Palladium-catalyzed Heck-type reaction of oximes with allylic alcohols: Synthesis of pyridines and azafluorenones

Article abstract of DOI:10.1039/c5cc06958k

We describe herein a palladium-catalyzed Heck-type reaction of O-acetyl ketoximes and allylic alcohols to synthesise pyridines. This protocol allows the robust synthesis of pyridines and azafluorenones in good to excellent yields with tolerance of various functional groups under mild conditions. The reaction is supposed to go through an oxidative addition of oximes to palladium(0) complexes, generating an alkylideneamino-palladium(ii) species, which is utilized as a key intermediate to capture the nonbiased alkenes for carbon-carbon bond formation.

Full text of DOI:10.1039/c5cc06958k

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ARTICLE TYPE
Palladium-Catalyzed Heck-Type Reaction of Oximes with Allylic Alcohols:
Synthesis of Pyridines and Azafluorenones
Meifang Zheng, Pengquan Chen, Wanqing Wu, Huanfeng Jiang*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
participation
of
transition
metals
to
form
active
We describe herein a palladium-catalyzed Heck-type reaction
of O-acetyl ketoximes and allylic alcohols to pyridines. This
protocol allows robust synthesis of pyridines and
azafluorenones in good to excellent yields with tolerance of
10 various functional groups under mild conditions. The
reaction is supposed to go through an oxidative addition of
alkylideneaminopalladium(II) species, which tautomerized to the
key iminylpalladium(II) intermediates, making the following
50 alkylpalladium-catalyzed oxidative Heck-type reaction possible
(Scheme 1, c).10,11 In this regard, based on our previous work on
oximes12 and allylic alcohols as alkyl ketone resourses13, we
design the possible [3 + 3] type cyclization with these two
substrates and suppose the reaction to go through a palladium-
55 catalyzed Heck-Type coupling of oximes with alkenes, with high
efficiency under mild reaction conditions.
oximes
to
palladium(0)
complexes
generating
alkylideneamino-palladium(II) species, which is utilized as a
key intermediate to capture the nonbiased alkenes for
15 carbon–carbon bond formation.
HR
HL
HL HR
+
PdX
(a) Ar
The N-heterocycles are some of the most important building
blocks in organic chemistry.1 Among that, pyridines are one of
the most significant building blocks, which not only exist
extensively in pharmaceuticals, agrochemicals, and functional
20 materials, but also serve as useful synthetic intermediates in
modern organic synthesis.2 Considering the large spectrum of
fascinating applications, the synthesis of pyridine derivatives has
long been an area of intense interest, and a number of different
methods have been devised for their preparation.3 However,
25 challenges still remains in the scope of group tolerance and
equivalent usage of catalysts. Therefore, the development of
methodologies for a more direct and efficient access to different
substituted and specifically functionalized frameworks is always
a great challenge in modern synthetic organic chemistry.
Ar
R
Ar
R
R
Ar
Ar
R
PdIILn
R'
H
OH
R'
R'
R'
Ar PdII
(b)
+
H
PdIILn
OH
Ar
O
Ar
OH
(c) This work
NOAc
R'
R''
R''
Pd0
R'
OH
N
R2
R1
-HOAc,
-H2O, -H2
R1
R2
Pd0
Cu,O2
O
R''
H
NH2
NH
PdOAc
R2
HN
R1
PdOAc
H
R'
+
R1
R'
R1
R2 R''
OH
R2
Scheme 1 Selective β-H elimination of Heck reaction
30
The development of catalytic C-C bond-forming reactions
remains one of the main challenges in organic chemistry.4 Among
the transition metal-catalyzed reactions known to form C-C bonds,
the palladium-catalyzed oxidative coupling by Mizoroki-Heck
stands out as one of the most valuable synthetic tools.5 Since its
With the ability of palladium to reduce oxime N-O bonds, we
60 chose 3,4-dihydronaphthalen-1(2H)-one O-acetyl oxime (1a) and
but-3-en-2-ol (2a) as model substrates and screened different
additives and other reaction conditions (Table 1). To our delight,
the desired product 3aa could be detected in 56% yield when the
model reaction was conducted in CH3CN with CuBr2 as additive
65 in the presence of Pd(OAc)2 catalyst under dioxygen atmosphere
35 first report in 1970s, lots of efforts have been devoted to its
utilization, and it is now fully recognized as one of the most
significant methods for carbon–carbon bond formations.6 Given
that most of the oxidative Heck reaction was limited to active
alkenes or styrenes due to the poor reactivity of unactivated
40 olefins7 and the dilemma of selective β-H elimination8 (Scheme 1,
a), therefore, transition metal-catalyzed olefination of nonbiased
allylic alcohols, without the prior functionalization, is even more
environmentally friendly and versatile (Scheme 1, b).9 According
to previous reports, oximes and their derivatives can be used as
45 “internal oxidant” towards transition metal-catalyzed oxidative C-
H functionalization and cleavage of the N-O bond by the
o
at 80 C for 24 h (entry 1). The screening of different additives,
including Cu(OAc)2, KI, and AgNO3, revealed that 3aa could
also be formed in lower yields (entries 2-4). And Cu(OAc)2 was
found to be the best additive and the yield of 3aa could reach
70 87% (entry 2). However, with other additives, such as LiBr,
NH4Br, Bu4NBr, and AgOAc, only trace amount of 3aa was
detected (entries 5-8). The model reaction was then tested using
other palladium catalytic system, and Pd(OAc)2 was found to be
the most suitable catalyst system for the target reaction (entries 9-
75 11). No reaction was observed in the absence of palladium
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catalyst (entry 12), while with the absence of Cu(OAc)2, the 35 yield (3qa). Notably, L(-)-carvone derived oximes could transfer
reaction could give 10% yield of product 3aa (entry 13). The
to 3ra in 43% yield.
View Article Online
DOI: 10.1039/C5CC06958K
yield was unsatisfactory with the decrease of the reaction
Table 2 Pd-catalyzed synthesis of substituted pyridines from different
o
oximesa
temperature (entry 14), while raising the temperature to 100 C
5
improved the yield to 91% (entry 15). When the reaction was
carried out in N2 atmosphere, only trace amount of 3aa was
detected by GC-MS (entry 17).
Table 1 Screening for optimal reaction conditionsa
entrya
1
catalyst
additive
CuBr2
base
solvent
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
yieldb (%)
56
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
2
Cu(OAc)2
KI
87 (87)
10
3
4
AgNO3
LiBr
25
5
trace
trace
trace
trace
57
6
NH4Br
7
Bu4NBr
AgOAc
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
--
8
9
PdCl2
Pd(OTf)2
10
11
12
13
63
Pd2(dba)3
---
trace
n.d.
10
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
14c
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
35
15d
16e
91
78
17f
trace
a
10 Reaction conditions: Unless otherwise noted, the reaction was carried
out with 1a (0.2 mmol), 2a (0.4 mmol), Pd catalyst (5 mol %), additive
o
b
(20 mol %) and base (1.5 equiv) in solvent (1 mL) at 80 C for 24 h.
Yield determined by GC-MS with dodecane as internal standard, and
isolated yield in the parentheses. c The reaction was carried out at 60 oC. d
o
15 The reaction was carried out at 100 C. e The reaction was carried out in
f
the open air. The reaction was carried out in N2 atmosphere.
a
40
Reaction conditions: Unless otherwise noted, the reaction was carried
With the optimal reaction conditions in hand, we subsequently
explored the reaction scope. The oxime substrates derived from
other aryl ketones such as tetralones, propiophenones and 2-
20 phenylacetophenones could afford the products 3aa-3na in good
to excellent yields, respectively. Besides, oximes derived from
aliphatic ketones afforded the pyridine derivatives 3oa-3ra in
moderate to good yields. To be specific, chroman-4-one oxime
could afford 3da in 59% yield. The formation of 3da and 3ea
25 were inert under these conditions, indicating that the palladium
catalyst preferentially reacts with the N-O bond of the oxime
acetate over the carbon-halogen bonds. Other aryl functionalized
amides could also undergo the pathway well. The 2-furan-
substituted and 3-furan-substituted oximes could be tolerated in
30 this transformation, generating 3ia and 3ja in 56% and 74%
yields, respectively. It is noteworthy that alkyl-substituted oximes
were also suitable substrates in this reaction with good yields
(3oa to 3ra). For example, propone oximes that contained short
alkyl chains gave the products 2,6-dimethylpyrudine in moderate
out with 1 (0.5 mmol), 2a (1.0 mmol), Pd(OAc)2 (5 mol %), Cu(OAc)2
(20 mol %) and K2CO3 (1.5 equiv) in CH3CN (1 mL) at 80 oC for 16-24 h.
We next focused our attention on the scope and generality of
the olefin substrates in the oxidative coupling with oxime 1a.
45 This transformation displayed high functional group tolerance
and proved to be a quite general method. Both aliphatic and
aromatic allylic alcohols could undergo the protocol with good to
excellent yields (Table 3). Alkyl-substituted allyl alcohols were
found to be suitable substrates for this transformation and
50 transferred to the desired products in good yields (3aa to 3ad).
Even the bulky aromatic allylic alcohols with methyl, methoxyl
and fluoro on aryl rings all gave good to excellent yields of the
corresponding pyridines (3af-3ah). To be specifically, 3ah could
be obtained in 35% yield, which implied the steric hindrance had
55 no much effect on this transformation. And the substrate with aryl
substitution of 1-(thiophen-3-yl)prop-2-en-1-ol underwent the
Heck reaction smoothly and gave the corresponding product 3ak
2
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a Reaction conditions: Unless otherwise noted, the reaction was carried
in 66% yield. As for the application of hexa-1,5-dien-3-ol in this
reaction, hydrogen immigration product 3aj was obtained in 45%
yield, which may further support the role of palladium in the β-H
25 out with 1 (0.5 mmol), 2 (1.0 mmol), Pd(OAc)2 (5 mol %), Cu(OAc)2 (20
mol %) and K2CO3 (1.5 equiv) in CH3CN (1 mL) at 80 oC for 16-24 h.
View Article Online
DOI: 10.1039/C5CC06958K
Based on the experimental results17 and previous reports, a
elimination.
Besides,
with
the
application
of
2-
plausible mechanism is proposed in Scheme 2. Firstly, the
oxidative addition of the oxime N-O bond to Pd(0) species easily
30 transformed to palladium enamide intermediate A. Subsequent
tautomerization affords the enamine-derived amido-Pd(II) species
B.11 Further isomerization of this species results in the conversion
of this N-bound enamido-Pd(II) B species to its C-bound isomer
C.18 Followed by Mizoroki-Heck reaction of allylic alcohol 2a
35 inserting into the carbon-palladium bond of alkylpalladium
species C forms intermediate species D.19 Then, intermediate D
undergoes β-H elimination to give intermediate E and regenerates
the active palladium catalyst.14 The intramolecular condensation
of the amine and ketone moieties of intermediate E forms F.
40 Finally, the dehydrative oxidation gives the pyridine product
3aa.20 Alternative mechanism is shown in the Supporting
Information.
5
methylenepropane-1,3-diol as the coupling reagent, the yield of
the desired product 3al sharply decreased to 14% and 50% yield
of 3ai was obtained.14
Table 3 Pd-catalyzed synthesis of substituted pyridines from different
10 allylic alcoholsa
N
O2
3aa
F
H2O
1a
Pd(0)
NH2
O
PdOAc
oxidative
addition
N
HPdOAc
H
H
E
H elimanation
A
tautomerization
O
AcO
Pd
PdOAc
H
HN
HN
a Reaction conditions: Unless otherwise noted, the reaction was carried
out with 1a (0.5 mmol), 2 (1.0 mmol), Pd(OAc)2 (5 mol %), Cu(OAc)2
(20 mol %) and K2CO3 (1.5 equiv) in CH3CN (1 mL) at 80 oC for 16-24 h.
D
B
15
Furthermore, with 1-indanone oximes as substrate, different
azafluorenones could be obtained in this system.15 For example,
the reaction of 2,3-dihydro-1H-inden-1-one O-acetyl oxime (1w)
afforded the corresponding 4-azafluorenones in good yield.
Pleasingly, when 5,6-dihydro-7H-cyclopenta[b]pyridin-7-one O-
NH
PdOAc
H
2a
C
Scheme 2 Possible mechanism
20 acetyl oxime (1x) was applied, 39% yield of 4,5-diazafluorenone
was obtained.16
45
In summary, we have successfully developed a palladium-
catalyzed strategy to construct pyridines from O-acetyl oximes
and nonbiased alkenes. This protocol provides a possible pathway
for the insertion of alkenes to oximes. With the operational
simplicity, efficiency and functional group compatibility, this
Table 4 Synthesis of azafluorenones a
R'
N
R''
Pd(OAc)2 5 mol%
Cu(OAc)2 20 mol%
K2CO3 1.5 equiv.
O2 (1 atm), CH3CN
NOAc
R''
R'
OH
50 protocol will expand the scope of pyridine derivatives.
Furthermore, the present method also enables the direct
construction of a diverse array of azafluorenone cores, which may
find applications in natural product synthesis and medicinal
chemistry.
O
1w
2
3
entry
R’, R’’
R’ = Me, R’’ = H
oximes
yield (%)
45
1
R’ = H, R’’ = H,
R’ = H, R’’ = Me
67
47
55
The authors thank the National Natural Science Foundation of
China (21172076, 21202046 and 21420102003), the Fundamental
Research Funds for the Central Universities (2014ZP0004), and
the Doctoral Fund of the Department of Education of Guangdong
(sybzzxm201310) for financial support.
2
3
4
R’ = H, R’’ = H
39
60 Notes and references
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School of Chemistry and Chemical Engineering, South China University
2012, 14, 1760; (c) L, Qin, X. Ren, Y. Lu, Y. Li and J. Zhou,
of Technology, Guangzhou 510640, China. Fax: +86 20-87112906; Tel:
+86 20-87112906; E-mail: jianghf@scut.edu.cn
Angew. Chem. Int. Ed., 2012, 51, 5915.
(a) M. Chen, J. Wang, Z. Chai, C. You and A. Lei,ViAewdvA.rtSicylentOhn.line
Catal., 2012, 354, 341; (b) M. Vellakkaran, M. M. S. Andappan
and N. Kommu, Eur. J. Org. Chem., 2012, 4694; (c) Z. Shi, M.
Boultadakis-Arapinis and F. Glorius, Chem. Commun., 2013, 49,
6489.
9
DOI: 10.1039/C5CC06958K
† Electronic Supplementary Information (ESI) available: Experimental
75
80
85
90
1
5 section, characterization of all compounds, copies of H and 13C NMR
spectra for selected compounds. See DOI: 10.1039/b000000x/
1
For recent reviews, (a) J. A. Bull, J. J. Mousseau, G. Pelletier and
A. B. Charette, Chem. Rev., 2012, 112, 2642; (b) N. R. Candeias,
C. Brancol, P. M. P. Gois, C. A. M. Afonso and A. F. Trindade,
Chem. Rev., 2009, 109, 2703; (c) M. T. Aranda, P. Perez and R.
Gonzalez, Curr. Org. Synth., 2009, 6, 325; (d) N. T. Patil and Y.
Yamamoto, Chem. Rev., 2008, 108, 3395; (e) B. Alcaide, P.
Almendros and C. Aragoncillo, Chem. Rev., 2007, 107, 4437; (f)
X.-F. Wu and M. Beller in Heterocycles from Double-
Functionalized Arenes: Transition Metal Catalyzed Coupling
Reactions, RSC, 2015; (g) X.-F. Wu and M. Beller in Economic
Synthesis of Heterocycles: Zinc, Iron, Copper, Cobalt, Manganese
and Nickel Catalysts, RSC, 2014; (h) X.-F. Wu, H. Neumann and
M. Beller, Chem. Rev., 2013, 113, 1.
10 For recent reviews of Pd-catalyzed using N-O bond as an internal
oxidant, see: (a) M. Kitamura and K. Narasaka, Chem. Rec., 2002,
2, 268; (b) K. Narasaka and M. Kitamura, Eur. J. Org. Chem.,
2005, 4505; (c) H. Huang, X. Ji, W. Wu and H. Jiang, Chem. Soc.
Rev., 2015, 44, 1155.
11 For examples of Pd-catalyzed using N-O bond as an internal
oxidant, see: (a) J. Wu, X. Cui, L. Chen, G. Jiang and Y. Wu, J.
Am. Chem. Soc., 2009, 131, 13888; (b) W. P. Hong, A. V. Iosub
and S. S. Stahl, J. Am. Chem. Soc., 2013, 135, 13664; (c) T.
Gerfaud, L. Neuville and J. Zhu, Angew. Chem., Int. Ed., 2009, 48,
572; (d) Y. Tan and J. F. Hartwig, J. Am. Chem. Soc., 2010, 132,
3676; (e) F. W. Patureau and F. Glorius, Angew. Chem., Int. Ed.,
2011, 50, 1977; (f) A. Faulkner and J. F. Bower, Angew. Chem.
Int. Ed., 2012, 51, 1675; (g) A. Faulkner, J. S. Scott and J. F.
Bower, Chem. Commun., 2013, 49, 1521; (h) C. Chen, L. Hou, M.
Cheng, J. Su and X. Tong, Angew. Chem. Int. Ed., 2015, 54, 1.
10
15
20
25
30
35
40
45
50
55
60
65
70
2
3
(a) C. Allais, J.-M. Grassot, J. Rodriguez and T. Constantieux
Chem. Rev. 2014, 114, 10829; (b) S. Zheng, Q. Zhong, M.
Mottamal, Q. Zhang, C. Zhang, E. LeMelle, H. McFerrin and G.
Wang, J. Med. Chem., 2014, 57, 3369; (c) J. Bonin, C. Costentin, 95 12 (a) X. Tang, L. Huang, C. Qi, W. Wu and H. Jiang, Chem.
M. Robert and J-M. Savéant, Org. Biomol. Chem., 2011, 9, 4064;
(d) D. M. Stout and A. I. Meyers, Chem. Rev., 1982, 82, 223; (e)
C.-P. Cao, W. Lin, M.-H. Hu, Z.-B. Huang and D.-Q. Shi, Chem.
Commun., 2013, 49, 6983.
For examples of pyridine synthesis, see: (a) Y. Wei and N. 100
Yoshikai, J. Am. Chem. Soc., 2013, 135, 3756; (b) Z.-H. Ren, Z.-
Y. Zhang, B.-Q. Yang, Y.-Y. Wang and Z.-H. Guan, Org. Lett.,
2011, 13, 5394; (c) K. Wu, Z. Huang, C. Liu; H. Zhang and A.
Lei, Chem. Commun., 2015, 51, 2286; (d) L.-Y. Xi, R.-Y. Zhang,
S. Liang, S.-Y. Chen and X.-Q. Yu, Org. Lett., 2014, 16, 5269; (e) 105
H. Huang, X. Ji, W. Wu, L. Huang and H. Jiang, J. Org. Chem.,
2013, 78, 3774; (f) K. Parthasarathy, M. Jeganmohan and C.-H.
Cheng, Org. Lett., 2008, 10, 325.
Commun., 2013, 49, 9597; (b) H. Huang, X. Ji, X. Tang, M.
Zhang, X. Li and H. Jiang, Org. Lett., 2013, 15, 6254; (c) X. Tang,
L. Huang, Y. Xu, J. Yang, W. Wu and H. Jiang, Angew. Chem.,
Int. Ed., 2014, 53, 4205; (d) X. Tang, L. Huang, J. Yang, Y. Xu,
W. Wu and H. Jiang, Chem. Commun., 2014, 50, 14793.
13 (a) W. Wu and H. Jiang, Acc. Chem. Res., 2012, 45, 1736; (b) Y.
Wen, L. Huang, H. Jiang and H. Chen, J. Org. Chem., 2012, 77,
2029; (c) H. Chen, L. Huang, W. Fu, X. Liu and H. Jiang, Chem.
Eur. J. 2012, 18, 10497; (d) L. Huang, Q. Wang, J. Qi, X. Wu, K.
Huang and H. Jiang, Chem. Sci., 2013, 4, 2665; (e) L. Huang, J.
Qi, X. Wu, K. Huang and H. Jiang, Org. Lett., 2013, 15, 2330; (f)
Q. Wang, L. Huang, X. Wu and H. Jiang, Org. Lett., 2013, 15,
5940.
14 (a) M. Mahyari, M. S. Laeini and A. Shaabani, Chem. Commun.,
2014, 50, 7855; (b) Y. Gao, G. Hu, J. Zhong, Z. Shi, Y. Zhu, D. S.
Su, J. Wang, X. Bao and D. Ma, Angew. Chem., Int. Ed., 2013, 52,
2109; (c) G. Urgoitia, R. S. Martin, M. T. Herrero and E.
Domínguez, Green Chem., 2011, 13, 2161; (d) X. Zhang, X. Ji, S.
Jiang, L. Liu, B. L. Weeks and Z. Zhang, Green Chem., 2011, 13,
1891; (e) X. Feng, J.-J. Wang, Z. Xun, Z.-B. Huang and D.-Q. Shi.
J. Org. Chem., 2015, 80, 1025.
15 (a) C. Ferreri, C. Costantino, C. Chatgilialoglu, R. Boukherroub
and G. Manuel, J. Organometallic Chem., 1998, 554, 135; (b) H.
Wang, L. Li, X.-F. Bai, J.-Y. Shang, K.-F. Yang and L.-W. Xu,
Adv. Synth. Catal., 2013, 355, 341; (c) H. Hikawa, Y. Ino, H.
Suzuki and Y. Yokoyama, J. Org. Chem., 2012, 77, 7046; (d) H.
Hikawa, N. Matsuda, H. Suzuki, Y. Yokoyama and I. Azumaya,
Adv. Synth. Catal., 2013, 355, 2308.
16 (a) A. N. Campbel, P. B. White, I. A. Guzei and S. S. Stahl, J. Am.
Chem. Soc., 2010, 132, 15116; (b) M. A. Bigi and M. C. White, J.
Am. Chem. Soc., 2013, 135, 7831; (c) A. Sharma and J. F. Hartwig,
J. Am. Chem. Soc., 2013, 135, 17983; (d) T. Diao, T. J. Wadzinski
and S. S. Stahl, Chem. Sci., 2012, 3, 887; (e) W. Gao, Z. He, Y.
Qian, J. Zhao and Y. Huang, Chem. Sci., 2012, 3, 883.
4
5
For reviews, see: (a) L. F. Tietze, Chem. Rev., 1996, 96, 115; (b) G.
Zeni and R. C. Larock, Chem. Rev., 2004, 104, 2285; (c) J. Hassan, 110
M. Svignon, C. Gozzi, E. Schulz and M. Lemaire, Chem. Rev.,
2002, 102, 1359; (d) J. Corbet and G. Mignani, Chem. Rev., 2006,
106, 2651; (e) C.-J. Li, Chem. Rev., 2005, 105, 3095; (e) W. Wu
and H. Jiang, Acc. Chem. Res., 2014, 47, 2483.
(a) R. F. Heck, Acc. Chem. Res., 1979, 12, 146; (b) R. F. Heck, 115
Org. React., 1982, 27, 345; (c) R. F. Heck in Comprehensive
Organic Synthesis (Eds.: B. M. Trost, I. Fleming), Pergamon Press,
Oxford, 1991, 4, 833; (d) M. Kitamura and K. Narasaka, The
Chemical Record., 2002, 2, 268; (e) C. C. C. J. Seechurn, M. O.
Kitching, T. J. Colacot and V. Snieckus, Angew. Chem., Int. Ed., 120
2012, 51, 5062.
6
For recent selected examples of Heck reactions, see: (a) Y. Izawa,
C. Zheng and S. S. Stahl, Angew. Chem., Int. Ed., 2013, 52, 3672;
(b) S. Arai, T. Sato, Y. Koike; M. Hayashi and A. Nishida, Angew.
Chem., Int. Ed., 2009, 48, 4528; (c) C. Pi, Y. Li; X. L. Cui; H. 125
Zhang; Y. Han and Y. Wu, Chem. Sci., 2013, 4, 2675; (d) E. Alza,
L. Laraia, B. M. Ibbeson, S. Collins, W. R. J. D. Galloway, J. E.
Stokes, A. R. Venkitaraman and D. R. Spring, Chem. Sci., 2015, 6,
390; (e) C. M. McMahon and E. J. Alexanian, Angew. Chem. Int.
Ed., 2014, 53, 5974; (f) S. Ma and Z. Gu, Angew. Chem. Int. Ed., 130 17 See the Surpporting Information for the details of the control
2005, 44, 7512.
experiments.
7
(a) K. H. Jensen, T. P. Pathak and Y. Zhang, J. Am. Chem. Soc.,
2009, 131, 17074; (b) W. E. Werner, J. Am. Chem. Soc., 2010,
132, 13981; (c) R. J. DeLuca and M. S. Sigman, J. Am. Chem.
Soc., 2011, 133, 11454; (d) W. Erik, E. W. Werner, T.-S. Mei, A. 135
J. Burckle and M. S. Sigman, Science, 2012, 338, 1455; (e) X.
Tong, M. Beller and M. K. Tse, J. Am. Chem. Soc., 2007, 129,
4906; (f) G. Yue, K. Lei, H. Hirao and J. Zhou, Chem. Sci., 2013,
4, 2675; (g)M. Kitamura, D. Kudo, K. Narasaka, Arkivoc, 2006,
18
K. Okamoto, T. Oda, S. Kohigashi and K. Ohe, Angew.
Chem.,Int. Ed., 2011, 50, 11470.
19 (a) Y. Li, Z. Yu and S. Wu, J. Org. Chem., 2008, 73, 5647; (b) M.
Zheng, L. Huang, W. Wu and H. Jiang, Org. Lett., 2013, 15, 1838;
(c) A. J. Mota and A. Dedieu, J. Org. Chem., 2007, 72, 9669; (d)
T. Piou, L. Neuville and J. Zhu, Angew. Chem. Int. Ed., 2012, 51,
11561.
20 (a) R. Neumann and M. Lissel, J. Org. Chem., 1989, 54, 4607; (b)
R. Yan, J. Luo, C. Wang, C. Ma, G. Huang and Y. Liang, J. Org.
Chem., 2010, 75, 5395.
148.
140
8
(a) M. S. Chen and M. C. White, J. Am. Chem. Soc., 2004, 126,
1346; (b) A. Kubota, M. H. Emmert and M. S. Sanford, Org. Lett.,
4
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