Palladium-catalyzed highly regioselective arylation of allylamines with thiophenes and furans

Article abstract of DOI:10.1002/adsc.201200470

A palladium-catalyzed highly regioselective and stereoselective direct arylation of allylamine derivatives with a wide range of thiophenes and furans has been developed. In the presence of palladium(II) acetate [Pd(OAc) ₂] catalyst and appropriate oxidants, the coupling reaction proceeded with excellent group compatibility and high efficiency, leading exclusively to γ-arylated linear (E)-allylamines. It was found that the choice of solvent, olefin substrate and oxidant had an important influence on reaction efficiency, and the use of sterically demanding N,N-diprotected allylamines bearing a carbamate moiety is crucial for securing high regioselectivity and stereoslectivity. This method provides a straightforward approach for the efficient synthesis of various γ-heteroarylated, linear (E)-allylamines. Copyright

Full text of DOI:10.1002/adsc.201200470

FULL PAPERS
DOI: 10.1002/adsc.201200470
Palladium-Catalyzed Highly Regioselective Arylation of
Allylamines with Thiophenes and Furans
Zhen Jiang,a Lingjuan Zhang,a Chaonan Dong,a Zhongzheng Cai,a Weijun Tang,b
Huanrong Li,a Lijin Xu,a,* and Jianliang Xiaob
a
Department of Chemistry, Renmin University of China, Beijing 100872, Peopleꢀs Republic of China
Fax : (+86)-10-6251-6444; phone: (+86)-10-6251-1528; e-mail: xulj@chem.ruc.edu.cn
Liverpool Centre for Materials and Catalysis, Department of Chemistry, University of Liverpool, Liverpool L69 7ZD,
b
U.K.
Received: May 29, 2012; Revised: September 5, 2012; Published online: November 13, 2012
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200470.
Abstract: A palladium-catalyzed highly regioselec- efficiency, and the use of sterically demanding N,N-
tive and stereoselective direct arylation of allylamine diprotected allylamines bearing a carbamate moiety
derivatives with a wide range of thiophenes and is crucial for securing high regioselectivity and ster-
furans has been developed. In the presence of palla- eoslectivity. This method provides a straightforward
dium(II) acetate [PdACHTNUTRGENNG(U OAc)2] catalyst and appropriate approach for the efficient synthesis of various g-het-
oxidants, the coupling reaction proceeded with excel- eroarylated, linear (E)-allylamines.
lent group compatibility and high efficiency, leading
exclusively to g-arylated linear (E)-allylamines. It
was found that the choice of solvent, olefin substrate Keywords: allylamines; furans; palladium; regiose-
and oxidant had an important influence on reaction lective arylation; thiophenes
Introduction
tional groups renders them valuable substrates for
many types of reactions.[8,9] Consequently, much effort
Since the pioneering work of Fujiwara and Moritani, has been devoted to the efficient construction of
the synthetic scope and efficiency of Pd-catalyzed de- these useful compounds.[10–12] Recently, the palladium-
hydrogenative coupling reactions of arenes with ole- catalyzed coupling reaction of aromatic halides, their
fins (also referred to as Fujiwara–Moritani reactions) derivatives and arylboronic acids with allylamines has
have advanced significantly over the past decade.[1,2] It gained much interest in the preparation of biological-
is notable that a number of aromatic heterocycles, in- ly and synthetically important arylated allylamines,
cluding indoles, pyrroles, thiophenes, furans, pyridines, and several useful strategies to control the regioselec-
indolizines and azoles have been used as efficient cou- tivity have been developed.[11,12] Clearly, the direct
pling partners in these processes.[3–6] Despite these en- coupling of arenes with allylamines via C H bond ac-
À
couraging results, most of the effort has been concen- tivation would be more attractive and atom-economic,
trated on the arylation of electron-deficient olefins because no prefunctionalization of the aromatic sub-
and electron-neutral aliphatic olefins and styrenes, strates is required. In continuation of our interest in
with little attention being paid to the reactions with the regioselective arylation of electron-rich olefins,[13]
other types of olefins, such as allyl derivatives. Only herein we report that, in the presence of catalytic
in several cases were Pd-catalyzed dehydrogenative PdACTHNUGTRENUNG(OAc)2 and appropriate oxidants, N,N-diprotected
alkenylations of arenes involving electron-rich allyl allylamines undergo efficient terminal (g-)arylation
esters reported; but their synthetic utility is limited by with thiophenes and furans to give the (E)-allyla-
the requirement of a large excess of the arene reagent mines in good to excellent yields in a highly regiose-
and the problems in the control of regioselectivity lective and stereoselective manner.
and stereoselectivity.[7]
Allylamines are widely found in a number of natu-
ral and synthetic molecules with various biological ac-
tivities, and the presence of two highly versatile func-
Adv. Synth. Catal. 2012, 354, 3225 – 3230
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3225

Zhen Jiang et al.
FULL PAPERS
Table 1. Screening conditions for direct arylation of thiophene 1a with allylamine 2a.[a]
Entry
Solvent (v/v)
Oxidant (equiv.)
Yield [%][b]
1
2
3
4
5
6
7
8
DMSO
DMF
dioxane
CH3CN
THF
DCE
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
Ag2O (1)
16
31
32
0
30
34
27
31
27
35
33
42
36
34
39
78
16
89
10
67
68
37
5% DMSO/dioxane
5% DMF/dioxane
5% DMSO/THF
5% DMF/THF
5% DMSO/DCE
5% DMF/DCE
10% DMF/DCE
2% DMF/DCE
5% DMF/DCE
5% DMF/DCE
5% DMF/DCE
5% DMF/DCE
5% DMF/DCE
5% DMF/DCE
5% DMF/DCE
5% DMF/DCE
9
10
11
12
13
14
15
16
17
18[c]
19[c,d]
20[c,e]
21[c,f]
22[c,g]
Ag2CO3 (1)
CuACTHNUTRGEN(NUG OAc)2 (1)
Ag2CO3 (1)/Cu
Ag2CO3 (1)/Cu
Ag2CO3 (1)/Cu
Ag2CO3 (1)/Cu
Ag2CO3 (1)/Cu
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
G
CHTUNGTRENNUNG
[a]
Reaction conditions: 1a (1.5 mmol.), 2a (0.5 mmol), Pd
THF (tetrahydrofuran) (1.0 mL), 1008C, 14 h, in air.
Isolated yield. All reactions gave >99/1 regioselectivity and stereoselectivity as determined by H NMR.
Reaction temperature 1208C.
10 equiv. AcOH were added.
PdCl2 was used.
ACHTUNGRTEN(NNUG OAc)2 (5 mol%), oxidant, solvent DMSO (dimethyl sulfoxide),
[b]
[c]
[d]
[e]
[f]
1
Pd
Pd
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
[g]
Results and Discussion
tive coupling reactions of thiophenes and furans with
allyl esters afforded mixtures of regioisomers and
Preliminary screening for optimal reaction conditions stereoisomers.[7d] Aiming to improve the yield, the
was performed with thiophene 1a and N,N- performances of other oxidants, such as Ag2O,
A
ACHTUNGERTN(NUNG OAc)2 were evaluated (Table 1, en-
AHCTUNGTRENNUNG
as the catalyst and AgOAc as the oxidant under aero- producing the product 3aa in 78% yield (Table 1,
bic atmosphere conditions, the effect of solvents was entry 16). Further optimization revealed that the com-
firstly examined. It was obvious that the reaction was bined use of Ag2CO3 (1.0 equiv.) and CuACHTUNGTRENNUNG(OAc)2
sensitive to the solvents used (Table 1, entries 1–14), (0.2 equiv.) could enhance the yield of 3aa to 89%
with the mixed solvent system of 5% DMF (N,N-di- (Table 1, entry 18). It has been reported that carbox-
methylformamide) in DCE (1,2-dichloroethane) ylic acids could facilitate the Pd-catalyzed direct olefi-
giving rise to the best reactivity (Table 1, entry 12). It nation of arenes;[2] but the addition of AcOH in our
is notable that only the terminally arylated (E)-allyla- case only led to a significant drop in yield (Table 1,
mine 3aa was isolated in these reactions. The Z entry 19). Olefination with other palladium precursors
isomer or internal arylation product 4aa could not be gave diminished yields (Table 1, entries 20–22).
detected. This is remarkable since the dehydrogena-
3226
asc.wiley-vch.de
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 3225 – 3230

Palladium-Catalyzed Highly Regioselective Arylation of Allylamines with Thiophenes and Furans
Table 2. Regioselective and stereoselective direct arylation
of 2a with thiophenes and furans.[a]
tions. As shown in Table 2, all the reactions proceed-
ed smoothly to afford the corresponding g-arylated
(E)-allylamines in good to excellent yields, with no in-
ternal regioisomers or cis-isomers detected. It is
worth noting that a variety of functional groups, both
electron-donating and electron-withdrawing, were
well-tolerated to give the desired products in high
yields. Of particular note is that chlorinated thio-
phenes underwent highly chemoselective coupling
with good yields (Table 2, entries 3 and 15), leaving
À
the C Cl bond intact. The coupling always took place
Entry
Substrate
Yield [%][b] (product)
at C-5 in the olefination of 2-substituted (Table 2, en-
tries 1–14) and 2,3-disubstituted thiophenes (Table 2,
entry 15), and direct vinylation at C-3 was observed in
the case of 2,5-disubstituted thiophene (Table 2,
entry 17). Interestingly, 3-methylthiophene 1p provid-
ed a 5:2 mixture of 2- and 5-olefinated products,
which are inseparable by chromatography (Table 2,
entry 16). Benzothiophene 1r reacted well with 2a to
afford an inseparable mixture of 2- and 3-olefinated
products with the ratio of 2’/3’ being 5/1 (Table 2,
entry 18), while only the 2-olefinated product was ob-
tained when 3-methylbenzothiophene 1s was em-
ployed (Table 2, entry 19). Furans also proved to be
viable coupling partners to give the desired products
in good yields irrespective of the nature of the sub-
stituent attached to the furan ring (Table 2, en-
tries 20–24). Noteworthy is that all the substrates un-
derwent clean conversions without any allylic migra-
tion or partial deprotection.
The oxidative cross-coupling reaction was further
extended to other allylamine derivatives (Table 3).
Allylamines 2b–d were found to be efficiently arylat-
ed under the conditions established for 2a regardless
of the nature of substituent on the heteroaryl ring, ex-
clusively affording the corresponding (E)-allylamine
products (3ab–3kd) in good yields (Table 3, entries 1–
13). However, in the arylation of allylamine 2e, it was
found that the reaction products were only the g-ary-
lated N-Boc-allylamines (Table 3, entries 14–16), most
probably as a result of the deprotection of Cbz (car-
bobenzyloxy) group during the reaction. Notably, the
substituted allylamine 2f could also undergo smooth
arylation under the current reaction conditions
(Table 3, entries 17 and 18).
1
1b
1c
1d
1e
1f
1g
1h
1i
87 (3ba)
83 (3ca)
73 (3da)
88 (3ea)
85 (3fa)
71 (3ga)
75 (3ha)
63 (3ia)
75 (3ja)
79 (3ka)
83 (3la)
2
3
4
5
6
7
8
9
1j
11
12
1k
1l
13
14
15
1m
1n
1o
78 (3ma)
78 (3na)
80 (3oa)
16[c]
17[d]
18[e]
1p
1q
1r
80 (3pa)
58 (3qa)
79 (3ra)
19
1s
76 (3sa)
20
1t
66 (3ta)
69 (3ua)
65 (3va)
74 (3wa)
80 (3xa)
21
1u
1v
1w
1x
22
23
24[d]
[a]
Reaction conditions: heteroarene (3.0 mmol), allylamine
2a (1.0 mmol), Pd(OAc)2 (5 mol%), Ag2CO3 (1.0 mmol),
Cu(OAc)2 (0.2 mmol), 5% DMF/DCE (4.0 mL), 1208C,
14 h, in air. All reactions gave >99/1 regioselectivity and
stereoselectivity as determined by 1H NMR. Boc=tert-
butyloxycarbonyl.
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
The current palladium catalyst system was not re-
stricted to thiophenes and furans. As shown in
Scheme 1, the direct olefination of fluoroarenes (1a’
and 1b’) with allylamines occurred to provide the de-
sired products in satisfactory yields. We also tried the
reaction of other heteroarenes, such as indole, N-
methylindole, benzothiazole, benzoxazole and thia-
zole, but no reaction occurred.
[b]
[c]
Isolated yield.
A 5:2 mixture of 2- and 5-olefinated products was ob-
tained.
3-Olefinated product was obtained.
A 5:1 mixture of 2- and 3-olefinated products was ob-
tained.
[d]
[e]
The generality of this selective reaction was then
The steric and electronic properties of the allyl-
investigated by coupling 2a with a range of electroni-
ACHTUNGTRENaNGNU mine appear to impact significantly on the catalytic
cally and sterically diverse thiophenes, benzothio- activity and selectivity. Thus, using N-Boc-allylamine
phenes and furans under the optimal reaction condi- (tert-butyl allylcarbamate) 2g led to the formation of
Adv. Synth. Catal. 2012, 354, 3225 – 3230
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
3227

Zhen Jiang et al.
FULL PAPERS
a small amount of the branched olefin 4ag [Eq. (1)],
and no reaction was observed when 2g was replaced
with the less bulky N,N-dibenzylallylamine 2h, which
may poison the catalyst through coordination to palla-
dium. The success with the N,N-disubstituted allyl-
AHCTUNGTREGaNNUN mines 2a–f may be traced to the electron-withdraw-
ing carbonyl unit which discourages nitrogen coordi-
nation and to the bulkiness and possible chleation of
the allylamine with palladium. In the case of 2g, the
reduced steric bulk may encourage the migration of
the aryl group to the internal olefinic carbon, result-
ing in the formation of 4ag. Chelation-assisted regio-
control has been exploited in the arylation of allyla-
mines, vinyl ethers, allyl sulfones and allyl ester-
s.[7a,c,11b,14,15] No examples are known of heterocycles
such as thiophenes and furans, however.
Table 3. Regioselective and stereoselective direct arylation
of allylamines with thiophenes and furans.[a]
Conclusions
In conclusion, we have developed a mild and efficient
catalytic method for the direct olefination of thio-
phenes and furans with allylamines. The method
allows for highly regioselective and stereoselective ar-
ylation of allylamines, and a diverse range of func-
tional groups have been shown to be compatible with
the reaction conditions. Our results suggest that the
steric properties of these olefins may have important
impacts on the regiocontrol. Further investigations on
the mechanism of the reaction and synthetic applica-
tions are underway in our laboratory, and will be re-
ported in due course.
Entry
Substrate
1a
Olefin
Yield [%][b] (product)
1
2b
2b
2b
2b
2b
2b
2b
2b
2c
2c
2c
2d
2d
2e
2e
2e
2f
89 (3ab)
86 (3bb)
90 (3cb)
78 (3kb)
85 (3qb)
82 (3tb)
81 (3xb)
83 (3yb)
80 (3ac)
82 (3dc)
75 (3yc)
83 (3bd)
87 (3kd)
78 (3ae)
82 (3be)
82 (3ce)
81 (3af)
84 (3bf)
2
1b
1c
1k
1q
1t
1x
1y
1a
1d
1y
1b
1k
1a
1b
1c
1a
1b
3
4
5[c]
Experimental Section
6
7[c]
8
General Method
Unless otherwise noted, all experiments were carried out in
air. 1H NMR and 13C NMR spectra were recorded on
a Bruker Model Avance DMX 400 Spectrometer (1H
400 MHz and 13C 106 MHz, respectively). Chemical shifts
(d) are given in ppm and are referenced to residual solvent
peaks, and coupling constants (J) are reported in Hertz. The
heteroarenes, catalysts and other common materials and sol-
vents are commercially available, and were used as received
without further purification.
9
10
11
12
13
14
15
16
17
18
General Procedure for the Direct Arylation of N,N-
Diprotected Allylamines
2f
[a]
Reaction conditions: heteroarene (3.0 mmol), allylamine
(1.0 mmol), Pd(OAc)2 (5 mol%), Ag2CO3 (1.0 mmol),
Cu(OAc)2 (0.2 mmol), 5% DMF/DCE (4.0 mL), 1208C,
A
mixture of heteroarene (3.0 mmol), allylamine
G
(1.0 mmol), Pd(OAc)2 (11.2 mg, 5 mmol%), Cu(OAc)2
A
ACHTUNGTRENNUNG
G
(36.3 mg, 0.2 mmol), Ag2CO3 (275.8 mg, 1.0 mmol) in
5%DMF/DCE (4.0 mL) in a round-bottom flask was stirred
and heated at 1208C in air for 14 h. Then the flask was re-
moved from the oil bath and cooled to room temperature.
Water (20 mL) was added, and the mixture was extracted
with CH2Cl2 (3ꢂ10 mL). The combined organic layer was
14 h, in air. All reactions gave >99/1 regioselectivity and
stereoselectivity as determined by 1H NMR. Pht=phthal-
ACHTUNGTRENNUNGimidoyl, Ac=acetyl, Naph=naphthalenyl.
Isolated yield.
3-Olefinated product was obtained.
[b]
[c]
3228
asc.wiley-vch.de
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 3225 – 3230

Palladium-Catalyzed Highly Regioselective Arylation of Allylamines with Thiophenes and Furans
Scheme 1. Regioselective and stereoselective direct arylation of allylamines with fluoroarenes.
washed with brine, dried over Na2SO4, filtered, and concen-
trated under vacuum. The residue was then purified via
flash chromatography on silica gel using a mixture of ethyl
acetate and hexane (1/99 to 10/90) to give the pure product.
van, F. K. Esfahani, A. Zamani, Synthesis 2010, 1399–
1427; k) J. Le Bras, J. Muzart, Chem. Rev. 2011, 111,
1170–1214; l) L. McMurray, F. OꢀHara, M. J. Gaunt,
Chem. Soc. Rev. 2011, 40, 1885–1898; m) J. Wencel-
Delod, T. Droge, F. Liu, F. Glorius, Chem. Soc. Rev.
2011, 40, 4740–4761.
[3] a) N. P. Grimster, C. Gauntlett, C. R. A. Godfrey, M. J.
Gaunt, Angew. Chem. 2005, 117, 3185–3189; Angew.
Chem. Int. Ed. 2005, 44, 3125–3129; b) E. Capito, J. M.
Brown, A. Ricci, Chem. Commun. 2005, 1854–1856;
c) E. M. Beck, G. R. Hatley, M. J. Gaunt, J. Am. Chem.
Soc. 2006, 128, 2528–2529; d) E. M. Beck, G. R. Hatley,
M. J. Gaunt, Angew. Chem. 2008, 120, 3046–3049;
Angew. Chem. Int. Ed. 2008, 47, 3004–3007; e) A.
Garcia-Rubia, R. G. Arrayas, J. C. Carretero, Angew.
Chem. 2009, 121, 6633–6637; Angew. Chem. Int. Ed.
2009, 48, 6511–6515; f) S. R. Kandukuri, J. A. Schiffner,
M. Oestreich, Angew. Chem. 2012, 124, 1291–1295;
Angew. Chem. Int. Ed. 2012, 51, 1265–1269.
[4] a) M. Tani, S. Sakaguchi, Y. Ishii, J. Org. Chem. 2004,
69, 1221–1226; b) A. Maehara, T. Satoh, M. Miura, Tet-
rahedron 2008, 64, 5982–5986; c) J. Zhao, L. Huang, K.
Cheng, Y. Zhang, Tetrahedron Lett. 2009, 50, 2758–
2761; d) P. Li, J. Gu, Y. Ying, Y. He, H. Zhang, G.
Zhao, S. Zhu, Tetrahedron 2010, 66, 8387–8391; e) C.
Aouf, E. Thiery, J. Le Bras, J. Muzart, Org. Lett. 2009,
11, 4096–4099; f) A. Vasseur, J. Muzart, J. Le Bras,
Chem. Eur. J. 2011, 17, 12556–12560.
[5] a) S. H. Cho, S. J. Hwang, S. Chang, J. Am. Chem. Soc.
2008, 130, 9254–9256; b) J. Wu, X. Cui, L. Chen, G.
Jiang, Y. Wu, J. Am. Chem. Soc. 2009, 131, 13888–
13889; c) M. Ye, G.-L. Gao, J.-Q. Yu, J. Am. Chem.
Soc. 2011, 133, 6964–6967.
[6] a) D. Cheng, T. Gallagher, Org. Lett. 2009, 11, 2639–
2641; b) Y. Yang, K. Cheng, Y. Zhang, Org. Lett. 2009,
11, 5606–5609; c) J. Koubachi, S. Berteina-Raboin, A.
Mouaddib, G. Guillaumet, Synthesis 2009, 271–276;
d) M. Miyasaka, K. Hirano, T. Satoh, M. Miura, J. Org.
Acknowledgements
Financial support from the National Natural Science Founda-
tion of China (21072225, 21172258 and 91127039), the Fun-
damental Research Funds for the Central Universities, and
the Research funds of Renmin University of China
(11XNL011) is gratefully acknowledged.
References
[1] a) I. Moritani, Y. Fujiwara, Tetrahedron Lett. 1967,
1119–1122; b) C. Jia, W. Lu, T. Kitamura, Y. Fujiwara,
Org. Lett. 1999, 1, 2097–2100; c) C. Jia, D. Piao, J. Oya-
mada, W. Lu, T. Kitamura, Y. Fujiwara, Science 2000,
287, 1992–1995; d) C. Jia, T. Kitamura, Y. Fujiwara,
Acc. Chem. Res. 2001, 34, 633–639.
[2] a) G. Dyker, Angew. Chem. 1999, 111, 1808–1822;
Angew. Chem. Int. Ed. 1999, 38, 1698–1712; b) V. Ri-
tleng, C. Sirlin, M. Pfeffer, Chem. Rev. 2002, 102, 1731–
1770; c) F. Kakiuchi, N. Chatani, Adv. Synth. Catal.
Adv. Syn. Catal. 2003, 345, 1077–1101; d) K. Fumitoshi,
K. Takuya, Synthesis 2008, 3013–3039; e) B. Li, S. Yang,
Z. Shi, Synlett 2008, 949–957; f) X. Chen, K. M. Engle,
D. H. Wang, J. Q. Yu, Angew. Chem. 2009, 121, 5196–
5217; Angew. Chem. Int. Ed. 2009, 48, 5094–5115; g) R.
Giri, B.-F. Shi, K. M. Engle, N. Maugel, J.-Q. Yu,
Chem. Soc. Rev. 2009, 38, 3242–3272; h) T. W. Lyons,
M. S. Sanford, Chem. Rev. 2010, 110, 1147–1169; i) T.
Satoh, M. Miura, Chem. Eur. J. 2010, 16, 11212–11222;
j) B. Karimi, H. Behzadnia, D. Elhamifar, P. F. Akha-
Adv. Synth. Catal. 2012, 354, 3225 – 3230
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
3229

Zhen Jiang et al.
FULL PAPERS
Chem. 2010, 75, 5421–5424; e) H. Jiang, Z. Feng, A.
Wang, X. Liu, Z. Chen, Eur. J. Org. Chem. 2010, 1227–
1230; f) S. Cui, L. Wojtas, J. C. Antilla, Org. Lett. 2011,
13, 5040–5043.
kahara, N. Germain, T. Ohshima, K. Mashima, Angew.
Chem. 2012, 124, 154–158; Angew. Chem. Int. Ed. 2012,
51, 150–154; l) T. Xiong, Y. Li, L. Miao, Q. Zhang, Q.
Zhang, Chem. Commun. 2012, 48, 2246–2248; m) P.
Mukherjee, R. A. Widenhoefer, Angew. Chem. 2012,
124, 1434–1436; Angew. Chem. Int. Ed. 2012, 51, 1405–
1407.
[7] a) D. Pan, M. Yu, W. Chen, N. Jiao, Chem. Asian J.
2010, 5, 1090–1093; b) D. Pan, N. Jiao, Synlett 2010,
1577–1588; c) X. Shang, Y. Xiong, Y. Zhang, L. Zhang,
Z. Liu, Synlett 2012, 259–262; d) Z. Li, Y. Zhang, Z.
Liu, Org. Lett. 2012, 14, 74–77; e) Y. Zhang, Z. Li, Z.
Liu, Org. Lett. 2012, 14, 226–229.
[8] a) R. B. Cheikh, R. Chaabouni, A. Laurent, P. Mison,
A. Nafti, Synthesis 1983, 685–700; b) B. M. Trost, D. L.
Van Vranken, Chem. Rev. 1996, 96, 395–422; c) D. Ba-
savaiah, A. J. Rao, T. Satyanarayana, Chem. Rev. 2003,
103, 811–892; d) Z. Lu, S. Ma, Angew. Chem. 2008, 120,
264–303; Angew. Chem. Int. Ed. 2008, 47, 258–297;
e) B. M. Trost, T. Zhang, J. D. Sieber, Chem. Sci. 2010,
1, 427–440.
[9] For some recent examples, see: a) X. Sun, L. Zhou, W.
Li, X. Zhang, J. Org. Chem. 2008, 73, 1143–1146; b) T.
Jiang, J. Li, Chem. Commun. 2009, 7236–7238; c) B.
Weiner, A. Baeza, T. Jerphagnon, B. L. Feringa, J. Am.
Chem. Soc. 2009, 131, 9473–9474; d) G. C. Tsui, F.
Menard, M. Lautens, Org. Lett. 2010, 12, 2456–2459;
e) A. D. Worthy, C. L. Joe, T. E. Lightburn, K. L. Tan,
J. Am. Chem. Soc. 2010, 132, 14757–14759; f) X. Zhao,
D. Liu, H. Guo, Y. Liu, W. Zhang, J. Am. Chem. Soc.
2011, 133, 19354–19357; g) H. Wang, Y. Wang, D.
Liang, L. Liu, J. Zhang, Q. Zhu, Angew. Chem. 2011,
123, 5796–5799; Angew. Chem. Int. Ed. 2011, 50, 5678–
5681; h) R. J. DeLuca, M. S. Sigman, J. Am. Chem. Soc.
2011, 133, 11454–11457; i) M.-B. Li, Y. Wang, S.-K.
Tian, Angew. Chem. 2012, 124, 3022–3025; Angew.
Chem. Int. Ed. 2012, 51, 2968–2971.
[10] For some recent examples, see: a) V. Pace, F. Martinez,
M. Fernandez, J. V. Sinisterra, A. R. Alcantara, Org.
Lett. 2007, 9, 2661–2664; b) M. Utsunomiya, Y. Miya-
moto, J. Ipposhi, T. Ohshima, K. Mashima, Org. Lett.
2007, 9, 3371–3374; c) D. F. Fischer, Z. Xin, R. Peters,
Angew. Chem. 2007, 119, 7848–7851; Angew. Chem. Int.
Ed. 2007, 46, 7704–7707; d) R. E. Kinder, Z. Zhang, R.
Widenhoefer, Org. Lett. 2008, 10, 3157–3159; e) G. Liu,
G. Yin, L. Wu, Angew. Chem. 2008, 120, 4811–4814;
Angew. Chem. Int. Ed. 2008, 47, 4733–4736; f) T. Nishi-
kata, B. H. Lipshutz, Chem. Commun. 2009, 6472–6474;
g) T. Nagano, S. Kobayashi, J. Am. Chem. Soc. 2009,
131, 4200–4201; h) H. Hikawa, Y. Yokoyama, J. Org.
Chem. 2011, 76, 8433–8439; i) R. Ghosh, A. Sarkar, J.
Org. Chem. 2011, 76, 8508–8512; j) K. Ye, H. He, W.
Liu, L. Dai, G. Helmchen, S. You, J. Am. Chem. Soc.
2011, 133, 19006–19014; k) K. Das, R. Shibuya, Y. Na-
[11] For Pd-catalyzed Heck b-arylation of allylamines, see:
a) K. Olofsson, M. Larhed, A. Hallberg, J. Org. Chem.
2000, 65, 7235–7239; b) K. Olofsson, H. Sahlin, M.
Larhed, A. Hallberg, J. Org. Chem. 2001, 66, 544–549;
c) J. Wu, J. F. Marcous, I. W. Davis, P. J. Reider, Tetra-
hedron Lett. 2001, 42, 159–162; d) C. A. Baxter, E.
Cleator, M. Alam, A. J. Davies, A. Goodyear, M.
OꢀHagan, Org. Lett. 2010, 12, 668–671.
[12] For Pd-catalyzed Heck g-arylation of allylamines, see:
a) P. Y. Johnson, J. Q. Wen, J. Org. Chem. 1981, 46,
2767–2771; b) C. A. Busacca, Y. Dong, Tetrahedron
Lett. 1996, 37, 3947–3950; c) D. Alvisi, E. Blart, B. F.
Bonini, G. Mazzanti, A. Ricci, P. Zani, J. Org. Chem.
1996, 61, 7139–7146; d) Y. Dong, C. A. Busacca, J. Org.
Chem. 1997, 62, 6464–6465; e) H. B. Ripin, .D. E. Bour-
assa, T. Brandt, M. J. Castaldi, H. N. Frost, J. Hawkins,
P. J. Johnson, S. S. Massett, K. Neumann, J. Phillips,
J. W. Raggon, P. R. Rose, J. L. Rutherford, B. Sitter,
A. M. Stewart, M. G. Vetelino, L. Wei, Org. Process
Res. Dev. 2005, 9, 440–450; f) N. Galaffu, S. P. Man,
R. D. Wilkes, J. R. H. Wilson, Org. Process Res. Dev.
2007, 11, 406–413; g) A. Dhami, M. F. Mahon, M. D.
Lloyd, M. D. Threadgill, Tetrahedron 2009, 65, 4751–
4765; h) M. V. Reddington, D. C. Bryant, Tetrahedron
Lett. 2011, 52, 181–183; i) E. W. Werner, M. S. Sigman,
J. Am. Chem. Soc. 2011, 133, 9692–9695; j) S. Cacchi,
G. Fabrizi, A. Goggiamani, A. Sferrazza, Org. Biomol.
Chem. 2011, 9, 1727–1730; k) P. Prediger, L. F. Barbosa,
Y. Genisson, C. R. D. Correia, J. Org. Chem. 2011, 76,
7737–7749.
[13] a) M. Liu, Z. Hyder, Y. Sun, W. Tang, L. Xu, J. Xiao,
Org. Biomol. Chem. 2010, 8, 2012–2015; b) J. Ruan,
J. A. Iggo, N. G. Berry, J. Xiao, J. Am. Chem. Soc. 2010,
132, 16689–16699; c) Y. Deng, Z. Jiang, M. Yao, D. Xu,
L. Zhang, H. Li, W. Tang, L. Xu, Adv. Synth. Catal.
2012, 354, 899–907.
[14] P. Nilsson, M. Larhed, A. Hallberg, J. Am. Chem. Soc.
2001, 123, 8217–8225.
[15] a) T. Llamas, R. G. Arrayas, J. C. Carretero, Adv.
Synth. Catal. 2004, 346, 1651–1654; b) D. Pan, A. Chen,
Y. Su, W. Zhou, S. Li, W. Jia, J. Xiao, Q. Liu, L. Zhang,
N. Jiao, Angew. Chem. 2008, 120, 4807–4810; Angew.
Chem. Int. Ed. 2008, 47, 4729–4732; c) Y. Sun, N. Jiao,
Org. Lett. 2009, 11, 2980–2983.
3230
asc.wiley-vch.de
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 3225 – 3230