Pd(II)-catalyzed oxidative Heck-type reaction of triarylphosphines with alkenes via carbon-phosphorus bond cleavage

Article abstract of DOI:10.1016/j.tet.2013.01.025

A Pd(II)-catalyzed oxidative Heck-type reaction of triarylphosphines with alkenes via carbon-phosphorus bond cleavage was reported. Under the optimal reaction conditions, most reactions proceeded smoothly to give the expected coupling products in acceptable to high yields.

Full text of DOI:10.1016/j.tet.2013.01.025

Tetrahedron 69 (2013) 2102e2106
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Pd(II)-catalyzed oxidative Heck-type reaction of triarylphosphines
with alkenes via carbonephosphorus bond cleavage
*
Ming-Tao Ma, Jian-Mei Lu
College of Chemistry and Materials Engineering, Wenzhou University, Chashan University Town, Wenzhou, Zhejiang Province 325035,
People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
A Pd(II)-catalyzed oxidative Heck-type reaction of triarylphosphines with alkenes via carbonephosphorus
bond cleavage was reported. Under the optimal reaction conditions, most reactions proceeded smoothly to
give the expected coupling products in acceptable to high yields.
Received 24 November 2012
Received in revised form 2 January 2013
Accepted 8 January 2013
Ó 2013 Elsevier Ltd. All rights reserved.
Available online 16 January 2013
Keywords:
Palladium
Oxidative Heck reaction
Triarylphosphines
Carbonephosphorus bond cleavage
Coupling reaction
PdCl2, AgOOCCF3
R
3
+
Ar PAr2
1
Ar
1. Introduction
R
NaOAc, CH3CN
60 oC, 24 h
2
The palladium-catalyzed Heck reaction is one of the most ver-
satile methods for the formation of carbonecarbon bonds, which
traditionally employs organic (pseudo)halides as the electrophiles.1
Triarylphosphines are frequently introduced as the ligands to fa-
Scheme 1. Pd(II)-catalyzed oxidative Heck-type reaction between triarylphosphines 1
and alkenes 2.
presence of PdCl2 (10.0 mol %) using AgOOCCF3 (3.0 equiv) as the
oxidant in CH3CN (2.0 mL) at 60 ꢀC for 24 h was chosen as the model
reaction to find the most suitable base (Table 1, entries 1e7). Best
results were observed with NaOAc as the base (55%) over KHCO3
(11%) and Na2CO3 (23%) (Table 1, entries 1, 6 and 7). No reaction took
place when all the other bases, such as KOH, KOtBu, K2CO3 and
HCOONa, respectively, were used (Table 1, entries 2e5). In the sec-
ond round, using NaOAc as the base, various oxidants were exam-
ined, and it was found that AgOOCCF3 is the best one (Table 1, entry 1
vs entries 8e13). Finally, when the amount of AgOOCCF3 was in-
creased to 5.0 equiv, the yield was further increased to 96% (Table 1,
entry 14). Further study showed that the introduction of oxidant is
essential, and no reaction occurred when no AgOOCCF3 was added
(Table 1, entry 15). In addition, it was found that O2 was not a good
oxidant. In the case of using O2 as the oxidant, PPh3 was easily
transformed to Ph3PO and no desired product was observed.
cilitate such
a
transformation.2 Previously, Pd-aryl/P-aryl in-
terchanges were observed when triarylphosphines were used as
the ligands in the palladium-catalyzed Heck reaction and other
coupling reactions, resulting in the undesirable by-products.3,4
However, the use of triarylphosphines as the arylating reagents in
transition metal-catalyzed coupling reactions have not been re-
ported. During the past years, the oxidative Heck reaction, which
usually employs organometallic compounds as one of the sub-
strates, has attracted much attention and has become an efficient
complement to the traditional Heck reaction.5,6 Herein, we
report the Pd(II)-catalyzed oxidative Heck-type reaction of triar-
ylphosphines with alkenes via carbonephosphorus bond cleavage
(Scheme 1).7e9
2. Results and discussion
With the optimal reaction conditions realized, we then first
explored the scope and limitations of this Pd(II)-catalyzed oxidative
Heck-type reaction between triarylphosphines 1 and acrylates 2
(Table 2). It was found that the substituents on the triar-
ylphosphines have significant effect on the reactions. For example,
when tris(4-methoxyphenyl)phosphine was used as the substrate,
At the outset of our investigations, the reaction of triphenyl-
phosphine 1a (0.5 mmol) and methyl acrylate 2a (0.6 mmol) in the
* Corresponding author. Tel./fax: þ86 577 86689300; e-mail address: ljm@
wzu.edu.cn (J.-M. Lu).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.01.025

M.-T. Ma, J.-M. Lu / Tetrahedron 69 (2013) 2102e2106
2103
Table 1
Table 3
Optimization for the reaction conditions
PdCl2-catalyzed reaction of triarylphosphines 1 with styrenes 2
PdCl2, oxidant,
PdCl2, AgOOCCF3
R'
CO2Me
+
Ph PPh2
1a
Ar PAr2
+
1
Ar
CO2Me
base, CH3CN
Ph
NaOAc, CH3CN
R'
3
2
2a
3a
60 oC, 24 h
60 oC, 24 h
Entrya
Oxidant
Base
Yieldb (%)
Entrya
1 (Ar)
2 (R0)
Yieldb (%)
1
2
3
4
5
6
7
8
AgOOCCF3
AgOOCCF3
AgOOCCF3
AgOOCCF3
AgOOCCF3
AgOOCCF3
AgOOCCF3
DDQ
NaOAc
KOH
55
1
2
3
4
5
6
7
8
1a (C6H5)
2c (C6H5)
3l, 76
ND
ND
ND
ND
11
1a
1a
1a
1a
1a
1a
1a
2d (4-MeC6H4)
2e (4-ClC6H4)
2f (4-FC6H4)
2g (3-FC6H4)
2h (3-MeC6H4)
2i (2-FC6H4)
3m, 79
3n, 74
3o, 78
3p, 88
3q, 78
3r, 77
3s, 78
3m, 77
3q, 71
3t, 62
KOtBu
K2CO3
HCOONa
KHCO3
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
23
ND
ND
28
ND
23
ND
96
ND
2j (2,5-Me2C6H3)
9
K2S2O8
9
10
11
1b (4-MeC6H4)
1f (3-MeC6H4)
1f
2c
2c
2e
10
11
12
13
14c
15
Cu(OAc)2
Cu(OTf)2
AgOAc
Me3NO
AgOOCCF3
d
a
All reactions were carried out using 1 (0.5 mmol), 2 (0.6 mmol), AgOOCCF3
(5.0 equiv), NaOAc (4.0 equiv), PdCl2 (10.0 mol %) in CH3CN (2.0 mL) at 60 ꢀC for 24 h.
b
Isolated yields.
a
Unless otherwise specified, all reactions were carried out using 1a (0.5 mmol),
2a (0.6 mmol), oxidant (3.0 equiv), base (4.0 equiv), PdCl2 (10.0 mol %) in CH3CN
(2.0 mL) at 60 ꢀC for 24 h.
under identical conditions. In this case, product 3a was isolated in
39% yield, and no 3-cyclohexyl methyl acrylate was observed, in-
dicating that only the phenyl group can be transferred in this oxi-
dative Heck-type reaction (Scheme 2).
b
Isolated yields.
5.0 equiv of AgOOCCF3 was added.
c
CO2Me
Table 2
PdCl2-catalyzed reaction of triarylphosphines 1 with acrylates 2
PdCl2, AgOOCCF3
PdCl2, AgOOCCF3
+
P
R
Ar PAr2
1
+
CO2Me NaOAc, CH3CN
Ar
NaOAc, CH3CN
R
60 oC, 24 h
3
2a
2
60 oC, 24 h
1h
3a, 39%
Entrya
1 (Ar)
2 (R)
Yieldb (%)
Scheme 2. Reaction of diphenylcyclohexylphosphine 1b with methyl acrylate 2a
under identical conditions.
1
2
3
4
5
1b (4-MeC6H4)
1c (4-FC6H4)
1d (4-MeOC6H4)
1e (2-MeC6H4)
1f (3-MeC6H4)
2a (CO2Me)
3b, 70
3c, 59
3d, 30
3e, 7
2a
2a
2a
2a
To clarify the reaction pathway, some control experiments were
carried out:
3f, 94
1) the reaction between Ph3PO and methyl acrylate was carried
out under identical conditions (Scheme 3), and no reaction
occurred, which may suggest that Ph3PO was not the real re-
action partner in this reaction;
1g
6
2a
3g, 21
P
3
O
7
8
9
10
1a (C6H5)
2b (CO2Bun)
2b
2b
2b
3h, 96
3i, 68
3j, 64
3k, 95
1b
1c
1f
PdCl2, AgOOCCF3
+
No reaction
Ph3PO
a
CO2Me
NaOAc, CH3CN
All reactions were carried out using 1 (0.5 mmol), 2 (0.6 mmol), AgOOCCF3
60 oC, 24 h
(5.0 equiv), NaOAc (4.0 equiv), PdCl2 (10.0 mol %) in CH3CN (2.0 mL) at 60 ꢀC for 24 h.
b
Isolated yields.
Scheme 3. Reaction of Ph3PO with methyl acrylate under identical conditions.
product 3d was only obtained in 30% yield (Table 2, entry 3). Ste-
rically-hindered tris(2-methylphenyl)phosphine was not a good
reaction partner, and only 7% yield of the corresponding product 3e
was obtained (Table 2, entry 4). Triheteroarylphosphine, such as
tri(2-furyl)phosphine was also tested under identical conditions,
and the corresponding product 3g was only obtained in 21% yield
(Table 2, entry 6).
2) the reaction between the prepared PdCl2(PPh3)2 and methyl
acrylate was carried out under identical conditions and the
desired product 3a was achieved in 98% yield (Scheme 4),
which may suggest that PdCl2(PPh3)2 is involved in this Pd(II)-
catalyzed oxidative Heck-type reaction;
Subsequently, some other triarylphosphines 1 and styrenes 2
were subjected to the identical conditions to test the reaction gen-
erality further (Table 3). As can be seen from Table 3, all reactions
performed well to give the expected coupling products in moderate
to high yields. It was found that the substituents on the styrenes
have no obvious effect on the reaction. For example, both electron-
rich (4-Me and 3-Me) and -poor (4-Cl, 4-F and 3-F) substituents on
the aryl ring of styrenes have almost no effect on the reactions.
Furthermore, sterically-hindered (2,5-Me2) substituents on the aryl
ring of styrene do not affect the reaction (Table 2, entry 8).
Moreover, unsymmetric diphenylcyclohexylphosphine 1h was
also utilized as the substrate in the reaction with methyl acrylate 2a
AgOOCCF3 (5.0 equiv)
PdCl2(PPh3)2
NaOAc (4.0 equiv)
CO2Me
3a, 98%
+
CH3CN (2.0 mL), 60 oC
24 h
Ph
CO2Me
Scheme 4. Reaction of PdCl2(PPh3)2 with methyl acrylate.
3) after the reaction was completed, a thin layer of Ag mirror can
be observed on the wall of the reaction tube, which may sug-
gest that AgOOCCF3 acts as an oxidant and the Pd(II) species is
the active catalytic species in this reaction;

2104
M.-T. Ma, J.-M. Lu / Tetrahedron 69 (2013) 2102e2106
4) after acidifying the reaction mixture, the formation of diphe-
4.2. Experimental procedures
nylphosphinic acid was detected by LCeMS (see Supplementary
data for the details).
4.2.1. General procedure. Under N2 atmosphere, NaOAc (4.0 equiv),
PPh3 1a (0.5 mmol), PdCl2 (10.0 mol %), AgOOCCF3 (5.0 equiv),
CH3CN (2.0 mL) and methyl acrylate 2a (0.6 mmol) were succes-
sively added into a Schlenk reaction tube. Then the mixture was
stirred at 60 ꢀC for 24 h. After cooling to room temperature, the
solvent was evaporated in vacuo and then purified by flash column
chromatography on silica gel to give the pure product 3a.
Based on the previous investigations9b and the above results,
a plausible mechanism for this Pd(II)-catalyzed oxidative Heck-type
reaction of triarylphosphines with alkenes is outlined in Scheme 5.
First, in the presence of NaOAc and AgOOCCF3, PdCl2 will coordinate
with PPh3 to give complex A. Subsequently, an intra- or in-
termolecular nucleophilic attack by Xꢁ on the coordinated phos-
phorus atom will result in the phenyl-transferred intermediate C,
probably via intermediate B. Complex C reacts with the alkenes via
Heck process to liberate products 3 and another complex D, which
will then be transformed to intermediate E in the presence of
a base. Ligand exchange between complex E and PPh3 will give
complex F, which was oxidized by AgOOCCF3 to complex A to fur-
nish the catalytic cycle, along with the release of compound G,
which will be then hydrolyzed and oxidized to diphenylphosphinic
acid when the reaction mixture was exposed to air.
4.2.2. Compound 3a.10 A colorless liquid. 1H NMR (300 MHz, CDCl3,
TMS)
d
3.80 (s, 3H), 6.44 (d, J¼16.2 Hz, 1H), 7.37e7.39 (m, 3H),
7.50e7.54 (m, 2H), 7.70 (d, J¼16.2 Hz, 1H). 13C NMR (75 MHz, CDCl3)
d
51.6, 117.7, 128.0, 128.8, 130.2, 134.3, 144.8, 167.4.
4.2.3. Compound 3b.10 A white solid. 1H NMR (300 MHz, CDCl3,
TMS)
d
2.37 (s, 3H), 3.80 (s, 3H), 6.39 (d, J¼16.2 Hz, 1H), 7.19 (d,
J¼8.1 Hz, 2H), 7.42 (d, J¼8.1 Hz, 2H), 7.67 (d, J¼16.2 Hz,1H). 13C NMR
(75 MHz, CDCl3)
167.6.
d 21.4, 51.6, 116.7, 128.0, 129.6, 131.6, 140.7, 144.8,
NaOAc
Ph
P
X
4.2.4. Compound 3c.11 A white solid. 1H NMR (300 MHz, CDCl3,
AgOOCCF3
Ph
X
Ph
X
TMS)
d
3.81 (s, 3H), 6.37 (d, J¼16.2 Hz, 1H), 7.08 (t, J¼8.4 Hz, 2H),
PdCl2
X
7.51 (dd, J¼5.1, 8.4 Hz, 2H), 7.66 (d, J¼16.2 Hz, 1H). 13C NMR
+
Pd
PPh3
B
PPh3
(125 MHz, CDCl3)
(d, JCeF¼2.3 Hz), 129.9 (d, JCeF¼8.5 Hz), 130.7 (d, JCeF¼3.3 Hz), 143.5,
163.9 (d, JCeF¼249.9 Hz), 167.3.
d
51.7, 116.0 (d, JCeF¼21.8 Hz), 117.6
PPh2X
Pd Ph
PPh3
X
X Pd X
PPh3
C
PPh3
A
R
4.2.5. Compound 3d.11 A white solid. 1H NMR (300 MHz, CDCl3,
AgOOCCF3
X
Heck process
TMS)
d
3.79 (s, 3H), 3,83 (s, 3H), 6.31 (d, J¼15.9 Hz, 1H), 6.90 (d,
R
J¼8.7 Hz, 2H), 7.47 (d, J¼8.7 Hz, 2H), 7.65 (d, J¼15.9 Hz, 1H). 13C
H
Ph
Ph3P Pd PPh3
F
3
NMR (75 MHz, CDCl3)
161.3, 167.7.
d 51.5, 55.2, 114.2, 115.1, 127.0, 129.7, 144.5,
Ph3P Pd PPh2X
D
X
PPh3
Pd
PPh2X
base
4.2.6. Compound 3e.12 A colorless liquid. 1H NMR (300 MHz, CDCl3,
G
PPh3
.
[O]
H2O
base HX
TMS)
d
2.44 (s, 3H), 3.81 (s, 3H), 6.36 (d, J¼15.9 Hz, 1H), 7.19e7.31
(m, 3H), 7.55 (d, J¼7.2 Hz, 1H), 7.99 (d, J¼15.9 Hz, 1H). 13C NMR
PPh2X
E
O
P
Ph
(125 MHz, CDCl3) d 19.8, 51.7, 118.9, 126.3, 126.4, 130.0, 130.8, 133.4,
Ph
OH
137.6, 142.6, 167.5.
X = OOCCF3 or OAc or Cl
4.2.7. Compound 3f.12 A colorless liquid. 1H NMR (300 MHz, CDCl3,
Scheme 5. Plausible mechanism.
TMS)
d
2.26 (s, 3H), 3.70 (s, 3H), 6.33 (d, J¼15.9 Hz, 1H), 7.07e7.22
(m, 4H), 7.57 (d, J¼15.9 Hz, 1H). 13C NMR (75 MHz, CDCl3)
d 21.2,
3. Conclusion
51.5, 117.4, 125.1, 128.62, 128.65, 131.0, 134.2, 138.4, 144.9, 167.4.
In conclusion, we have reported herein the Heck-type reaction of
triarylphosphines with various alkenes in the presence of a catalytic
amount of PdCl2. The reaction requires AgOOCCF3 as the oxidant and
NaOAc as the base. A plausible mechanism for this type of Pd(II)-
catalyzed oxidative Heck-type reaction was also given. Efforts are
underway to elucidate the mechanistic details of this reaction and to
determine its scope and limitations in this laboratory.
4.2.8. Compound 3g.13 A yellow liquid. 1H NMR (300 MHz, CDCl3,
TMS)
d
3.79 (s, 3H), 6.32 (d, J¼15.6 Hz, 1H), 6.47 (dd, J¼1.8, 3.3 Hz,
1H), 6.61 (d, J¼3.3 Hz, 1H), 7.44 (d, J¼15.6 Hz, 1H), 7.48 (d, J¼1.8 Hz,
1H). 13C NMR (125 MHz, CDCl3)
144.7, 150.9, 167.5.
d 51.6, 112.2, 114.8, 115.5, 131.2,
4.2.9. Compound 3h.11 A colorless liquid. 1H NMR (300 MHz, CDCl3,
TMS)
d
0.96 (t, J¼7.2 Hz, 3H), 1.37e1.49 (m, 2H), 1.64e1.73 (m, 2H),
4. Experimental section
4.1. General remarks
4.20 (t, J¼6.9 Hz, 2H), 6.43 (d, J¼16.2 Hz, 1H), 7.33e7.37 (m, 3H),
7.48e7.53 (m, 2H), 7.68 (d, J¼16.2 Hz, 1H). 13C NMR (75 MHz, CDCl3)
d
13.6, 19.1, 30.6, 64.2, 118.1, 127.9, 128.7, 130.0, 134.3, 144.4, 166.9.
1H and 13C NMR spectra were recorded on a Bruker Avance AV-II
300 MHz or Bruker Avance AV-III 500 MHz spectrometer for solu-
tion in CDCl3 with tetramethylsilane (TMS) as an internal standard;
J-values are in Hertz. Commercially obtained reagents were used
without further purification. Flash column chromatography was
carried out using Huanghai 300e400 mesh silica gel at increased
pressure. The mass analyzer types for the high resolution mass
spectra (HRMS) are FT-ICR (for EI). LCeMS was detected on Brucker
Esquire HCTspectrometer, and themassanalyzer typeision trap(ESI).
4.2.10. Compound 3i.14 A colorless liquid. 1H NMR (500 MHz, CDCl3,
TMS)
d
0.96 (t, J¼7.5 Hz, 3H), 1.40e1.47 (m, 2H), 1.66e1.71 (m, 2H),
2.36 (s, 3H), 4.20 (t, J¼7.0 Hz, 2H), 6.39 (d, J¼16.0 Hz, 1H), 7.18 (d,
J¼8.0 Hz, 2H), 7.42 (d, J¼8.0 Hz, 2H), 7.65 (d, J¼16.0 Hz, 1H). 13C
NMR (125 MHz, CDCl3)
d 13.7, 19.2, 21.4, 30.8, 64.3, 117.2, 128.0,
129.5, 131.7, 140.5, 144.5, 167.2.
4.2.11. Compound 3j.11 A colorless liquid. 1H NMR (300 MHz, CDCl3,
TMS)
d
0.96 (t, J¼7.2 Hz, 3H), 1.38e1.50 (m, 2H), 1.64e1.74 (m, 2H),

M.-T. Ma, J.-M. Lu / Tetrahedron 69 (2013) 2102e2106
2105
4.21 (t, J¼6.3 Hz, 2H), 6.36 (d, J¼16.2 Hz, 1H), 7.07 (t, J¼8.7 Hz, 2H),
7.51 (dd, J¼5.4, 8.7 Hz, 2H), 7.64 (d, J¼16.2 Hz, 1H). 13C NMR
d 21.4, 123.7, 127.2, 127.6, 128.6, 128.7, 128.8, 133.1, 136.0, 136.9,
138.3. IR (CH2Cl2) n 1585, 1486, 1270, 1082, 1003, 969, 862, 812, 783,
(125 MHz, CDCl3)
d
13.6, 19.1, 30.7, 64.4, 115.9 (d, JCeF¼21.8 Hz),
736 cmꢁ1. MS (EI, m/z) (%): 228 (Mþ, 98), 178 (100); HRMS (EI):
118.0 (d, JCeF¼2.3 Hz), 129.8 (d, JCeF¼8.5 Hz), 130.7 (d, JCeF¼3.4 Hz),
calcd for C15H13Cl [M]þ: 228.0706; found: 228.0705.
143.1, 163.8 (d, JCeF¼249.6 Hz), 166.9.
Acknowledgements
4.2.12. Compound 3k.14 A colorless liquid. 1H NMR (300 MHz,
CDCl3, TMS)
d
0.96 (t, J¼7.2 Hz, 3H), 1.40e1.49 (m, 2H), 1.64e1.73
Financial support from the National Natural Science Foundation
of China (No. 21002072) is greatly appreciated.
(m, 2H), 2.35 (s, 3H), 4.20 (t, J¼6.9 Hz, 2H), 6.42 (d, J¼15.9 Hz, 1H),
7.16e7.32 (m, 4H), 7.65 (d, J¼15.9 Hz, 1H). 13C NMR (75 MHz, CDCl3)
d
13.6, 19.1, 21.1, 30.7, 64.2, 117.9, 125.1, 128.6, 130.9, 134.3, 138.4,
Supplementary data
144.6, 167.0.
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2013.01.025.
These data include MOL files and InChiKeys of the most important
compounds described in this article.
4.2.13. Compound 3l.15 A white solid. 1H NMR (300 MHz, CDCl3,
TMS)
(125 MHz, CDCl3)
d
7.08 (s, 2H), 7.20e7.35 (m, 6H), 7.47e7.50 (m, 4H). 13C NMR
d
126.5, 127.6, 128.66, 128.70, 137.3.
4.2.14. Compound 3m.15 A white solid. 1H NMR (300 MHz, CDCl3,
TMS)
References and notes
d
2.35 (s, 3H), 7.04 (d, J¼16.5 Hz, 1H), 7.10 (d, J¼16.5 Hz, 1H),
7.16 (d, J¼7.8 Hz, 2H), 7.23 (t, J¼7.8 Hz, 1H), 7.34 (t, J¼7.8 Hz, 2H),
1. (a) Mizoroki, T.; Mori, K.; Ozaki, A. Bull. Chem. Soc. Jpn. 1971, 44 581e581; (b)
Heck, R. F.; Nolley, J. P., Jr. J. Org. Chem. 1972, 37, 2320e2322; (c) Heck, R. F.
Palladium Reagents in Organic Synthesis; Academic: London, 1985; (d)
Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009e3066; (e) Whit-
combe, N. J.; Hii, K. K.; Gilbson, S. E. Tetrahedron 2001, 57, 7449e7476; (f)
Dounary, A. B.; Overman, L. E. Chem. Rev. 2003, 103, 2945e2964; (g) Alonso, F.;
Beletskaya, I. P.; Yus, M. Tetrahedron 2005, 61, 11771e11835; (h) Felpin, F.-X.;
Nassar-Hardy, L.; Le Callonnec, F.; Fouquet, E. Tetrahedron 2011, 67, 2815e2831.
2. (a) Fu, G. C. Acc. Chem. Res. 2008, 41, 1555e1564; (b) Birkholz, M.-N.; Freixa, Z.;
van Leeuwen, P. W. N. M. Chem. Soc. Rev. 2009, 38, 1099e1118 and references
therein.
3. For some selected examples, please see: (a) O’Keefe, D. F.; Dannock, M. C.;
Marcuccio, S. M. Tetrahedron Lett. 1992, 33, 6679e6680; (b) Hunt, A. R.;
Stewart, S. K.; Whiting, A. Tetrahedron Lett. 1993, 34, 3599e3602; (c)
Hermann, W. A.; Broßmer, C.; Ofele, K.; Beller, M.; Fischer, H. J. Organomet.
Chem. 1995, 491, C1eC4; (d) Baranano, D.; Hartwig, J. F. J. Am. Chem. Soc.
7.41 (d, J¼7.8 Hz, 2H), 7.49 (d, J¼7.5 Hz, 2H). 13C NMR (125 MHz,
CDCl3) d 21.2, 126.37, 126.41, 127.4, 127.7, 128.61, 128.62, 129.4, 134.5,
137.48, 137.50.
4.2.15. Compound 3n.16 A white solid. 1H NMR (500 MHz, CDCl3,
TMS)
d
7.05 (d, J¼16.5 Hz, 1H), 7.09 (d, J¼16.5 Hz, 1H), 7.26e7.38 (m,
5H, Ar), 7.44 (d, J¼8.5 Hz, 2H, Ar), 7.51 (d, J¼7.0 Hz, 2H, Ar). 13C NMR
(125 MHz, CDCl3)
133.2, 135.9, 137.0.
d 126.5, 127.4, 127.6, 127.9, 128.7, 128.8, 129.3,
4.2.16. Compound 3o.15 A white solid. 1H NMR (300 MHz, CDCl3,
TMS)
6.97e7.10 (m, 4H), 7.23e7.44 (m, 3H), 7.48e7.51 (m, 4H). 13
NMR (75 MHz, CDCl3)
€
~
d
C
1995, 117, 2937e2938; (e) Segelstein, B. E.; Butler, T. W.; Chenard, B. L. J. Org.
Chem. 1995, 60, 12e13; (f) Ahman, J.; Wolfe, J. P.; Troutman, M. V.; Palucki,
d
115.5 (d, JCeF¼21.6 Hz), 126.4, 127.4, 127.6,
ꢀ
127.9 (d, JCeF¼8.0 Hz), 128.4, 128.7, 133.4, 137.1, 162.2
(d, JCeF¼245.6 Hz).
M.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 1918e1919; (g) Zheng, N.;
McWilliams, J. C.; Fleitz, F. J.; Armstrong, J. D., III; Volante, R. P. J. Org. Chem.
1998, 63, 9606e9607; (h) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998,
€
ꢀ
€
120, 3694e3703; (i) Bjorkman, M.; Langstrom, B. J. Chem. Soc., Perkin Trans. 1
2000, 3031e3034; (j) Yin, J.; Buchwald, S. L. Org. Lett. 2000, 2, 1101e1104;
(k) Sundermeirer, M.; Zapf, A.; Beller, M.; Sans, J. Tetrahedron Lett. 2001, 42,
6707e6710; (l) Ghosh, A.; Sieser, J. E.; Riou, M.; Cai, W.; Rivera-Ruiz, L. Org.
Lett. 2003, 5, 2207e2210.
4.2.17. Compound 3p.15 A white solid. 1H NMR (500 MHz, CDCl3,
TMS)
d
6.92 (t, J¼8.0 Hz, 1H), 7.01 (d, J¼15.6 Hz, 1H), 7.07 (d,
J¼15.6 Hz, 1H), 7.17e7.35 (m, 6H), 7.47 (d, J¼7.5 Hz, 2H). 13C NMR
(125 MHz, CDCl3)
d
112.7 (d, JCeF¼21.8 Hz), 114.3 (d, JCeF¼21.4 Hz),
4. For some selected papers on mechanistic details, please see: (a) Kikukawa, K.;
Yamane, T.; Ohbe, Y.; Takagi, M.; Matsuda, T. Bull. Chem. Soc. Jpn. 1979, 52,
1187e1190; (b) Ortiz, J. V.; Havlas, Z.; Hoffmann, R. Helv. Chim. Acta 1984, 67,
1e17; (c) Kong, K. C.; Cheng, C.-H. J. Am. Chem. Soc. 1991, 113, 6313e6315; (d)
Farina, V.; Krishnan, B. J. Am. Chem. Soc. 1991, 113, 9585e9595; (e) Herrmann,
122.4, 126.6, 127.4, 127.9, 128.7, 130.0, 136.8, 139.7 (d, JCeF¼7.7 Hz),
163.1 (d, JCeF¼243.8 Hz).
4.2.18. Compound 3q.15 A white solid. 1H NMR (300 MHz, CDCl3,
€
W. A.; Broßmer, C.; Priermeier, T.; Ofele, K. J. Organomet. Chem. 1994, 481,
97e108; (f) Morita, D. K.; Still, J. K.; Norton, J. R. J. Am. Chem. Soc. 1995, 117,
8576e8581; (g) Goodson, F. E.; Wallow, T. I.; Novak, B. M. J. Am. Chem. Soc. 1997,
119, 12441e12453; (h) Grushin, V. V. Organometallics 2000, 19, 1888e1900; (i)
de La Torre, G.; Gouloumis, A.; Vazquez, P.; Torres, T. Angew. Chem., Int. Ed. 2001,
40, 2895e2898; (j) Kwong, F. Y.; Chan, K. S. Organometallics 2001, 20,
TMS)
d
2.34 (s, 3H), 7.00e7.11 (m, 3H), 7.18e7.34 (m, 6H), 7.46e7.49
21.4, 123.7, 126.4, 127.2, 127.5,
(m, 2H). 13C NMR (125 MHz, CDCl3)
d
ꢁ
128.40, 128.44, 128.5, 128.6, 128.8, 137.2, 137.4, 138.1.
2570e2578.
4.2.19. Compound 3r. A white solid. Mp: 100e101 ꢀC. 1H NMR
5. (a) For recent reviews, please see: Su, Y.-J.; Jiao, N. Curr. Org. Chem. 2011, 15,
3362e3388; (b) Bras, J. L.; Muzart, J. Chem. Rev. 2011, 111, 1170e1214.
6. For some more recent papers on oxidative Heck reaction, please see: (a)
Nordqvist, A.; Bjoerkelid, C.; Andaloussi, M.; Jansson, A. M.; Mowbray, S. L.;
Karlen, A.; Larhed, M. J. Org. Chem. 2011, 76, 8986e8998; (b) Liu, Y.; Li, D.; Park,
C.-M. Angew. Chem., Int. Ed. 2011, 50, 7333e7336; (c) Gottumukkala, A. L.;
Teichert, J. F.; Heijnen, D.; Eisink, N.; van Dijk, S.; Ferrer, C.; van den
Hoogenband, A.; Minnaard, A. J. J. Org. Chem. 2011, 76, 3498e3501; (d) Sun, P.;
Zhu, Y.; Yang, H.-L.; Yan, H.; Lu, L.-H.; Zhang, X.; Mao, J.-C. Org. Biomol. Chem.
2012, 10, 4512e4515; (e) Inamoto, K.; Kawasaki, J.-P.; Hiroya, K. u; Kondo, Y.;
Doi, T. Chem. Commun. 2012, 4332e4334; (f) Schmidt, B.; Elizarov, N. Chem.
Commun. 2012, 4350e4352; (g) Khoobi, M.; Alipour, M.; Zarei, S.; Jafarpour, F.;
Shafiee, A. Chem. Commun. 2012, 2985e2987.
(300 MHz, CDCl3, TMS)
NMR (125 MHz, CDCl3)
JCeF¼3.5 Hz), 126.7, 127.0, 127.1, 127.9, 128.7, 128.8 (d, JCeF¼8.5 Hz),
d C
7.04e7.25 (m, 8H), 7.36e7.64 (m, 3H). 13
d
115.8 (d, JCeF¼22.0 Hz), 120.9, 124.2 (d,
137.3, 160.5 (d, JCeF¼248.3 Hz). IR (CH2Cl2)
n
1573, 1478, 1450, 1264,
1230, 1205, 1090, 963, 840, 783, 757, 734 cmꢁ1. MS (EI, m/z) (%): 198
(Mþ, 100); HRMS (EI): calcd for C14H11F [M]þ: 198.0845; found:
198.0840.
4.2.20. Compound 3s.17 1H NMR (500 MHz, CDCl3, TMS)
d 2.31
(s, 3H), 2.39 (s, 3H), 6.95 (d, J¼16.0 Hz, 1H), 6.99e7.02 (m, 2H),
7. For example on arylphosphonic acids as the substrates, please see: Inoue, A.;
Shinokubo, H.; Oshima, K. J. Am. Chem. Soc. 2003, 125, 1484e1485.
8. For example on tetraarylphosphonium halides as the substrates, please see:
Hwang, L. K.; Na, Y.; Lee, J.; Do, Y.; Chang, S. Angew. Chem., Int. Ed. 2005, 44,
6166e6169 and references therein.
7.22e7.36 (m, 4H), 7.48e7.51 (m, 3H). 13C NMR (125 MHz, CDCl3)
d
19.8, 21.1, 125.3, 126.4, 126.9, 127.4, 128.6, 129.0, 131.2, 133.5, 135.6,
137.3, 137.8.
9. For pioneering work on the Pd-mediated Heck reaction using triarylphosphines
as the substrates, please see: (a) Asano, R.; Moritani, I.; Fujiwara, Y.; Teranishi, S.
Bull. Chem. Soc. Jpn. 1973, 46, 2910e2911; (b) Kikukawa, K.; Takagi, M.; Matsuda,
T. Bull. Chem. Soc. Jpn. 1979, 52, 1493e1497.
4.2.21. Compound 3t. A white solid. Mp: 88e89 ꢀC. 1H NMR
(300 MHz, CDCl3, TMS)
d
7.03 (s, 2H), 7.06 (d, J¼7.5 Hz, 1H),
7.22e7.33 (m, 5H), 7.39e7.44 (m, 2H). 13C NMR (125 MHz, CDCl3)
10. Lu, J.-M.; Ma, H.; Li, S.-S.; Ma, D.; Shao, L.-X. Tetrahedron 2010, 66, 5185e5189.

2106
M.-T. Ma, J.-M. Lu / Tetrahedron 69 (2013) 2102e2106
11. Karimi, B.; Enders, D. Org. Lett. 2006, 8, 1237e1240.
12. Diebold, C.; Schweizer, S.; Becht, J.-M.; Le Drian, C. Org. Biomol. Chem. 2010, 8,
4834e4836.
15. Gao, T.-T.; Jin, A.-P.; Shao, L.-X. Beilstein J. Org. Chem. 2012, 8, 1916e1919.
16. Tang, Y.-Q.; Chu, C.-Y.; Zhu, L.; Qian, B.; Shao, L.-X. Tetrahedron 2011, 67,
9479e9483.
13. Hopf, H.; Abhilash, K. G. Synlett 2009, 3349e3351.
14. Chen, T.; Gao, J.; Shi, M. Tetrahedron 2006, 62, 6289e6294.
17. Kabalka, G. W.; Al-Masum, M.; Mereddy, A. R.; Dadush, E. Tetrahedron Lett.
2006, 47, 1133e1136.