent-1-yn-3-yl acetate (4n): Eluent:
1,3-Diphenylbuta-1,2-diene (2a): [4h] Eluent: PE, 0.088 g, 85%, yellow
PE/EA = 10/1, 2.45 g, 80%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ
=
1
oil. H NMR (400 MHz, CDCl3):
δ = 7.34-7.32 (m, 2H), 7.21-7.13 (m,
7.44-7.39 (d, J = 4Hz, 1H), 7.33-7.15 (m, 3H), 2.04 (s, 3H), 2.02- 1.99
6H), 7.09-7.03 (m, 2H), 6.34 (q, J = 2.4 Hz, 1H), 2.08 (d, J = 3.2 Hz,
3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
= 206.8, 136.4, 134.6,
(m, 1H), 1.88 (q, J = 3.6 Hz, 2H), 1.72 (s, 3H), 1.05 (t, J = 1.8 Hz, 3H)
δ
ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ = 169.4, 133.9, 131.5, 129.9,
128.7, 128.5, 127.11, 127.09, 126.9, 125.9, 104.6, 96.7, 16.9 ppm.
129.5, 128.5, 124.5, 90.5, 83.6, 75.8, 34.5, 26.0, 21.9, 8.7 ppm.
[4h]
1-(2-Methylphenyl)-3-pethylbuta-1,2-diene (2b):
Eluent: PE,
HRMS (ESI) m/z calcd for C14H16ClO2 (M+H)+ 251.08333, found
+
1
0.091 g, 83%, yellow oil. H NMR (400 MHz, CDCl3):
δ
= 7.46 (d, J =
251.08340.
7.6 Hz, 2H), 7.38-7.30 (m, 3H), 7.23-7.19 (m, 1H), 7.17-7.10 (m, 3H),
3-methyl-1-(3-bromophenyl)pent-1-yn-3-yl acetate (4o): Eluent:
PE/EA = 10/1, 2.91 g, 81%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ =
6.66 (q, J = 3.2 Hz, 1H), 2.40 (s, 3H), 2.23 (d, J = 2.8 Hz, 3H) ppm.
13C{1H} NMR (100 MHz, CDCl3):
δ = 207.5, 136.5, 135.2, 132.6,
7.45-7.42 (m, 1H), 7.36-7.19 (m, 3H), 2.07 (s, 3H), 2.04-2.01 (m, 1H),
1.95-1.88 (m, 2H), 1.73 (s, 3H), 1.08 (t, J = 1.8 Hz, 3H) ppm. 13C{1H}
130.6, 128.4, 127.5, 126.91，126.86, 126.1，125.8, 103.4, 94.1,
20.0, 16.9 ppm.
NMR (100 MHz, CDCl3): δ = 169.4, 134.2, 131.7, 130.1, 129.5, 128.6,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 8 of 10
View Article Online
DOI: 10.1039/C8OB00781K
ARTICLE
Journal Name
[4h]
1-(3-Methylphenyl)-3-phenylbuta-1,2-diene (2c):
Eluent: PE, 125.62, 125.60, 123.6, 103.4, 93.3, 16.9 ppm. IR(KBr) ν: 2994,
2837,1939, 1635, 1446, 1379cm-1.
1
0.091 g, 83 %, yellow oil. H NMR (400 MHz, CDCl3):
δ
= 7.48 (d, J =
2-Phenyl-nona-2,3-diene (2k): [4h] Eluent:PE, 0.075 g, 83%, colorless
7.6 Hz, 2H), 7.33 (t, J = 7.6 Hz, 2H), 7.25-7.14 (m, 4H), 7.03 (d, J = 7.2
1
Hz, 1H), 6.46 (q, J = 2.8 Hz, 1H), 2.33 (s, 3H), 2.23 (d, J = 2.0 Hz, 3H)
oil. H NMR (400 MHz, CDCl3):
δ = 7.39 (m, 2H), 7.30-7.26 (t, J = 7.6
ppm. 13C{1H} 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,
Hz, 2H), 7.15 (t, J = 7.2 Hz ,1H), 5.46-5.41 (m, 1H), 2.11-2.07 (m, 5H),
1.49-1.42 (m, 2H), 1.34-1.27 (m, 4H), 0.87 (t, J = 7.2 Hz, 3H) ppm.
13C{1H} NMR (100 MHz, CDCl3):
δ = 204.2, 137.8, 128.3, 126.3,
16.8 ppm.
125.7, 100.3, 93.2, 31.5, 29.06, 29.02, 22.6, 17.3, 14.2 ppm. IR(KBr)
[4h]
ν: 2969, 2871,1956, 1605, 1498, 1458, 1379cm-1.
1-(4-Methylphenyl)-3-phenylbuta-1,2-diene(2d):
Eluent: PE,
0.091g, 83%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ
= 7.45 (d, J =
[4h]
1,4-diphenylpenta-2,3-diene (2l):
Eluent: PE/EA = 20/1, yellow
7.41-7.19 (m,
oil, 0.192 g, 87 %. 1H NMR (400 MHz, CDCl3):
δ =
7.6Hz , 2H), 7.31 (t, J = 7.2 Hz , 2H), 7.23-7.20 (m, 3H), 7.10 (d , J =
7.6 Hz, 2H), 6.44 (q, J = 2.8 Hz, 1H), 2.32 (s, 3H), 2.21 (d, J = 2.0 Hz,
10H), 5.59(s, 1H), 3.44(m, 2H), 2.09(m, 3H)ppm.7.43-7.38 (m, 2H),
7.36-7.27 (m, 6H), 7.25-7.16 (m, 2H), 5.63-5.56 (m, 1H), 3.45 (d, J =
7.2Hz, 2H), 2.11 (d, J = 2.8 Hz, 3H) ppm. 13C{1H} NMR (100 MHz,
3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ = 206.5, 136.8, 136.5,
131.4, 129.4, 128.4, 126.9, 126.8, 125.7, 104.3 96.4, 21.2, 16.8 ppm.
1-(2-Methoxyphenyl)-3-phenylbuta-1,2-diene(2e):[4h] Eluent: PE/EA
CDCl3):
δ = 204.8, 140.5, 137.4, 128.6, 128.5(d, J = 6.7Hz), 126.6,
1
= 10/1, 0.095 g, 81%, yellow oil. H NMR(400 MHz, CDCl3):
δ = 7.43
126.3, 128, 100.9, 92.6, 35.9, 17.2ppm. IR(KBr) ν: 3037, 2937, 2868,
1943, 1603, 1497, 1452, 1380cm-1.
(d, J = 7.6 Hz, 2H), 7.36 (d, J = 7.6 Hz, 1H), 7.26(t, J = 7.6 Hz, 2H),
7.16-7.09(m, 2H), 6.90(d, J = 2.4 Hz, 1H), 6.84(t, J = 7.2 Hz, 1H),
6.78(d, J = 8.4 Hz, 1H), 3.73(s, 3H), 2.17(d, J = 2.8 Hz, 3H)ppm.
[4h]
3-(3-phenylbuta-1,2-dienyl)pyridine(2m):
Eluent: PE/EA = 2/1,
= 8.55(d, J =
1
13C{1H} NMR (100 MHz, CDCl3):
δ = 207.1, 156.0, 136.5, 131.5,
128.3, 128.1, 128.0, 127.7, 126.7, 125.7, 122.7, 120.7, 110.9, 103.6,
90.5, 55.4, 16.7ppm. IR(KBr) ν: 2947, 2849,1942, 1600, 1498,
yellow oil, 0.149 g, 72 %. H NMR (400 MHz, CDCl3):
δ
1.6 Hz, 1H), 8.42(d, J = 4.8 Hz, 1H), 7.58 (dd, J = 1.6, 8.0 Hz, 1H),
7.43(d, J = 7.6 Hz, 2H ) , 7.32(t, J = 7.2 Hz, 2H), 7.24-7.16(m, 2H),
6.43(q, J = 2.4Hz, 1H), 2.22(d, J = 2.8 Hz, 3H)ppm. 13C{1H} NMR (100
1388cm-1.
MHz, CDCl3):
127.4, 125.9, 123.6, 105.4, 93.3, 16.7 ppm.
δ = 207.2, 148.4, 148.1, 135.7, 133.6, 130.5, 128.5,
[4h]
1-(2-Chlorophneyl)-3-phenylbuta-1,2-diene (2f):
Eluent: PE,
δ = 7.45-7.40
0.105 g, 87%, yellow oil. 1H NMR (400 MHz, CDCl3):
[4h]
Phenyl-3-trimethylsilylbuta-1,2-diene (2n):
Eluent: PE, 0.085 g,
(m, 3H), 7.34-7.28 (m, 3H), 7.22-7.19 (m, 1H), 7.14-7.05 (m, 2H),
1
6.91 (q, J = 2.8 Hz, 1H), 2.21 (d, J = 2.6 Hz, 3H) ppm. 13C{1H} NMR
84%, colorless oil. H NMR (400 MHz, CDCl3):
δ = 7.27-7.20 (m, 4H),
(100 MHz, CDCl3):
128.0, 127.2, 126.8, 125.8, 104.8, 93.1, 16.7 ppm.
δ = 207.8, 135.9, 132.2, 129.9, 128.5, 128.4,
7.13-7.10 (m, 1H), 5.81 (q, J = 2.8 Hz, 1H), 1.81 (d, J = 2.8 Hz, 3H),
0.15 (s, 9H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ
= 205.7, 136.1,
[4h]
1-(4-Chlorophneyl)-3-phenylbuta-1,2-diene (2g):
0.110 g, 91%, yellow oil. 1H NMR (400 MHz, CDCl3):
8.4 Hz, 2H), 7.29(t, J = 7.6 Hz, 2H), 7.24-7.18 (m, 5H), 6.39 (q, J = 2.4
Hz, 1H), 2.19 (d, J = 3.2 Hz, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
Eluent: PE,
128.5, 125.9, 125.8, 95.4, 88.5, 15.1, -1.7 ppm.
δ
= 7.41(d, J =
[4h]
1-(4-Methylphneyl)-3-trimethylsilylbuta-1,2-diene (2o):
Eluent:
δ = 7.36
PE, 0.089 g, 82%, colorless oil. 1H NMR (400 MHz, CDCl3):
（d, J = 8.0 Hz, 2H）, 7.26（d, J = 8.0 Hz, 2H）, 8.23（q, J = 2.8
δ
= 207.0, 136.1, 133.2, 132.7, 128.9, 128.6, 128.1, 127.3, 125.9,
105.1, 95.8, 16.8ppm.
Hz, 1H）, 2.50(s, 3H), 2.00(d, J = 2.8 Hz, 3H）,1.33(s, 9H)ppm.
[10d]
13C{1H} NMR (100 MHz, CDCl3):
δ = 201.6, 135.9, 133.40, 129.34,
1-(4-bromophneyl)-3-phenylbuta-1,2-diene(2h):
0.125g, 88%, yellow oil. 1H NMR (400 MHz, CDCl3):
Eluent: PE,
δ
= 7.44-7.39 (m,
126.4, 112.4, 94.1, 34.3, 29.3, 21.2, 14.8, -1.7ppm.
4H), 7.34-7.30 (m, 2H), 7.22-7.16 (m, 3H), 6.40 (q, J = 2.8 Hz, 1H),
[4h]
1-(4-Chlorophenyl)-3-trimethylsilylbuta-1,2-diene (2p):
Eluent:
2.21 (d, J = 2.8 Hz, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ
=
1
PE, 0.102 g, 86%, colorless oil. H NMR (400 MHz, CDCl3):
δ = 6.25
207.1, 136.0, 133.7, 131.9, 128.6, 128.5, 128.3, 127.3, 125.9，
(d, J = 8.4 Hz, 2H), 6.19 (d, J = 8.4 Hz, 2H), 5.04 (q, J = 2.8 Hz, 1H),
0.83 (d, J = 2.8 Hz, 3H), 0.16 (s, 9H) ppm. 13C{1H} NMR (100 MHz,
120.7, 105.2, 95.7, 16.8 ppm.
[4h]
1-(4-Trifluoromethylphenyl)-3-phenylbuta-1,2-diene(2i):
PE, 0.119 g, 87%, yellow oil. 1H NMR (400 MHz, CDCl3):
Eluent:
CDCl3): δ = 202.0, 134.9, 131.9, 128.7, 127.6, 113.1, 93.5, 34.3, 29.5,
14.7, -1.6ppm.
δ
= 7.50 (d, J
= 8.0 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.30 (t,
[4h]
3-(Naphthalen-2-yl)-3-trimethylsilylbuta-1,2-diene (2q):
Eluent:
J = 7.6 Hz, 2H), 7.21(t, J = 7.2 Hz, 1H), 6.45 (q, 2.8 Hz, 1H), 2.21 (d, J
= 2.8 Hz, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ = 207.9, 138.7,
1
PE, 0.089 g, 71%, white solid. H NMR (400 MHz, CDCl3):
δ = 6.72-
6.77 (m, 3H), 6.60 (s, 1H), 6.47-6.36 (m, 3H), 5.23 (q, J = 2.8 Hz, 1H),
0.85 (d, J = 2.8 Hz, 3H), 0.16 (s, 9H) ppm. 13C {1H} NMR (100 MHz,
135.8, 128.7, 127.5, 127.1, 126.0, 125.7(q, J = 3.3 Hz), 123.1,105.4,
95.9, 16.7 ppm. IR(KBr) ν: 2949, 2867, 1943, 1761, 1624, 1496,
1386cm-1.
CDCl3):
δ = 202.5, 134.0, 133.9, 132.5, 128.2, 127.8, 127.7, 126.2,
[4h]
125.4, 125.0, 124.6, 113.0, 94.6, 34.4, 29.3, 14.9, -1.7 ppm. IR(KBr)
1-(Naphthylen-1-yl)-3-phenylbuta-1,2-diene (2j):
Eluent: PE,
δ = 8.26 (d, J
ν: 2989, 2837,1953, 1635, 1468, 1370cm-1.
1
0.103 g, 80%, yiellow solid. H NMR (400 MHz, CDCl3):
1,3-diphenylpenta-1,2-diene (2r):[11] Eluent: PE/EA=100/1; 0.081 g,
73%, colorless oil. 1H NMR (400 MHz, CDCl3):
δ = 7.47-7.41 (m, 2 H,),
7.36-7.25 (m, 6 H), 7.24-7.14 (m, 2 H), 6.56 (t, J = 3.2 Hz, 1 H, CH=),
2.67-2.48 (m, 2 H), 1.19 (t, J = 7.6 Hz, 206.2, 136.2, 134.7, 128.7,
128.4, 126.99,δH, CH3);13C {1H}NMR (100 MHz, CDCl3):δ = 126.96,
126.7, 126.0, 111.6, 98.6, 23.1, 12.5.
= 6.8 Hz, 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), 7.38 (t, J = 7.6 Hz, 1H), 7.32 (t, J =
7.6 Hz, 2H), 7.21 (t, J = 7.2 Hz, 1H), 7.21 (q, J = 2.0 Hz, 1H), 2.26 (d, J
= 2.4 Hz, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
δ = 208.1, 136.4,
134.0, 130.9, 130.6, 128.7, 128.5, 127.6, 127.0, 126.1, 125.8, 125.7,
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 9 of 10
View Article Online
DOI: 10.1039/C8OB00781K
Journal Name
ARTICLE
1-(4-methylpenta-2,3-dien-2-yl)benzene (5a): [10d] Eluent: PE, 0.067 1-(4-methylhexa-2,3-dien-2-yl)benzene (5j): [10d] Eluent: PE, 0.071 g,
83%, yellow oil. 1H NMR (400 MHz, CDCl3):
= 7.39-7.37 (m, 2H),
7.30-7.28 (m, 2H), 7.17-7.15 (m, 1H), 2.06 (s, 6H), 1.78 (s, 2H), 1.05-
1.01 (m, 3H) ppm. 13C {1H} NMR (100 MHz, CDCl3):
= 201.3, 139.0,
g, 84%, yellow oil. 1H NMR (400 MHz, CDCl3):
7.55 (s, 1H), 7.42-7.35 (m, 3H), 6.01 (q, J = 2.7 Hz, 1H), 1.85 (d, J =
2.7 Hz, 3H), 0.17 (s, 9H) ppm. 13C {1H} NMR (100 MHz, CDCl3):
δ
= 7.76-7.71 (m, 3H),
δ
δ
δ
=
128.3, 126.2, 125.7, 103.4, 100.1, 27.6, 18.8, 17.6, 12.5 ppm.
202.1, 138.7, 128.1, 126.1, 125.8, 98.2, 96.9, 20.4, 17.4 ppm. IR(KBr)
ν: 2992, 2867,1963, 1634, 1557, 1510, 1467, 1381cm-1.
1-fluoro-2-(4-methylhexa-2,3-dien-2-yl)benzene (5k):Eluent: PE,
0.086 g, 90%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.32-7.27 (m,
[10d]
1-methyl-4-(4-methylpenta-2,3-dien-2-yl)benzene (5b):
PE, 0.076 g, 88%, yellow oil. 1H NMR (400 MHz, CDCl3):
Eluent:
1 H), 7.15-7.11 (m, 1H), 7.08-6.96 (m, 2H), 2.08 (s, 3H), 2.04-2.01
(m, 2H), 1.76 (s, 3H), 1.06-1.02 (m, 3H) ppm. 13C {1H} NMR (100
δ
= 7.35-7.31
MHz, CDCl3):
δ = 202.9 ( d, J = 1.7 Hz), 160.5 (d, J = 247.6 Hz), 129.3
(m, 2H), 7.18-7.13 (m, 2H), 2.38 (s, 3H), 2.09 (s, 3H), 1.83 (s, 6H)
ppm. 13C {1H} NMR (100 MHz, CDCl3):
= 201.8, 135.9, 135.8, 129.1,
(d, J = 4.0 Hz), 127.8 (d, J = 8.2 Hz), 127.5 (d, J = 11.7 Hz), 123.8 (d, J
=3.6 Hz), 116.2 (d, J = 22.7 Hz), 101.5 (d, J =1.3 Hz), 95.8, 27.5, 19.6,
19.1, 12.3 ppm. HRMS (ESI) m/z calcd for C13H16F+ (M+H)+
191.12306, found 191.12286.
1-fluoro-3-(3-methylhexa-2,3-dien-2-yl)benzene (5l): [10d] Eluent: PE,
0.086 g, 90%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.25-7.21 (m,
1H), 7.15 (d, J = 8Hz, 1 H), 7.08-7.04 (m, 1H), 6.86-6.81 (m, 1H),
2.11-2.05 (m, 2H), 2.03 (s, 3H), 1.78 (s, 3H), 1.03 (t, J = 4 Hz, 3H)
ppm. 13C {1H} NMR (100 MHz, CDCl3):
δ
125.7, 98.2, 96.8, 21.2, 20.5, 17.5 ppm. IR(KBr) ν: 2993, 2873,1962,
1654, 1577, 1510, 1450, 1374cm-1.
[10d]
1-chloro-3-(4-methylpenta-2,3-dien-2-yl)benzene (5c):
Eluent:
1
PE, 0.088 g, 91%, yellow oil. H NMR (400 MHz, CDCl3):
δ
= 7.33 (s,
1H), 7.22-7.16 (m, 2H), 7.15-7.11 (m, 1H), 2.02 (s, 3H), 1.80 (s, 6H)
ppm. 13C {1H} NMR (100 MHz, CDCl3):
= 202.3, 141.1, 134.3, 129.5,
δ
126.1, 125.9, 123.9, 97.7, 97.5, 20.4, 17.2 ppm.
δ = 201.6, 164.5, 162.1, 141.7
(d, J = 7.2 Hz), 129.6 (d, J = 8.2 Hz), 121.3 (d, J =2.6 Hz), 112.6 (q, J =
38.6 Hz), 104.1, 99.6 (d, J =2.5 Hz), 27.6, 18.9, 17.5, 12.4 ppm.
1-fluoro-2-(4-methylpenta-2,3-dien-2-yl)benzene (5d): Eluent: PE,
0.081 g, 92%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ
= 7.15-7.12 (m,
1H), 7.03-6.99 (m, 1H), 6.88-6.82 (m, 2H), 1.94 (s, 3H), 1.64 (s, 6H)
ppm. 13C {1H} NMR (100 MHz, CDCl3):
= 203.7 (d, J = 1.5 Hz), 160.5
[10d]
1-fluoro-4-(4-methylhexa-2,3-dien-2-yl)benzene (5m):
PE, 0.087 g, 92%, yellow oil. 1H NMR (400 MHz, CDCl3):
Eluent:
δ
δ
= 7.35-7.31
(d, J = 247.5 Hz), 129.4 (d, J = 3.8 Hz), 127.9 (d, J = 8.2 Hz), 127.5 (d,
J =11.6 Hz), 123.9 (q, J = 3.6 Hz), 116.2 (d, J = 22.7 Hz), 95.1 (d, J =
1.5 Hz), 93.8, 20.5, 19.5 ppm. HRMS (ESI) m/z calcd for
C12H14F+(M+H)+ 177.10741, found 177.10725.
(m, 2 H), 7.01-6.96 (m, 2H), 2.12-2.07 (m, 2H), 2.06 (s, 3H), 1.79 (s,
3H), 1.03 (t, J = 3 Hz, 3H) ppm. 13C {1H} NMR (100 MHz, CDCl3):
201.1, 161.6 (d, J = 243.5 Hz), 127.1 (d, J =7.8 Hz), 115.2, 115.0,
δ
=
103.7, 99.4, 27.6, 19.2, 17.8, 12.6 ppm.
1-fluoro-3-(4-methylpenta-2,3-dien-2-yl)benzene (5e):[10d] Eluent:
1-chloro-3-(4-methylhexa-2,3-dien-2-yl)benzene (5n): [10d] Eluent: PE,
0.091 g, 88%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.33 (s, 1 H),
PE, 0.084 g, 92%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.25-
7.21 (m, 1H), 7.14-7.11 (d, J = 8.1 Hz, 1H), 7.06-7.02 (d, J = 12.0 Hz,
7.24-7.19 (m, 2H), 7.15-7.11 (m, 1H), 2.11-2.06 (m, 2H), 2.03 (s, 3H),
1H), 6.88-6.83 (m, 1H), 2.03 (s, 3H), 1.79 (s, 6H) ppm. 13C {1H} NMR
1.79 (s, 3H), 1.03 (t, J = 3 Hz, 3H) ppm. 13C {1H} NMR (100 MHz,
(100 MHz, CDCl3):
129.6 (d, J = 8.3 Hz), 121.5 (d, J =2.6 Hz), 112.7 (q, J = 38.6 Hz),
δ = 201.7, 164.5, 162.1, 141.7 (d, J = 7.4 Hz),
CDCl3):
δ = 201.5, 141.1, 134.3, 129.5, 126.1, 125.6, 123.8, 104.1,
99.5, 27.5, 18.9, 17.5, 12.4 ppm.
104.2, 99.7, 22.5, 18.9 ppm.
1-fluoro-4-(4-methylpenta-2,3-dien-2-yl)benzene (5f):[10d] Eluent: PE,
1-bromo-3-(4-methylhexa-2,3-dien-2-yl)benzene (5o): Eluent: PE,
0.109 g, 87%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.41-7.39 (m,
0.084 g, 92%, yellow oil. 1H NMR (400 MHz, CDCl3):
(m, 2H), 6.99-6.96 (m, 2H), 2.03 (s, 3H), 1.79 (s, 6H) ppm. 13C {1H}
NMR (100 MHz, CDCl3): = 201.8 (d, J = 2Hz), 162.8, 160.2, 134.8 (d,
δ = 7.32-7.28
1H), 7.35-7.30 (m, 1 H), 7.24-7.20 (m, 1H), 7.18-7.02 (m, 1H), 2.11-
2.08 (m, 2H), 2.07 (s, 3H), 1.81 (s, 3H), 1.06 (t, J = 4 Hz, 3H) ppm. 13C
{1H} NMR (100 MHz, CDCl3):
δ = 201.3, 142.8, 139.5, 128.3, 128.2,
δ
125.7, 123.1, 103.2, 100.2, 27.6, 19.1, 17.5, 12.4 ppm. HRMS (ESI)
J = 3.1Hz), 127.2 (d, J = 7.8Hz), 115.1 (d, J = 21.3Hz), 97.3, 97.2, 20.6,
17.5 ppm. IR(KBr) ν: 2996, 2874, 1962, 1607, 1498, 1451, 1376,
1234cm-1.
m/z calcd for C13H16Br+(M+H)+ 251.04299, found 251.04298.
1-methyl-4-(4-methylpenta-2,3-dien-2-yl)benzene (5p): Eluent: PE,
0.078 g, 84%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.28 (d, J = 2
1-bromo-3-(4-methylpenta-2,3-dien-2-yl)benzene (5g): Eluent: PE,
Hz, 2H), 7.11 (d, J = 2 Hz, 2H), 2.32 (s, 3H), 2.06 (s, 3H), 2.07-2.02 (m,
0.101 g, 86%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ
= 7.38-7.36
(m, 1H), 7.31-7.29 (m, 1H), 7.21-7.17 (m, 1H), 6.99-6.97 (m, 1H),
2.04 (s, 3H), 1.78 (s, 6H) ppm. 13C {1H} NMR (100 MHz, CDCl3):
2H), 1.78 (s, 3H), 1.03 (t, J = 1.8 Hz, 3H) ppm. 13C {1H} NMR (100
MHz, CDCl3):
δ = 201.1, 135.9, 135.8, 129.0, 125.6, 103.2, 100.1,
δ
=
27.7, 21.3, 18.9, 17.6, 12.5 ppm. HRMS (ESI) m/z calcd for
C14H19+(M+H)+187.14813, found 187.14836.
202.4, 141.0, 134.3, 129.5, 129.4, 125.9, 123.9, 97.7, 97.4, 20.5,
17.3 ppm. HRMS (ESI) m/z calcd for C12H14Br+ (M+H)+ 237.02734,
found 237.02737.
1-fluoro-4-(3-phenylbuta-1,2-dienyl)benzene (5q): Eluent: PE, 0.099
g, 83%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.43- 7.41 (m, 1H),
1-bromo-4-(4-methylpenta-2,3-dien-2-yl)benzene (5h):[10d] Eluent:
7.40-7.38 (m, 1H), 7.38-7.36 (m, 2H), 7.34-7.29 (m, 2H), 7.23-7.18
PE, 0.108 g, 91%, yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.44-
(m, 1H), 7.02-6.96 (m, 2H), 2.18 (s, 3H), 2.16 (s, 3H) ppm. 13C {1H}
7.41 (m, 2H), 7.31-7.27 (m, 2H), 2.06 (s, 3H), 1.75 (s, 6H) ppm. 13C
NMR (100 MHz, CDCl3):
δ = 205.6 (d, J = 2.1Hz), 162.1 (d, J =
{1H} NMR (100 MHz, CDCl3):
98.2, 97.1, 20.6, 17.6 ppm.
δ = 202.1, 138.9, 128.2, 125.8, 122.8,
244.3Hz), 137.2, 133.3 (d, J = 3.2Hz), 128.6, 127.5 (d, J = 7.9Hz),
127.1, 125.9, 115.5 (d, J = 21.4Hz), 102.6, 101.7, 17.1, 17.0 ppm.
HRMS (ESI) m/z calcd for
239.12309.
C
17H16F+ (M+H)+ 239.12306, found
2-(4-methylpenta-2,3-dien-2-yl)thiophene (5i): [10d] Eluent: PE, 0.068
g, 83%, yellow oil. 1H NMR (400 MHz, CDCl3):
= 7.13-7.11 (m, 1H),
6.96-6.93 (m, 1H), 6.86-6.83 (m, 1H), 2.05 (s, 3H), 1.79 (s, 6H) ppm.
13C {1H} NMR (100 MHz, CDCl3):
= 201.1, 145.1, 127.5, 124.1, 122.4,
δ
1-chloro-4-(3-phenylbuta-1,2-dienyl)benzene (5r): Eluent: PE, 0.108
1
δ
g, 85%, yellow oil. H NMR (400 MHz, CDCl3):
δ = 7.43-7.41 (m, 2H),
98.1, 94.5, 20.6, 18.3 ppm. IR(KBr) ν: 2942, 1950, 1531, 1447,
7.36-7.34 (m, 3H), 7.33-7.30 (m, 1H), 7.29-7.27 (m, 1H), 7.24-7.21
1374cm-1.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 10 of 10
View Article Online
DOI: 10.1039/C8OB00781K
ARTICLE
Journal Name
(m, 1H), 2.21 (s, 3H), 2.18 (s, 3H) ppm. 13C {1H} NMR (100 MHz,
I. Satyanarayana, L. Mohan, A. Edukondalu, J. Org. Chem.,
2016, 81, 987-999.
a) S.-M. Ma, S.-C. Yu and S.-H. Yin, J. Org. Chem. 2003, 68,
8996-9002; b) M. Yokota, K. Fuchibe, M. Ueda, Y. Mayumi
and J. Ichikawa, Org. Lett., 2009, 11, 3994-3997.
M. Brossat, M.-P. Heck and C. Mioskowski, J. Org. Chem.,
2007, 72, 5938-5941.
CDCl3):
δ = 205.9, 137.1, 135.8, 132.6, 128.63, 128.61, 127.2, 127.1,
5
126.0, 103.0, 101.8, 16.9, 16.8 ppm. HRMS (ESI) m/z calcd for
C17H16Cl+(M+H)+ 255.09350, found 255.09341.
6
7
8
9
J.-K. Kuang and S.-M. Ma, J. Am. Chem. Soc., 2010, 132
1786-1787.
,
Conflicts of interest
Y.-L. Wang, W.-L. Zhang and S.-M. Ma, J. Am. Chem. Soc.
2013, 135, 11517-11520.
a) C. Deutsch, B. H. Lipshutz and N. Krause, Angew. Chem. Int.
Ed., 2007, 46, 1650-1653; b) H. Ito, Y. Sasaki and M.
Sawamura, J. Am. Chem. Soc., 2008, 130, 15774-15775.
There are no conflicts to declare.
Acknowledgements
10 a) S.-T. Chang, Q.-H. Li, R,-T. Chiang, H.-M. Gau, Tetrahedron,
2012, 68, 3956-3962; b) Q.-H. Li, H.-M. Gau, Synlett. 2012,
The authors are grateful to the Fundamental Research Funds for the
Central Universities, Southwest University for Nationalities (No.
2018NZD06) and the Sichuan Provincial Department of science and
technology support program (No. 2015NZ0033) for financial
support.
5
,
747-750; c) Q.-H. Li, Y. Ding, X.-J. Yang, Chin. Chem. Lett.,
2014, 25, 1296-1300; d) Z. Zhang, S. Mo, G. Zhang, X.-B.
Shao, Q.-H. Li, Y. Zhong. Synlett. 2017, 5, 611-614; e) Z.
Zhang,X.-B. Shao, G. Zhang, Q.-H. Li, X.-Y. Li, Synthesis. 2017
49, 3643-3653.
,
11 Y.-J. Cai, X.-J. Tang, S.-M. Ma, Chem. Eur. J. 2016, 22, 2266-
2269.
12 Z.-S. Chen, X.-H. Duan, L.-Y. Wu, S. Ali, K.-G. Ji, P. -X. Zhou, X.-
Y. Liu, Y.-M. Liang, Y.-M. Chem.-A. Eur. 2011,17, 6918-6921.
Notes and references
1
a) M. Orgasawara, T. Nagano and T. Hayashi, J. Org. Chem.,
2005, 70, 5764-5767; b) A. Hoffmann-Röder and N. Krause,
Angew. Chem. Int. Ed., 2004, 43, 1196-1216.
2
a) T. G. Back, K. N. Clary and D. Gao, Chem. Rev. 2010, 110
,
4498-4553; b) S.-C. Yu and S.-M. Ma, Chem. Commun., 2011,
47, 5384-5418; c) S.-C. Yu and S.-M. Ma, Angew. Chem. Int.
ed., 2012, 51, 3074-3112; c) N. N. Bhuvan Kumar, Manab
Chakravarty, N. Satish Kumar, K. V. Sajna, K. C. Kumara
Swamy, J. Chem. Sci., 2009, 121, 23-36; d) K. C. Kumara
Swamy, Mandala Anitha, G. Gangadhararao, R. Rama Suresh,
Pure. Appl. Chem., 2017, 89, 367-378; e) Y. Hu, S. Li, Z.-L.
Wang, Y.-B. Yao, T.-J. Li, C.-X. Yu, C.-S. Yao, J. Org. Chem.,
2018, 83, 3361-3366; f) C.-J. Ni, J.-F. Chen, Y.-W. Zhang, Y.-D.
Hou, D. Wang, X.-F. Tong, S.-F. Zhu, Q.-L. Zhou, Org. Lett.,
2017, 19, 3668-3671.
3
For recent reviews on the synthesis of allenes, see: a) L. K.
Sydnes, Chem. Rev. 2003, 103, 1133-1150; b) N. Krause, A.
Hoffmann-Röder, Tetrahedron 2004, 60, 11671-11694; c) K.
M. Brummond, J. E. Deforrest, Synthesis 2007, 6, 795-818; d)
N. Krause, V. Belting, C. Deutsch, J. Erdsack, H. Fan, B. Gockel,
A. Hoffmann-Röder, N. Morita, F. Volz, Pure Appl. Chem.,
2008, 80
Asymmetry 2009, 20, 259-271; f) R. K. Neff, D. E. Frantz, ACS
Catal. 2014, , 519-528.
, 1063-1069; e) M. Ogasawara, Tetrahedron:
4
4
For selected recent reports on the synthesis of allenes, see: a)
B. Bolte, Y. Odabachian, F. Gagosz, J. Am. Chem. Soc. 2010,
132, 7294-7296; b) M. Kalek, J. Stawinski, Adv. Synth. Catl.
2011, 353, 1741-1755; c) Q. Xiao, Y. Xia, H. Li, Y. Zhang, J.-B.
Wang, Angew. Chem. Int. Ed. 2011, 50, 1114-1117; Angew.
Chem. 2011, 123, 1146-1149; d) X.-Z. Yu, J.-L. Zhang, Adv.
Synth. Catl. 2011, 353, 1265-1268; e) M. L. Hossain, F. Ye, Y.
Zhang, J.-B. Wang, J. Org. Chem. 2013, 78, 1236-1241; f) T.
Hashimoto, K. Sakata, F. Tamakuni, M. J. Dutton, K. Maruoka,
Nat. Chem., 2013,
Zhao, Z.-G. Zhang, T. Ayad, V. Ratovelomanana-Vidal, ACS
Catal., 2014, , 44-48; h) Q.-H. Li, J.-Y. Jeng, H.-M. Gau, Eur. J.
5, 240-244; g) Z. Wu, F. Berhal, M.-M.
4
Org. Chem., 2014, 31, 7916-7923; i) Q.-H. Li, J.-W. Liao, Y.-L.
Huang, R.-T. Chiang, H.-M. Gau, Org. Biomol. Chem., 2014, 12
7634-7642; j) G. Gangadhararao, K. C. K. Swamy,
Tetrahedron 2014, 70, 2643-2653; k) W. Wei, J. -W. Wen, D.-
S. Yang, M.-Y. Guo, Y.-Y. Wang, J.-M. You, H. Wang, Chem.
,
Commun. 2015, 51, 768-771; l) X.-J. Tang, Y.-L. Han, S.-M. Ma,
Org. Lett. 2015, 18, 1176-1179; m) J. Ruchti, E. M. Carreria,
Org. Lett. 2016, 18, 2174-2176; n) M. Periasamy, P. O. Reddy,
10 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins