Pd-catalyzed decarboxylative coupling of arylalkynyl carboxylic acids with allyl ethers: Regioselective synthesis of branched 1,3-enynes

Article abstract of DOI:10.1016/j.tet.2015.10.036

This work reported an efficient and novel method to prepare branched 1,3-enynes via Pd(II)-catalyzed decarboxylative coupling of arylalkynyl carboxylic acids with allylic ethers under mild conditions. Various arylalkynyl carboxylic acids and allylic ether

Full text of DOI:10.1016/j.tet.2015.10.036

Accepted Manuscript
Pd-Catalyzed Decarboxylative Coupling of Arylalkynyl Carboxylic Acids with Allyl
Ethers: Regioselective Synthesis of Branched 1, 3-Enynes
Jun-Ying Jiao, Xing-Guo Zhang, Xiao-Hong Zhang
PII:
S0040-4020(15)30136-8
10.1016/j.tet.2015.10.036
TET 27208
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 24 August 2015
Revised Date: 12 October 2015
Accepted Date: 15 October 2015
Please cite this article as: Jiao J-Y, Zhang X-G, Zhang X-H, Pd-Catalyzed Decarboxylative Coupling
of Arylalkynyl Carboxylic Acids with Allyl Ethers: Regioselective Synthesis of Branched 1, 3-Enynes,
Tetrahedron (2015), doi: 10.1016/j.tet.2015.10.036.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
To create your abstract, type over the instructions in the template box below.
Fonts or abstract dimensions should not be changed or altered.
Leave this area blank for abstract info.
Pd-Catalyzed Decarboxylative Coupling of
Arylalkynyl Carboxylic Acids with
Allyl Ethers: Regioselective Synthesis of Branched 1, 3-Enynes
Jun-Ying Jiao, Xing-Guo Zhang, Xiao-Hong Zhang*
a college of chemical and materials engineering, Wenzhou University, Wenzhou 325035, China
Author to whom correspondence should be addressed; E-Mail: kamenzxh@wzu.edu.cn

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Pd-Catalyzed Decarboxylative Coupling of Arylalkynyl Carboxylic Acids with Allyl Ethers:
Regioselective Synthesis of Branched 1, 3-Enynes
Jun-Ying Jiao, Xing-Guo Zhang, Xiao-Hong Zhang*
a college of chemical and materials engineering, Wenzhou University, Wenzhou 325035, China
Author to whom correspondence should be addressed; E-Mail: kamenzxh@wzu.edu.cn
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
This work reported an efficient and novel method to prepare branched 1, 3-enynes via Pd(II)-
catalyzed decarboxylative coupling of arylalkynyl carboxylic acids with allylic ethers under
mild conditions. Various arylalkynyl carboxylic acids and allylic ethers could participate in the
reaction, regioselectively affording the desired branched 1, 3-enynes in moderate to good yields.
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
decarboxylative coupling; arylalkynyl carboxylic
acid; allylic ether; 1, 3-enyne
1. Introduction
mild conditions, giving the branched 1, 3-enynes in moderate to
good yields. Moreover, O2 was used as the sole oxidant and
therefore only CO2 and water were formed as the by-products in
the reaction, which is a green and environmentally benign
procedure. Herein, we reported the results in detail.
The 1, 3-enyne moiety attracted much interest owing to its
existence in many naturally occurring and pharmaceutically
active compounds.1 For example, terbinafine, containing the 1, 3-
enyne moiety, exhibited strong antimycotic activity and was
used currently for the treatment of skin mycoses.2 1, 3-Enynes
were also versatile building blocks for the synthesis of
aphthalenes,3 heterocyclic compounds 4, conjugated alkenes 5 and
so on. Therefore, much attention had been paid to the synthesis
2. Results and discussion
We chose phenylpropiolic acid (1a) and allyl phenyl ether
(2a) as the model substrates to optimize suitable conditions using
Pd(OAc)2 as catalyst, DPPP as ligand at 80 °C under N2 (Table
1). It was found that solvent, catalyst, ligand, oxidant and
reaction temperature critically affected the decarboxylative
coupling reaction efficiency. Solvents such as HOAc/DCE,
HOAc, MeCN, DMSO and Ac2O were less effective than
HOAc/MeCN (entries 2-6), whereas the desired product 3 was
obtained in 39 % yield when using a mixed solvent of
HOAc/MeCN (entry 1). Three commonly used catalyst
precursors, such as Pd(PPh3)4, Pd2(dba)3 and Pd(CF3COO)2
(entries 7-9) were next surveyed to give worse results than
Pd(OAc)2 (entry 1). Among the ligands screened, 1,3-
bis(diphenylphosphino)propane (DPPP) turned out to be the
6
of 1, 3-enynes. Among various approaches available for 1,3-
enynes, by far the most common and convenient method widely
used was Sonogashira coupling reaction of terminal alkynes with
vinyl halides using palladium-copper,7 palladium,8 copper or
9
iron 10 as catalysts. However, these reactions were dependent on
preactivation of alkene with halide to form vinyl halide, which
required several extra synthetic steps and generated waste. Pd-
catalyzed coupling reaction of organometallic alkyne (Cu, Mg,
Si, Zn, Sn)11 with alkene and the alkynylation of alkenylmetals
(Al, B, Cu, Mg, Zr)12 afforded alternative two methods, but
suffered from some intrinsic shortcomings, including difficult
preparation of organometallic alkyne or alkene, poor functional
group compatibility, undesired by-products and low yields.
Therefore, it was deserved to seek for more economical and
convenient methodologies to provide 1, 3-enynes.
best,
while
2,2’-bipyridyl
(bpy),
1,1'-
(DPPF),
(DPPE),
bis(diphenylphosphino)ferrocene
bis(diphenylphosphino)ethane
bis(diphenylphosphino)butane (DPPB), triphenylphosphine
(PPh3) and 1,10-phenanthroline were not that effective (entries
11-16). Notably, only trace of decarboxylative product can be
detected in the absence of ligand (entry 10), showing the ligand
played an indispensable role in the reaction. Subsequently, the
reaction was tried to proceed under air and O2, affording the
decarboxylative coupling product 3 in 42 and 67 % yields,
respectively (entries 17, 18). Encouraged by these results,
reaction temperatures were evaluated to obtain the optimal
conditions (entries 19-21) and it was interesting to find the yield
of decarboxylative product could be dramatically increased to 72
Over the past decade, decarboxylative coupling reactions for
the alkynyl carboxylic acid substrates had been successfully
applied to construct the C-C,13 C-N14 or C-P15 bonds in organic
synthesis. These transformations were attracting due to the usage
of much cheap and available alkynyl carboxylic acid as coupling
partner, the release of harmless CO2 and the avoidance of
homocoupling products.16 As part of our ongoing efforts devoted
to the synthesis of 1, 3-enynes,17 we wished to report the Pd-
catalyzed decarboxylative coupling protocol for the synthesis of
1, 3-enyne using alkynyl carboxylic acid and unactivated allyl
ether as the coupling partner. The reaction could proceed under

2
ACCEPTED MANUSCRIPT
% when the reaction was performed at 30 °C by comparison with
80, 120 and
oC. To our delight, the reaction also
regioselectively afforded the branched ((2-methylene-4-
phenylbut-3-yn-1-yl)oxy)benzene Unfortunately,
(3).17
decreasing the amount of allyl phenyl ether (2a) to 0.3 mmol (1
equiv) as well as shortening the reaction time to 24 h resulted in
lower yields (entries 22, 23). Thus the optimal condition was
identified as followings: phenylpropiolic acid (1.0 equiv), allylic
ether (2 equiv), Pd(OAc)2 (10 mol%), DPPP (20 mol%),
HOAc/MeCN (v/v = 1:3), 30 oC, 48 h under O2.
Gratifyingly, the bulky 3-(naphthalene-1-yl)propiolic acid
underwent the decarboxylative coupling reaction with allyl
phenyl ether smoothly, giving 1-(3-(phenoxymethyl)but-3-en-1-
ynyl)naphthalene 14 in 48 % yield. It was notable that the
coupling reaction of phenylpropiolic acids with allyl phenyl
sulfide can also proceed well when the reaction temperature was
raised to 80 oC, providing the 1, 3-enyne products 15 and 16 with
sulfur atoms in acceptable yields. Unfortunately, the aliphatic
carboxylic acid, such as propiolic acid or 2-butynoic acid, was
intolerant to the catalytic system.
0
Table 1. Modification of the Typical Reaction Conditions a
Table 2. Pd-Catalyzed Decarboxylative Coupling of Alkynyl
Carboxylic Acids with Allyl Phenyl Ether (Sulfide) a,b
Yield(%)
Entry
Catalyst
Ligand
Solvent b
T(°C)
c
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(PPh3)4
Pd2(dba)3
Pd(CF3COO)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
DPPP
DPPP
DPPP
DPPP
DPPP
DPPP
DPPP
DPPP
DPPP
-
HOAc/MeCN
HOAc/DCE
HOAc
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
39
NR
20
trace
NR
NR
NR
25
MeCN
DMSO
Ac2O
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
22
trace
NR
15
31
53
bpy
DPPF
DPPE
DPPB
PPh3
11
1,10-
16
Pd(OAc)2
HOAc/MeCN
80
NR
phenanthroline
DPPP
DPPP
DPPP
DPPP
DPPP
DPPP
DPPP
17d
18e
19e
20e
21e
22e
23e
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
HOAc/MeCN
80
80
120
30
0
42
67
30
72
trace
53f
50g
30
30
a Reaction conditions: alkynyl carboxylic acids (0.3 mmol), allyl
phenyl ethers (0.6 mmol), Pd(OAc)2 (10 mol %), DPPP (20 mol
a
Reaction conditions: phenylpropiolic acid (0.3 mmol), allyl
phenyl ether (0.6 mmol), catalyst (10 mol %), ligand (20 mol %),
b
%), solvent (2 mL, v / v = 1:3), 30 °C, 48 h, under oxygen.
solvent (2 mL), 80 °C, 48 h, under N2 unless otherwise noted. b
v
Isolated yields. c The reaction was carried under 80 °C.
/ v = 1 : 3, c Isolated yields. d The reaction was carried out under
air. e The reaction was carried out under O2. f The amount of allyl
phenyl ether was 0.3 mmol. g Shorten the reaction to 24 h.
Subsequently, phenylpropiolic acids were examined with
respect to various allyl aryl ethers to afford 1, 3-enynes
derivatives (Table 3). The results demonstrated that allyl aryl
ethers having electron-donating groups favored the
decarboxylative coupling reaction than those with electron-
withdrawing groups. Methyl, ethyl, methoxy or benzyloxy ethers
provided 1, 3-enynes 17-22 in 63 %-82 % yields. Meanwhile,
fluoride, chloride and bromide ethers afforded 23-26 in 40 %-
57 % yields. And trace of desired product could be obtained
With the optimized conditions in hand, the scope of
arylalkynyl carboxylic acids was initially explored (Table 2).
The results showed that several functional groups on the phenyl
moiety, including methyl, methoxyl, fluoro, chloro, bromo, and
acetyl groups were tolerated in this decarboxylative coupling
procedure. Generally, the electron-donating substituents were
beneficial for the transformation, whereas the electron-
withdrawing groups decreased the efficiency. For example,
methyl substituted arylalkynyl carboxylic acids provided
when
1-(allyloxy)-4-nitrobenzene
was
reacted
with
phenylpropiolic acid. To our delight, phenyl homoallylic ether
such as (but-3-en-1-yloxy)benzene could smoothly undergo the
coupling reaction, giving the aimed product 27 in good yield.
But only 30 % yield of (3-(methoxymethyl)but-3-en-1-yn-1-
yl)benzene 28 could be isolated when allyl methyl ether was
reacted with phenylpropiolic acid, which showed that the
optimal reaction condition was more compatible to the aromatic
ether.
products 4-7 in more than 63
% yields, while 3-(4-
methoxyphenyl)propiolic acid gave its corresponding product 9
in 70 % yield. Meanwhile, chloride and bromide products (11
and 12) were obtained in 60 % and 63 % yields, respectively.
Products 10 and 13 bearing fluoride and acetyl groups were
isolated in 35% and 40 % yields, respectively. In the catalytic
decarboxylative coupling reaction, steric hindrance affected the
efficiency slightly. o, m,
phenylpropiolic acids afforded their corresponding products in
the similar yields except the relatively low yield of compound 8.
p -Methyl and 3,4-dimethyl
A possible mechanism for the present palladium (II)-
catalyzed decarboxylative coupling of phenylpropiolic acid with
allyl phenyl ether is proposed in Scheme 1. First, the reaction of

3
ACCEPTED MANUSCRIPT
Pd(OAc)2 with phenylpropiolic acid by releasing HOAc and CO2
affords an arylpalladium (II) species A.18 The insertion of the
double bond of allyl phenyl ether to A generates intermediate B,
which would be followed by β-H elimination to produce the
desired product 1,3-enyne 3 and Pd (0) with loss of a molecule
of HOAc. The resulting Pd (0) is then oxidized by O2 to
regenerate the Pd (II) catalyst.19
only CO2 and water were formed as the by-products. Various
alkynyl carboxylic acids could participate in the reaction,
regioselectively affording the desired branched 1, 3-enynes
in moderate to good yield. The proposed mechanism was
described.
4. Experimental Section
4.1 General
Table 3.
Pd-Catalyzed Decarboxylative Coupling of
Phenylpropiolic Acids with Allyl Aryl Ether a,b
Chemicals were either purchased or purified by standard
1
techniques. H NMR and 13C NMR spectra were measured on a
500 MHz spectrometer (1H at 500 MHz, 13C at 125 MHz), using
CDCl3 as the solvent with tetramethylsilane (TMS) as an internal
standard at room temperature. Chemical shifts are given in δ
relative to TMS, and the coupling constants J are given in hertz.
High-resolution mass spectra were recorded on an ESI-Q-TOF
mass spectrometer. All reactions under oxygen atmosphere were
conducted using standard Schlenk techniques. Melting points
were measured on X4 melting point apparatus (Beijing Tech.
Instrument) and uncorrected. Column chromatography was
performed using EM silica gel 60 (300-400 mesh).
4.2 Typical experimental procedure for the Pd(OAc)2-
catalyzed direct decarboxylative coupling of alkynyl
carboxylic acids with allyl ethers
Arylalkynyl carboxylic acids (0.3 mmol), allyl ethers (0.6
mmol), Pd(OAc)2 (10 mol %), and DPPP (20 mol %) were added
to a two necked flask, and then a mixed solvent of CH3CN (1.5
mL) and HOAc (0.5 mL) was added. The mixture was then
stirred at 30 °C for 48 h under oxygen. After the reaction was
complete, the mixture was washed with saturated aqueous
NaHCO3 solution and extracted with CH2Cl2 three times. The
combined organic layer was dried with anhydrous Na2SO4 and
evaporated in vacuum. The resulting crude product was purified
by flash chromatography on silica gel using hexane or
hexane/ethyl acetate (150:1) as the eluent to give the pure
products.
a
Reaction conditions: phenylpropiolic acids (0.3 mmol), allyl
aryl ether (0.6 mmol), Pd(OAc)2 (10 mol %), DPPP (20 mol %),
solvent (2 mL, v / v = 1:3), 30 °C, 48 h, under oxygen. b Isolated
yields.
Scheme 1 Plausible mechanism pathway
4.3. Characterization data
4.3.1 ((2-Methylene-4-phenylbut-3-yn-1-yl)oxy)benzene (3).17
1
Yellow oil, 72% yield (50.6 mg). H NMR (500 MHz, CDCl3) δ
7.48-7.47 (m, 2H), 7.34-7.29 (m, 5H), 6.99-6.98 (m, 3H), 5.71
(s, 1H), 5.68 (s, 1H), 4.65 (s, 2H). 13C{1H} NMR (125 MHz,
CDCl3) δ 158.5, 131.8, 129.6, 128.7, 128.5, 127.3, 122.9, 122.2,
121.3, 115.1, 90.9, 87.1, 69.7. LRMS (EI, 70 eV) m/z (%): 234
(M+, 51), 191 (16), 141 (23), 115 (100), 77 (17).
4.3.2 1-Methyl-4-(3-phenoxymethyl-but-3-en-1-ynyl)benzene (4).
1
17 Yellow oil, 75% yield (55.8 mg). H NMR (500 MHz, CDCl3)
δ 7.38 (d, J = 8.0 Hz, 2H), 7.34-7.30 (m, 2H), 7.15 (d, J = 8.0
Hz, 2H), 7.02-6.97 (m, 3H), 5.70 (s, 1H), 5.67 (s, 1H), 4.66 (s,
2H), 2.38 (s, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 158.6,
138.8, 131.7, 129.6, 129.2, 127.5, 121.7, 121.3, 119.9, 115.2,
91.1, 86.5, 69.8, 21.6. LRMS (EI, 70 eV) m/z (%): 248 (M+,
100), 233 (40), 153 (83), 139 (55), 129 (63).
3. Conclusions
4.3.3 1-Methyl-2-(3-phenoxymethyl-but-3-en-1-ynyl)benzene (5).
Yellow oil, 70% yield (52.1 mg). H NMR (500 MHz, CDCl3) δ
1
In conclusion, we had developed an efficient and mild
protocol to synthesize 1, 3-enyne compounds at low
temperature (30 oC) via Pd(OAc)2-catalyzed direct
decarboxylative coupling of alkynyl carboxylic acids with
unactived allyl ether. This method did not require the
preactivation of alkene with halide to form vinyl halide and
exemplified the ideals of atom and step economy. Moreover,
the procedure was also green and environmentally because
7.43 (d, J = 7.5 Hz, 1H), 7.32-7.29 (m, 2H), 7.24-7.19 (m, 2H),
7.17-7.13 (m, 1H), 7.00-6.97 (m, 3H), 5.70 (d, J = 1.0 Hz, 1H),
5.67 (s, 1H), 4.66 (s, 2H), 2.46 (s, 3H). 13C{1H} NMR (125
MHz, CDCl3) δ 158.6, 140.4, 132.1, 129.62, 129.61, 128.7,
127.6, 125.7, 122.8, 121.8, 121.3, 115.2, 91.0, 89.9, 69.9, 20.8.
HRMS (ESI): calcd for C18H17O + ([M + H]+) 249.1274, Found:
249.1277.

4
ACCEPTED MANUSCRIPT
4.3.4
1-Methyl-3-(3-phenoxymethyl-but-3-en-1-ynyl)-benzene
(d, J = 1.5 Hz, 1H), 4.65 (s, 2H), 2.60 (s, 3H). 13C{1H} NMR
(125 MHz, CDCl3) δ 197.3, 158.5, 136.7, 132.0, 129.7, 128.4,
127.8, 127.2, 123.5, 121.5, 115.2, 90.3, 90.1, 69.6, 26.7. HRMS
(6): 17 Yellow oil, 63 % yield (46.9 mg). H NMR (500 MHz,
CDCl3) δ 7.32-7.25 (m, 4H), 7.21 (t, J = 7.5 Hz, 1H), 7.14 (d, J =
7.5 Hz, 1H), 6.99-6.96 (m, 3H), 5.69 (d, J = 1.5 Hz, 1H), 5.66 (d,
J = 1.5 Hz, 1H), 4.63 (s, 2H), 2.33 (s, 3H). 13C{1H} NMR (125
MHz, CDCl3) δ 158.6, 138.2, 132.4, 129.61, 129.55, 128.9,
128.4, 127.4, 122.8, 122.0, 121.3, 115.2, 91.1, 86.8, 69.8, 21.3.
LRMS (EI, 70 eV) m/z (%): 248 (M+, 100), 153 (76), 152 (45),
139 (49), 129 (60).
1
(ESI): calcd for C19H17O2 ([M + H]+) 277.1223, Found:
+
277.1236.
4.3.12 1-(3-Phenoxymethyl-but-3-en-1-ynyl)-naphthalene (14).
Yellow oil, 48 % yield (40.9 mg). 1H NMR (500 MHz, CDCl3) δ
8.35 (d, J = 8.5 Hz, 1H), 7.86 (t, J = 8.0 Hz, 2H), 7.71 (d, J = 7.0
Hz, 1H), 7.59-7.52 (m, 2H), 7.45 (t, J = 8.0 Hz, 1H), 7.36-7.31
(m, 2H), 7.05-6.99 (m, 3H), 5.81 (s, 1H), 5.79 (d, J = 1.0 Hz,
1H), 4.77 (s, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 158.6,
133.4, 133.3, 130.7, 129.7, 129.2, 128.4, 127.7, 127.0, 126.6,
126.3, 125.3, 122.4, 121.4, 120.6, 115.2, 92.0, 89.2, 69.9. HRMS
4.3.5 1,2-Dimethyl-4-(3-phenoxymethyl-but-3-en-1-ynyl)benzene
(7). Colourless oil, 74 % yield (58.2 mg). H NMR (500 MHz,
1
CDCl3) δ 7.32-7.29 (m, 2H), 7.26 (s, 1H), 7.22 (d, J = 8.0 Hz,
1H), 7.09 (d, J = 8.0 Hz, 1H), 6.99 (d, J = 7.0 Hz, 3H), 5.68 (s,
1H), 5.65 (s, 1H), 4.64 (s, 2H), 2.27 (s, 3H), 2.25 (s, 3H).
13C{1H} NMR (125 MHz, CDCl3) δ 158.5, 137.6, 136.8, 132.9,
129.8, 129.6, 129.3, 127.5, 121.6, 121.3, 120.2, 115.2, 91.3,
86.2, 69.7, 19.9, 19.7. HRMS (ESI): calcd for C19H19O + ([M +
H]+) 263.1430, Found: 263.1438.
+
(ESI): calcd for C21H17O ([M + H]+) 285.1274, Found:
285.1264.
4.3.13 (2-methylene-4-phenylbut-3-yn-1-yl)(phenyl)sulfane (15).
Yellow oil, 45 % yield (33.8 mg). 1H NMR (500 MHz, CDCl3) δ
7.45-7.42 (m, 4H), 7.33-7.31 (m, 3H), 7.29-7.28 (m, 2H), 7.22
(d, J = 7.0 Hz, 1H), 5.49 (s, 1H), 5.41 (s, 1H), 3.71 (s, 2H).
13C{1H} NMR (125 MHz, CDCl3) δ 136.0, 131.9, 130.6, 129.0,
4.3.6 1,3-Dimethyl-5-(3-phenoxymethyl-but-3-en-1-ynyl)benzene
(8). Yellow oil, 50 % yield (39.3 mg). H NMR (500 MHz,
1
CDCl3) δ 7.30 (t, J = 7.5 Hz, 2H), 7.10 (s, 2H), 6.98-6.97 (m,
4H), 5.68 (s, 1H), 5.65 (s, 1H), 4.64 (s, 2H), 2.30 (s, 6H).
13C{1H} NMR (125 MHz, CDCl3) δ 158.5, 138.0, 130.6, 129.6,
129.5, 127.4, 122.5, 121.9, 121.3, 115.1, 91.3, 86.4, 69.7, 21.2.
HRMS (ESI): calcd for C19H19O + ([M + H]+) 263.1430, Found:
263.1437.
128.5, 128.4, 128.3, 126.7, 123.3, 123.1, 90.4, 88.8, 40.9. HRMS
(ESI): calcd for C17H15S
251.0894.
+
([M + H]+) 251.0889, Found:
4.3.14 1-(3-Phenylsulfanylmethyl-but-3-en-1-ynyl)naphthalene
1
(16). Yellow oil, 40 % yield (36.0 mg). H NMR (500 MHz,
CDCl3) δ 8.40 (d, J = 8.0 Hz, 1H), 7.84 (t, J = 9.0 Hz, 2H), 7.69-
7.67 (m, 1H), 7.60-7.56 (m, 1H), 7.55-7.51 (m, 1H), 7.49-7.43
(m, 3H), 7.30 (t, J = 7.5 Hz, 2H), 7.24-7.21 (m, 1H), 5.60 (s,
1H), 5.47 (d, J = 1.0 Hz, 1H), 3.82 (s, 2H). 13C{1H} NMR (125
MHz, CDCl3) δ 135.8, 133.5, 133.4, 130.8, 130.7, 129.1, 129.0,
128.4, 128.0, 127.0, 126.8, 126.6, 126.5, 125.3, 123.5, 120.8,
93.6, 88.6, 41.2. HRMS (ESI): calcd for C21H17S + ([M + H]+)
301.1045, Found: 301.1048.
4.3.7 1-Methoxy-4-(3-phenoxymethyl-but-3-en-1-ynyl)benzene
17
1
(9). Yellow oil, 70% yield (55.5 mg). H NMR (500 MHz,
CDCl3) δ 7.42-7.39 (m, 2H), 7.33-7.28 (m, 2H), 6.99-6.96 (m,
3H), 6.87-6.84 (m, 2H), 5.66 (dd, J = 3.0, 1.5 Hz, 1H), 5.63 (d, J
= 1.5 Hz, 1H), 4.64 (t, J = 1.5 Hz, 2H), 3.82 (s, 3H). 13C{1H}
NMR (125 MHz, CDCl3) δ 160.0, 158.6, 133.3, 129.6, 127.5,
121.4, 121.3, 115.2, 115.1, 114.2, 91.0, 85.8, 69.8, 55.4. LRMS
(EI, 70 eV) m/z (%): 264 (M+, 69), 141 (22), 128 (100), 127
(23), 102 (19).
4.3.15 1-Methyl-4-(2-methylene-4-phenyl-but-3-ynyloxy)benzene
1
(17). Yellow oil, 69 % yield (51.4 mg). H NMR (500 MHz,
4.3.8
1-Fluoro-4-(3-phenoxymethyl-but-3-en-1-ynyl)benzene
CDCl3) δ 7.49-7.45 (m, 2H), 7.35-7.33 (m, 3H), 7.11-7.10 (m,
2H), 6.91-6.85 (m, 2H), 5.70 (d, J = 1.5 Hz, 1H), 5.67 (d, J = 1.5
Hz, 1H), 4.62 (t, J = 1.5 Hz, 2H), 2.31 (s, 3H). 13C{1H} NMR
(125 MHz, CDCl3) δ 156.5, 131.9, 130.6, 130.1, 128.6, 128.5,
127.5, 123.0, 122.1, 115.1, 90.9, 87.2, 70.0, 20.6. LRMS (EI, 70
eV) m/z (%): 248 (M+, 29), 233 (28), 205 (18), 141 (26), 115
(100). HRMS (ESI): calcd for C18H17O + ([M + H]+) 249.1274,
Found: 249.1270.
(10). 17 Yellow oil, 35% yield (26.5 mg). 1H NMR (500 MHz,
CDCl3) δ 7.46-7.42 (m, 2H), 7.32-7.29 (m, 2H), 7.04-6.96 (m,
5H), 5.70 (d, J = 1.5 Hz, 1H), 5.67 (d, J = 1.5 Hz, 1H), 4.63 (s,
2H). 13C{1H} NMR (125 MHz, CDCl3) δ 162.8 (d, J = 248.8
Hz), 158.5, 133.8 (d, J = 8.75 Hz), 129.6, 127.2, 122.4, 121.4,
119.1, 115.8 (d, J = 22.5 Hz), 115.2, 89.8, 86.8, 69.7. LRMS (EI,
70 eV) m/z (%): 252 (M+, 54), 209 (15), 157 (20), 133 (100),
123 (12).
4.3.16 1-Methyl-2-(2-methylene-4-phenyl-but-3-ynyloxy)benzene
1
4.3.9
1-Chloro-4-(3-phenoxymethyl-but-3-en-1-ynyl)benzene
(18). Yellow oil, 63 % yield (46.9 mg). H NMR (500 MHz,
(11). 17 Yellow oil, 60% yield (48.3 mg). H NMR (500 MHz,
CDCl3) δ 7.38 (d, J = 8.0 Hz, 2H), 7.31-7.29 (m, 4H), 6.99-6.97
(m, 3H), 5.72 (s, 1H), 5.68 (s, 1H), 4.64 (s, 2H). 13C{1H} NMR
(125 MHz, CDCl3) δ 158.5, 134.8, 133.1, 129.6, 128.9, 127.2,
122.7, 121.5, 121.4, 115.2, 89.8, 88.1, 69.7. LRMS (EI, 70 eV)
m/z (%): 268 (M+, 46), 205 (22), 149 (59), 139 (100), 65 (27).
CDCl3) δ 7.49-7.47 (m, 2H), 7.34-7.33 (m, 3H), 7.18-7.15 (m,
2H), 6.92-6.86 (m, 2H), 5.74 (d, J = 1.5 Hz, 1H), 5.69 (s, 1H),
4.65 (s, 2H), 2.32 (s, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ
156.6, 131.8, 130.9, 128.6, 128.5, 127.7, 127.3, 126.9, 123.1,
121.8, 121.0, 111.9, 90.8, 87.2, 69.8, 16.4. HRMS (ESI): calcd
for C18H17O + ([M + H]+) 249.1274, Found: 249.1266.
1
4.3.10
1-Bromo-4-(3-phenoxymethyl-but-3-en-1-ynyl)benzene
4.3.17 1-Ethyl-4-(2-methylene-4-phenyl-but-3-ynyloxy)benzene
(19). Yellow oil, 67 % yield (52.7 mg). H NMR (500 MHz,
1
1
(12). 17 Yellow solid, mp: 79-80 °C, 63% yield (59.0 mg). H
NMR (500 MHz, CDCl3) δ 7.46 (d, J = 8.0 Hz, 2H), 7.32-7.29
(m, 4H), 7.00-6.97 (m, 3H), 5.72 (s, 1H), 5.69 (s, 1H), 4.64 (s,
2H). 13C{1H} NMR (125 MHz, CDCl3) δ 158.5, 133.3, 131.8,
129.6, 127.2, 123.0, 122.8, 122.0, 121.4, 115.2, 89.8, 88.2, 69.7.
LRMS (EI, 70 eV) m/z (%): 312 (M+, 29), 205 (25), 140 (98),
139 (100), 114 (20).
CDCl3) δ 7.49-7.47 (m, 2H), 7.34-7.33 (m, 3H), 7.14 (d, J = 8.5
Hz, 2H), 6.91 (d, J = 8.5 Hz, 2H), 5.71 (d, J = 1 Hz, 1H), 5.68 (s,
1H), 4.63 (s, 2H), 2.61 (q, J = 7.5 Hz, 2H), 1.23 (t, J = 7.5 Hz,
3H). 13C{1H} NMR (125 MHz, CDCl3) δ 156.6, 137.1, 131.9,
128.9, 128.6, 128.5, 127.6, 123.1, 122.1, 115.1, 90.9, 87.2, 70.0,
+
28.1, 15.9. HRMS (ESI): calcd for C19H19O ([M + H]+)
263.1430, Found: 263.1438.
4.3.11 1-[4-(3-Phenoxymethyl-but-3-en-1-ynyl)-phenyl]ethanone
(13). Yellow oil, 40% yield (33.1 mg). H NMR (500 MHz,
CDCl3) δ 7.91 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 8.5 Hz, 2H), 7.32-
7.29 (m, 2H), 7.00-6.97 (m, 3H), 5.76 (d, J = 1.5 Hz, 1H), 5.73
1
4.3.18
1,2-Dimethyl-4-(2-methylene-4-phenyl-but-3-
ynyloxy)benzene (20). Yellow oil, 82 % yield (64.5 mg). 1H
NMR (500 MHz, CDCl3) δ 7.50-7.48 (m, 2H), 7.35-7.34 (m,

5
ACCEPTED MANUSCRIPT
3H), 7.06 (d, J = 8.5 Hz, 1H), 6.82-6.81 (m, 1H), 6.75-6.73 (m,
1H), 5.72 (d, J = 1.5 Hz, 1H), 5.68 (d, J = 1.5 Hz, 1H), 4.63 (s,
2H), 2.26 (s, 3H), 2.22 (s, 3H). 13C{1H} NMR (125 MHz,
CDCl3) δ 156.7, 137.9, 131.8, 130.5, 129.3, 128.6, 128.5, 127.6,
123.1, 122.0, 116.8, 112.1, 90.8, 87.2, 69.9, 20.1, 18.9. HRMS
159.0, 131.8, 129.6, 128.4, 127.8, 123.5, 123.2, 120.9, 114.9,
89.9, 89.2, 66.3, 37.2. HRMS (ESI): calcd for C18H17O + ([M +
H]+) 249.1274, Found: 249.1273.
17
4.3.26 (3-(Methoxymethyl)but-3-en-1-yn-1-yl)benzene (28).
Yellow oil, 30 % yield (15.5 mg). 1H NMR (500 MHz, CDCl3) δ
7.47-7.45 (m, 2H), 7.32-7.31 (m, 3H), 5.62 (dd, J = 3.0, 1.5 Hz,
1H), 5.58 (dd, J = 3.0, 1.5 Hz, 1H), 4.04 (t, J = 1.5 Hz, 2H), 3.43
(s, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 131.8, 128.52,
128.49, 128.4, 123.1, 122.1, 90.3, 87.7, 74.7, 58.4. LRMS (EI,
70 eV) m/z (%): 172 (M+, 25), 142 (100), 127 (58), 115 (21), 77
(18).
+
(ESI): calcd for C19H19O ([M + H]+) 263.1430, Found:
263.1436.
4.3.19
1-Methoxy-4-(2-methylene-4-phenyl-but-3-
ynyloxy)benzene (21). Yellow oil, 66 % yield (52.3 mg). 1H
NMR (500 MHz, CDCl3) δ 7.48-7.45 (m, 2H), 7.34-7.32 (m,
3H), 6.94-6.91 (m, 2H), 6.87-6.83 (m, 2H), 5.69 (d, J = 1.5 Hz,
1H), 5.67 (s, 1H), 4.60 (s, 2H), 3.78 (s, 3H). 13C{1H} NMR (125
MHz, CDCl3) δ 154.4, 152.7, 131.8, 128.6, 128.5, 127.6, 123.0,
122.2, 116.3, 114.8, 90.9, 87.2, 70.7, 55.9. LRMS (EI, 70 eV)
m/z (%): 264 (M+, 48), 178 (22), 139 (12), 123 (100), 115 (54).
Supporting Information:
Copies of 1H and 13C NMR spectra for the products.
Acknowledgements
4.3.20
1-Benzyloxy-4-(2-methylene-4-phenyl-but-3-
We thank the National Natural Science Foundation of China
(No. 21302144) for financial support.
ynyloxy)benzene (22). Yellow solid, mp: 88-89 °C, 76 % yield
1
(77.6 mg). H NMR (500 MHz, CDCl3) δ 7.49-7.47 (m, 2H),
7.45-7.43 (m, 2H), 7.41-7.38 (m, 2H), 7.34-7.33 (m, 4H), 6.93
(s, 4H), 5.70 (d, J = 1.5 Hz, 1H), 5.68 (d, J = 1.5 Hz, 1H), 5.03
(s, 2H), 4.60 (s, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 153.6,
152.9, 137.5, 131.8, 128.7, 128.6, 128.47, 128.46, 128.0, 127.6,
123.0, 122.2, 116.2, 116.0, 90.9, 87.2, 70.9, 70.6. LRMS (EI, 70
eV) m/z (%): 340 (M+, 35), 249 (17), 221 (14), 178 (15), 91
(100).
References and notes
[1]
(a) Sheldrake, H. M.; Jamieson, G.; Pascu, S. I.; Burton, J.
W. Org. Biomol. Chem. 2009, 7, 238. (b) Chen, J. H.; Ying, L.;
Hansen, T. M.; Engler, M. M.; Lee, C. S.; Clari, J. J. L.; Forsyth, C.
J. Bioorg. Med. Chem. Lett. 2006, 16, 901. (c) El-Jaber, N.; Estevez-
Braun, A.; Ravelo, A. G.; Munoz-Munoz, O.; Rodriguez-Afonso,
A.; Murguia, J. R. J. Nat. Prod. 2003, 66, 722. (d) Fontana, A.;
d’Ippolito, G.; D’Souza, L.; Mollo, E.; Parameswaram, P. S.;
Cimino, G. J. Nat. Prod. 2001, 64, 131.
4.3.21 1-Fluoro-4-(2-methylene-4-phenyl-but-3-ynyloxy)benzene
1
(23). Yellow oil, 40 % yield (30.3 mg). H NMR (500 MHz,
CDCl3) δ 7.49-7.47 (m, 2H), 7.35-7.34 (m, 3H), 7.03-6.98 (m,
2H), 6.95-6.91 (m, 2H), 5.70 (s, 2H), 4.62 (s, 2H).13C{1H} NMR
(125 MHz, CDCl3) δ157.7 (d, J = 237.5 Hz), 154.6, 131.8,
128.7, 128.5, 127.3, 122.9, 122.3, 116.3 (d, J = 7.5 Hz), 116.0 (d,
J = 23.8 Hz), 91.0, 87.0, 70.5. HRMS (ESI): calcd for C17H14FO
+ ([M + H]+) 253.1023, Found: 253.1037.
[2]
(a) Alami, M.; Ferri, F.; Gasiain, Y. Tetrahedron Lett.
1996, 37, 57. (b) Iverson, S. L.; Uetrecht, J. P. Chem. Res. Toxicol.
2001, 14, 175.
[3]
X.; Liu, X. Y.; Liang, Y. M. Org. Lett. 2012, 14, 3344. (b) Xu. J. J.;
Burton, D. J. Org. Lett. 2006, 8, 2555.
[4]
Tetrahedron Lett. 2005, 46, 9409. (b) Chen, J. L.; Zheng, F.; Huang,
Y. G.; Qing, F. L. J. Org. Chem. 2011, 76, 6525. (c) Chun, Y. S.;
Lee, J. H.; Kim, J. H.; Ko, Y. O.; Lee, S-G. Org. Lett. 2011, 13,
6390.
(a) Song, X. R.; Xia, X. F.; Song, Q. B.; Yang, F.; Li, Y.
(a) Gracias, V.; Gasiecki, A. F.; Djuric, S. W.
4.3.22 1-Chloro-4-(2-methylene-4-phenyl-but-3-ynyloxy)benzene
1
(24). Yellow oil, 57 % yield (45.8 mg). H NMR (500 MHz,
CDCl3) δ 7.47-7.45 (m, 2H), 7.34-7.32 (m, 3H), 7.26-7.24 (m,
2H), 6.90 (d, J = 8.0 Hz, 2H), 5.67 (d, J = 3.0 Hz, 2H), 4.61 (s,
2H). 13C{1H} NMR (125 MHz, CDCl3) δ 157.1, 131.8, 129.5,
128.7, 128.5, 126.9, 126.3, 122.8, 122.4, 116.5, 91.1, 86.8, 70.0.
[5]
(a) Zweifel, G.; Polston, N. L. J. Am. Chem. Soc. 1970, 92,
4068. (b) Betzer, J. F.; Ardisson, J. Yves, J.; Pancrazi, A.
Tetrahedron Lett. 1997, 38, 2279.
[6]
+
HRMS (ESI): calcd for C17H14ClO ([M + H]+) 269.0728,
Found: 269.0737.
For selected papers on the synthesis of 1, 3-enyne, see: (a)
Li, X.; Peng, F.; Zhou, M.; Mo, M.; Zhao, R.; Shao, Z. Chem.
Commun., 2014, 50, 1745. (b) Mahrwald, R.; Quint, S.;
Tetrahedron. 2000, 56, 7463. (c) Hadi, V.; Yoo, K. S.; Jeong, M.;
Jung, K. W.; Tetrahedron Lett. 2009, 50, 2370. (d) Trost, B. M.;
Taft, B. R.; Masters, J.; Lumb, J-P.; J. Am. Chem. Soc. 2011, 133,
8502. (e) Bates, C. G.; Saejueng, P; Venkataraman,D;. Org. Lett.
2004, 6, 1441. (f) Zhang, Y. X.; Li, Z. J.; Liu, Z. Q.; Org. Lett. 2012,
14, 1226.
4.3.23 1-Chloro-2-(2-methylene-4-phenyl-but-3-ynyloxy)benzene
(25). Yellow oil, 50% yield (40.2 mg). H NMR (500 MHz,
1
CDCl3) δ 7.49-7.47 (m, 2H), 7.40 (dd, J = 8.0, 1.5 Hz, 1H), 7.35-
7.33 (m, 3H), 7.24-7.20 (m, 1H), 6.98 (dd, J = 8.0, 1.5 Hz, 1H),
6.95-6. 91 (m, 1H), 5.79 (dd, J = 3.0, 1.5 Hz, 1H), 5.70 (dd, J =
3.0, 1.5 Hz, 1H), 4.72 (t, J = 1.5 Hz, 2H). 13C{1H} NMR (125
MHz, CDCl3) δ 154.0, 131.89, 130.6, 128.7, 128.5, 127.8, 126.7,
123.5, 122.9, 122.2, 122.1, 114.4, 91.1, 86.8, 70.4. HRMS (ESI):
calcd for C17H14ClO + ([M + H]+) 269.0728, Found: 269.0738.
[7]
For selected papers on the Pd-Cu-catalyzed Sonogashira
coupling reactions, see (a) Feuerstein, M.; Chahen, L.; Doucet, H.;
Santelli, M. Tetrahedron. 2006, 62, 112. (b) Huang, M. M.; Feng, Y.
J.; Wu, Y. J. Tetrahedron. 2012, 68, 376. (c) Pal, M.; Parasuraman,
K.; Subramanian, V.; Dakarapu, R.; Yeleswarapu, K. R.
Tetrahedron Lett. 2004, 45, 2305. (d) Alami, M.; Crousse, B.; Ferri,
F. J. Organomet.Chem. 2001, 624, 114. (e) Souffrin, A.; Croix, C.;
Claude, M.; Massuard, V. Eur. J. Org. Chem. 2012, 2499.
4.3.24 1-Bromo-4-(2-methylene-4-phenyl-but-3-ynyloxy)benzene
1
(26). Yellow oil, 51% yield (47.7 mg). H NMR (500 MHz,
CDCl3) δ 7.48-7.44 (m, 2H), 7.40-7.39 (m, 2H), 7.35-7.32 (m,
3H), 6.88-6.84 (m, 2H), 5.68 (d, J = 1.0 Hz, 1H), 5.67 (d, J = 1.5
Hz, 1H), 4.61 (s, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 157.6,
132.5, 131.8, 128.7, 128.5, 127.0, 126.8, 122.4, 117.1, 113.6,
91.1, 86.8, 70.0. HRMS (ESI): calcd for C17H14BrO + ([M + H]+)
313.0223, Found: 313.0218.
4.3.25 (3-Methylene-5-phenoxypent-1-yn-1-yl)benzene (27).
Yellow oil, 59 % yield (44.0 mg). 1H NMR (500 MHz, CDCl3) δ
7.43-7.41 (m, 2H), 7.31-7.26 (m, 5H), 6.95-6.93 (m, 3H), 5.55-
5.54 (m, 1H), 5.45 (d, J = 1.5 Hz, 1H), 4.21 (t, J = 6.5 Hz, 2H),
2.73 (t, J = 6.5 Hz, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ
[8]
(a) Alevs, D.; Reis, J. S. D.; Luchese, C.; Nogueira, C. W.;
Zeni, G. Eur. J. Org. Chem. 2008, 377. (b) Li, J. H.; Zhang, X. D.;
Xie, Y. X. Eur. J. Org. Chem. 2005, 4256. (c) Novak, Z.; Szabo, A.;
Repasi, J. Kotschy, A. J. Org. Chem. 2003, 68, 3327.
[9]
(a) Wu, M. Y.; Mao, J. C.; Guo, J.; Ji, S. J. Eur. J. Org.
Chem. 2008, 4050. (b) Bates, C. G.; Saejuen, P.; Venkataraman, D.
Org. Lett. 2004, 6, 1441. (c) Saejueng, P.; Bates, C. G.;

6
ACCEPTED MANUSCRIPT
Venkataraman, D. Synthesis. 2005, 10, 1706. (d) Sun, P.; Yan, H.;
Lu, L.; Liu, D.; Rong, G.; Mao, J. Tetrahedron. 2013, 69, 6969
[10] (a) Xie, X,; Xu, X. B.; Li, H. F.; Xu, X. L.; Yang, J. Y.; Li,
Y. Z. Adv. Synth. Catal. 2009, 351, 1263. (b) Hatakeyama, T.;
Yoshimoto, Y.; Gabriel, T.; Nakamura, M. Org. Lett. 2008, 10, 5341.
[11]
For alkynylcopper, see: (a) Masuda, Y.; Murata, M.; Sato,
K.; Watanabe, S. Chem. Commun. 1998, 807. For
alkynylmagnesium, see: (b) Dang, H. P.; Linstrumelle, G.
Tetrahedron Lett. 1978, 191. For alkynyl-silicon, see: (c) Marshall, J.
A.; Chobanian, H. R.; Yanik, M. M. Org. Lett. 2001, 3, 4107. (d)
Heffron, T. P.; Trenkle, J. D.; Jamison, T. F. Tetrahedron. 2003, 59,
8913. For alkynyltin, see: (e) Stille, J. K.; Groh, B. L. J. Am. Chem.
SOC. 1987, 109, 813. (f) Pottier, L. R.; Peyrat, J. F.; Alami, M.;
Brion, J. D. Tetrahedron Lett. 2004, 45, 4035. (g) Stille, J. K.;
Simpson, J. H. J. Am. Chem. Soc. 1987, 109, 2138. For alkynylzinc,
see: (h) Negishi, E. I.; Qian, M. X.; Zeng, F. X.; Anastasia, L.;
Babinski, D. Org. Lett. 2003, 5, 1597.
[12]
For alkenylaluminum and alkenylzirconium, see: (a)
Negishi, E.; Okukado, N.; King, A. O.; Vanhorn, D. E.; Spiegel, B.
I. J. Am. Chem. Soc. 1978, 100, 2254. For alkenylboranes, see: (b)
H. Lipshutz, S. Sengupta, Org. React. 1992, 41, 135. For
alkenylcopper, see: (c) Nobuo. I.; Isao. A.; Hisashi. Y. J. Am. Chem.
Soc. 1986. 108, 3. (d) Marek. Z.; Jacek. R. B.; Wojciech. S. L.; J.
Organomet. Chem. 1999, 580, 354. For alkenylmagnesium, see: (e)
Tomihiro. N.; Takeshi. S.; Hiroshi. S.; Kazushige. A.; Hideaki. K.;
Kenichi. K.; Chem. Lett. 1996, 25, 549.
[13]
The selected papers on C-C forming decarboxylative
reactions: see: (a) Park, J.; Park, E.; Kim, A.; Park, S. A.; Lee, Y.;
Chi, K. W.; Jung, Y. H.; Kim, I. S. J. Org. Chem. 2011, 76, 2214.
(b) Moon, J.; Jang, M.; Lee, S. J. Org. Chem. 2009, 74, 1403. (c)
Zhang, W. W.; Zhang, X. G.; Li, J. H. J. Org. Chem. 2010, 75,
5259. (d) Moon, J.; Jeong, M.; Nam, H.; Ju, J. H.; Moon, J. H.; Jung,
H. M.; Lee, S. Org. Lett. 2008, 10, 945. (e) Hwang, J.; Park, K.;
Choe, J.; Min, H.; Song, K. H.; Lee, S. J. Org. Chem. 2014, 79,
3267. (f) Lv, W-X.; Zeng, Y-F.; Zhang, S-S.; Li, Q.; Wang, H. Org.
Lett. 2015, 17, 2972. (g) Li, X.; Yang, F.; Wu, Y. J. Org. Chem.
2013, 78, 4543.
[14]
The selected papers on C-N forming decarboxylative
reactions: see: (a) Park, K.; Heo, Y.; Lee, S. Org. Lett. 2013, 15,
3322. (b) Lim, J.; Park, K.; Byeun, A.; Lee, S. Tetrahedron Lett.
2014, 55, 4875. (c) Priebbenow, D. L.; Becker, P.; Bolm, C. Org.
Lett. 2013, 15, 6155.
[15]
The selected papers on C-P forming decarboxylative
reactions: see: (a) Hu, G.; Gao, Y.; Zhao, Y. Org. Lett. 2014, 16,
4464. (b) Zhou, M.; Chen, M.; Zhou, Y.; Yang, K.; Su, J.; Du, J.;
Song, Q. Org. Lett. 2015, 17, 1786. (c) Li, X.; Yang, F.; Wu, Y.; Wu,
Y. Org. Lett. 2014, 16, 992.
[16]
(a) Rijs, N. J.; O’Hair, R. A. J. Organometallics. 2012, 31,
8012. (b) Pyo, A.; Kim, Y. H.; Park, K.; Kim, G. C.; Choi, H. C.;
Lee, S. Appl. Organometal. Chem. 2012, 26, 650.
[17]
Lett. 2012, 14, 5242; Org
[18] Myers, A. G.; Tanaka, D.; Mannion, M. R. J. Am. Chem.
Soc. 2002, 124, 11250.
Shao, Y. L.; Zhang, X. H.; Han, J. S.; Zhong, P.; Org.
.
Lett 2014 16 3611.
.
,
,
[19]
(a) Hadi, V.; Yoo, K. S.; Jeong, M.; Jung, K. W.
Tetrahedron Lett. 2009, 50, 2370. (b) Zhang, Y. X.; Li, Z. J.; Liu, Z.
Q. Org. Lett. 2012, 14, 226. (c) Pan, D. L.; Chen, A. J.; Su, Y. J.;
Zhou, W.; Li, S.; Jia, W.; Xiao, J.; Liu, Q. J.; Zhang, L. G.; Jiao, N.
Angew. Chem. Int. Ed. 2008, 47, 4729.