Palladium-catalyzed highly regioselective and stereoselective decarboxylative arylation of unactivated olefins with aryl carboxylic acids

Article abstract of DOI:10.1016/j.tet.2017.03.007

Palladium(II)-catalyzed highly regioselective and stereoselective decarboxylative arylation of unactivated olefins with aryl carboxylic acids has been developed. This method is applicable to a variety of unactivated olefins, including allylamides, long ch

Full text of DOI:10.1016/j.tet.2017.03.007

Accepted Manuscript
Palladium-catalyzed highly regioselective and stereoselective decarboxylative
arylation of unactivated olefins with aryl carboxylic acids
Xubo Qin, Changjun Chen, Lingjuan Zhang, Jianbin Xu, Yixiao Pan, Haoqiang Zhao,
Jiahong Han, Huanrong Li, Lijin Xu
PII:
S0040-4020(17)30232-6
10.1016/j.tet.2017.03.007
TET 28513
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 30 December 2016
Revised Date: 1 March 2017
Accepted Date: 3 March 2017
Please cite this article as: Qin X, Chen C, Zhang L, Xu J, Pan Y, Zhao H, Han J, Li H, Xu L, Palladium-
catalyzed highly regioselective and stereoselective decarboxylative arylation of unactivated olefins with
aryl carboxylic acids, Tetrahedron (2017), doi: 10.1016/j.tet.2017.03.007.
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Graphical Abstract:
Palladium-catalyzed Highly Regioselective and Stereoselective Decarboxylative
Arylation of Unactivated Olefins with Aryl Carboxylic Acids
Xubo Qin, Changjun Chen, Lingjuan Zhang, Jianbin Xu, Yixiao Pan, Haoqiang Zhao,
Jiahong Han, Huanrong Li, Lijin Xu,*
Department of chemistry, Renmin University of China, Beijing 100872, China.

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Palladium-catalyzed Highly Regioselective
and Stereoselective Decarboxylative
Arylation of Unactivated Olefins with Aryl
Carboxylic Acids
Leave this area blank for abstract info.
Xubo Qin, Changjun Chen, Lingjuan Zhang, Jianbin Xu, Yixiao Pan, Haoqiang Zhao, Jiahong Han, Huanrong
Li, Lijin Xu,*
Department of chemistry, Renmin University of China, Beijing 100872, China.

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Palladium-catalyzed Highly Regioselective and Stereoselective Decarboxylative
Arylation of Unactivated Olefins with Aryl Carboxylic Acids
Xubo Qin, Changjun Chen, Lingjuan Zhang, Jianbin Xu, Yixiao Pan, Haoqiang Zhao, Jiahong Han,
Huanrong Li, Lijin Xu
Department of Chemistry, Renmin University of China, Beijing 100872, China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Palladium(II)-catalyzed highly regioselective and stereoselective decarboxylative arylation of
unactivated olefins with aryl carboxylic acids has been developed. This method is applicable to
a variety of unactivated olefins, including allylamides, long chain functionalized olefins and
purely aliphatic olefins, leads to the formation of linear E-configured products in high yields.
Both electron-rich and electron-deficient aryl carboxylic acids are suitable arylation reagents. It
was found that the choice of solvent, catalyst precursor and oxidant had an important influence
on reaction efficiency. As a co-solvent and ligand, DMSO is critical to catalysis. This
chemistry expands the scope of decarboxylative arylation of olefins with aryl carboxylic acids,
and provides a rapid access to useful linear arylation products of unactivated olefins.
Available online
Keywords:
decarboxylative
aryl carboxylic acid
arylation
palladium
unactivated olefin
2016 Elsevier Ltd. All rights reserved
.
1. Introduction
work well for the decarboxylative Heck coupling of
arenecarboxylic acids with a variety of olefins, but in the
arylation of electronically nonbiased olefins room for
improvement in terms of reaction conditions, substrate scope,
selectivity and catalyst loading still exists.9 Recently, Jiang and
co-workers realized the Pd(TFA)2-catalyzed highly regioselective
decarboxylative coupling reaction of aryl carboxylic acids with
electron-rich allylic alcohols to exclusively produce the β-aryl
ketones and aldehydes in high yields without detecting the
formation of β-arylated allylic alcohol products.10 More recently,
the group of Jana reported two palladium(II) catalytic systems
that could catalyze decarboxylative Heck reaction of electron-
rich and electron-deficient aryl carboxylic acids with olefins at
room temperature, respectively, but the arylation of non-activated
olefins is plagued with a higher catalyst loading (20 mol%
Pd(TFA)2) and limited substrate scope.11 Obviously, developing a
general and efficient catalytic procedure for selective arylation of
unactivated olefins with aryl carboxylic acids remains
challenging. In continuing our investigation of selective arylation
of unactivated olefins,12 we became interested in studying the
decarboxylative coupling reaction of unactivated olefins with
aryl carboxylic acids. Herein we report that the combination of
Pd(TFA)2 and Ag2CO3 in 5% DMSO-THF could constitute an
efficient catalytic system for highly selective arylation of various
unactivated olefins with both eletcron-rich and electron-deficient
Palladium-catalyzed Heck reaction of aryl halides with olefins
has been regarded as one of the most powerful and reliable
methods for the formation of carbon-carbon bonds in organic
synthesis.1,2 Although a number of effective palladium catalytic
systems demonstrating high reactivities and selectivities have
been developed over the past several decades, a major limitation
of this chemistry is its strong reliance on the use of halogenated
substrates. In recent years, the transition-metal catalyzed
decarboxylative cross-coupling reaction has been subjected to
extensive investigation in the construction of various C-C and C-
X bonds because the readily available, stable and structural
diverse carboxylates are employed as the sources of carbon
nucleophiles to replace the traditional halides and organometal
reagents.3 In this context, the use of inexpensive, stable and
easily accessible aryl carboxylic acids as arylating reagents has
attracted increasing research attention.4-7 In 2002, Myers and co-
workers first reported the decarboxylative coupling reaction of
arylcarboxylic acids with α,β-unsaturated carbonyls and styrene
in 5% DMSO-DMF with Pd(TFA)2 as the catalyst and Ag2CO3 as
the oxidant, and aryl carboxylic acids have proved to be reliable
arylating reagents in these reactions.8a,b The subsequent
mechanistic studies indicated DMSO functions as both solvent
and a ligand.8c Following this significant lead, Su and co-workers
developed several palladium catalytic systems that could
———
Corresponding author. Tel.: +86-10-6251-1528; fax: +86-10-6251-6664; e-mail: 20050062@ruc.edu.cn (L. Xu).

2
Tetrahedron
ACCEPTED MANUSCRIPT
12
p-xylene/DMSO(20/1)
70
46
33
28
19
32
22
12
24
63
32
6
aryl carboxylic acids, and a number of functional groups on
Pd(TFA)
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
2
both coupling partners were compatible with the reaction
conditions.
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27c
28d
29e
DMF/DMSO(20/1)
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(OAc)2
PdCl2
THF/DMSO(10/1)
2. Results and discussion
THF/DMSO(30/1)
THF/DMSO(20/1)
At the onset of our investigations, the olefination of 2,6-
dimethoxybenzoic acid (1a) with N,N-(Boc)2 allylamine 2a was
chosen as the model reaction to screen the optimal reaction
conditions (Table 1). With Pd(TFA)2 as the catalyst and Ag2CO3
as the oxidant, the effect of different solvents was firstly
examined. A solvent screening revealed that DMSO gave the
desired product, terminal arylated (E)-allylamide 3aa, in 19%
yield with a small amount of the decarboxylative protonation
product (4%) (Table 1, entry 7), but only the decarboxylative
protonation reaction was observed in other solvents, such as
toluene, 1, 4-dioxane, p-xylene, THF, CH3CN and DMF (Table 1,
entries 1-6).13 With an aim to improve the reaction efficiency, the
performance of the mixed solvent systems was then evaluated
(Table 1, entries 8-13). It was found that a 20:1 mixture of
THF/DMSO was the most effective reaction medium, producing
3aa in 90% yield without the protodecarboxylation being
detected (Table 1, entry 10). Notably, although a mixture of
toluene/DMSO (20:1) worked well for the arylation of allylic
alcohols with aryl carboxylic acids,10 it only provided 3aa in a
moderate yield (Table 1, entry 8). Varying the amount of DMSO
resulted in significantly decreased reactivity (Table 1, entries 14
and 15), suggesting that a specified volume of DMSO is critical
for catalysis in this catalytic system.8,10,14 It is believed that
DMSO acts both cosolvent and ligand in this transformation.
With THF/DMSO (20/1) as the reaction medium, further
optimization showed that employing other palladium precursors
diminished the reaction efficiency (Table 1, entries 16-20).
Replacing Ag2CO3 with other oxidants led to a remarkable drop
in yield (Table 1, entries 21-26). Although Su’s catalytic systems
could work well in the coupling reaction of arenecarboxylic acids
with alkyl-substituted olefins,9 they failed to catalyze the reaction
of 1a and 2a (Table 1, entries 27 and 28). Moreover, the catalytic
system consisting of Pd(TFA)2 and BQ with DMF/DMSO (20:1)
as the solvent, reported to be capable of catalyzing the arylation
of unactivated olefins with aryl carboxylic acids at room
temperature,11 proved to be completely ineffective in our case
(Table 1, entry 29). It should be stressed that in all cases no
observation of internal arylation or partial deprotection was made.
THF/DMSO(20/1)
Pd(PPh3)2Cl2
Pd(PPh3)4
Pd2(dba)3
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(OAc)2
Pd(TFA)2
THF/DMSO(20/1)
THF/DMSO(20/1)
THF/DMSO(20/1)
THF/DMSO(20/1)
THF/DMSO(20/1)
THF/DMSO(20/1)
THF/DMSO(20/1)
THF/DMSO(20/1)
THF/DMSO(20/1)
DMSO/DMF/dioxane
DMF/DMSO(20/1)
DMF/DMSO(20/1)
Ag2CO3
AgOAc
Ag2O
Ag2SO4
Cu(OAc)2
BQ
28
NR
NR
NR
NR
NR
O2(1 atm)
BQ
O2(1 atm)
BQ
a
Reaction conditions: 1a (0.2 mmol.), 2a (0.24 mmol), catalyst (5.0 mol%),
base (1.0 mmol), solvent (2.1 ml), 85 °C, 8 h. E/Z ratio of 3aa is >99/1 as
determined by H NMR. When the Z-isomer could not be detected, a value
of >99/1 was assigned. ND: not detected. NR: no reaction.
1
b Isolated yield.
c 1a (0.2 mmol.), 2a (0.4 mmol), Pd(TFA)2 (10.0 mol%), BQ (0.24 mmol), 1-
AdCO2H (0.8 mmol) and DMSO/DMF/dioxane (2.1 mL, 1:15:5), 120 °C, 1 h.
d1a (0.2 mmol.), 2a (0.4 mmol), Pd(OAc)2 (10.0 mol%), O2 (1.0 atm),
DMSO/DMF (2.1 mL, 1:20), 120 °C, 10 h.
e 1a (0.2 mmol.), 2a (0.4 mmol), Pd(TFA)2 (20.0 mol%), BQ (0.4 mmol),
DMSO/DMF (3.15 mL, 1:20), 25 °C, 36 h.
With the optimal reaction conditions in hand, we then
investigated the generality of this coupling reaction of 1a with a
range of unactivated olefins. As shown in Table 2, 1a reacted
smoothly with N,N-disubstituted allylamides (2b-2e) to
exclusively afford the corresponding γ-arylated (E)-allylamides
(3ab-3ae) in good to excellent yields without the formation of
internal regioisomer or cis-isomer, but the presence of α-
substituents in allylamide substrates (2c,2d) slightly impacted the
reaction efficiency (3ac,3ad). The N-substituted allyamide 2f
was also reactive, exclusively delivering the corresponding
product 3af in 88% yield. Interestingly, the long chain olefins, 2-
(but-3-en-1-yl)isoindoline-1,3-dione (2g) and 2-(pent-4-en-1-
yl)isoindoline-1,3-dione (2h), also successfully engaged in this
transformation to produce the products 3ag and 3ah in 70% and
65% yields, respectively, and the migration of the C=C double
bond along the aliphatic chain and the internal arylation were not
observed. The coupling reaction of 1a with other functionalized
olefins (2i–2l) was also studied. It was found that the olefins 2i,
2j and 2l underwent highly regioselective arylation, exclusively
affording the arylated products (3ai, 3aj, 3al) in 65-85% yields.
The reaction of 2k also proceeded smoothly to give the linear
arylated product 3ak as the major products with the Z-isomer and
the internal arylated olefin as minor products, but no formation of
allylic isomers was detected. Allylbenzene (2m) and 1-allyl-4-
methoxybenzene (2n) displayed excellent reactivity, and the
products (3am, 3an) were obtained in excellent yields.
Vinylcyclohexane (2o) turned out to be a good coupling partner,
giving rise to the product 3ap in 93% yield. Hex-1-ene (2p)
could also be applied in this transformation, but a mixture of
styrenyl product and allylic product was produced.
Table 1
Optimization of reaction conditions. a
3aa(%)b
ND
ND
ND
ND
ND
ND
19
Entry
[Pd]
Solvent
toluene
dioxane
THF
Oxidant
Ag2CO3
1
2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
3
4
CH3CN
5
p-xylene
6
DMF
7
DMSO
8
65
toluene/DMSO(20/1)
dioxane/DMSO(20/1)
THF/DMSO(20/1)
CH3CN/DMSO(20/1)
9
40
10
11
90
30

3
1
Table 2
yields. E/Z ratios of the products were determined by H NMR. When the
ACCEPTED MANUSCRIPT
Pd-catalyzed olefination of 1a with various unactivated olefins.a
Z-isomer could not be detected, a value of >99/1 was assigned.
The reaction is not limited to aryl carboxylic acids only;
heteroaryl carboxylic acids participated equally well. As can be
seen from Table 3, 3-methylthiophene-2-carboxylic acid (1g) and
3,4,5-trichlorothiophene-2-carboxylic acid (1h) displayed good
reactivity to furnish the corresponding products (3ga, 3gb, 3ha,
3hb) in high yields. Notably, in the case of 1g, no C5-olefination
was observed. Furthermore, 3-methylbenzo[b]thiophene-2-
carboxylic acid (3i) and 3-methylbenzofuran-2-carboxylic acid
(3j) were also reactive, affording the products (3ia, 3ib, 3ja) in
moderate yields. However, under the current conditions, benzoic
acid, 2-methoxybenzoic acid and pyridine-2-carboxylic acid
completely failed to undergo olefination.
a
Reaction conditions: 1a (0.2 mmol), 2 (0.24 mmol), Pd(TFA)2 (5.0 mol%),
Ag2CO3 (0.2 mmol), THF/DMSO (2.1 ml, 20:1), 100 °C, 8 h. Isolated yields.
1
E/Z ratios of the products were determined by H NMR. When the Z-isomer
could not be detected, a value of >99/1 was assigned.
b Reaction time 12 h.
Scheme 1. The coupling reaction of fluorinated aryl carboxylic acids 1 with
unactivated olefins 2.
The oxidative cross-coupling reaction was further extended to
other aryl carboxylic acids as shown in Table 3. The electron-rich
aryl carboxylic acid 1b proved to be an efficient coupling partner,
providing the corresponding (E)-arylated allylamide products
(3ba, 3bb, 3bc, 3bi, 3bm, 3bn) in good to excellent yields.
Likewise, good results were also achieved in the olefination of
electron-rich aryl carboxylic acids 1e and 1f (3ea, 3eb, 3ec, 3fa).
Importantly, the halogenated aryl carboxylic acids 1c and 1d
could be well applied in this transformation to give the products
(3ca, 3da, 3dc, 3di) in 76-89% yields, and C-X (X = Cl, Br)
bonds remained intact in this process, thereby offering an
opportunity for further elaboration.
To further demonstrate the potential of our catalytic system,
the olefination of electron-deficient fluorinated aryl carboxylic
acids was then examined (Scheme 1). It was found that the
coupling reaction of 3k-3m with 1a proceeded smoothly under
the optimized reaction conditions, affording the desired products
(3ka-3ma) in good yields. It is worth mentioning that the more
electron-deficient 2,3,4,5,6-pentafluorobenzoic acid (1n) was
also compatible in this transformation, and the products 3na and
3nb were isolated in good yields.
Table 3
Pd-catalyzed coupling reaction of arylcarboxylic acids 1 with unactivated
olefins 2.a
Scheme 2. Intermolecular competition experiments.
To gain insight into the mechanism of this oxidative
olefination, the following control experiments were carried out as
shown in Scheme 2. The competition reaction between 1a and 1n
with 2a under the standard reaction conditions revealed 3aa to be
the sole product, indicating that the more electron-rich substrate
was transformed preferentially (Scheme 2a). When an equimolar
mixture of 2b and 2g underwent coupling reaction with 1a, the
desired products 3ab and 3ag were formed in 66% and 22%
yields, respectively (Scheme 2b). The higher reactivity observed
in the reactions of allylamide 2b might be attributed to the
a Reaction conditions: 1 (0.2 mmol), 2 (0.24 mmol), Pd(TFA)2 (5.0 mol%),
Ag2CO3 (0.2 mmol), THF/DMSO (2.1 ml, 20:1), 100 °C, 8 h. Isolated

4
Tetrahedron
ACCEPTED MANUSCRIPT
preference for chelation between the carbonyl O atom and the
To an oven-dried pressure tube were sequentially added aryl
Pd atom. A similar chelation effect has also been reported in the
carboxylic acid 1 (0.2 mmol), olefin 2 (0.24 mmol), Pd(TFA)2
(3.33 mg, 5.0 mol%), Ag2CO3 (55.2 mg, 0.2 mmol), THF (2.0
mL) and DMSO (0.10 mL) under nitrogen at room temperature.
After degassing three times, the reaction mixture was heated at
100 °C for 8 h, and then was cooled to room temperature. Water
(20.0 mL) was added, and the mixture was extracted with ethyl
acetate (3 × 5.0 mL). The combined organic layer was washed
with brine, dried over anhydrious Na2SO4, filtered and
concentrated under reduced pressure. The residue was purified by
silica gel column chromatography (eluant: hexane/ethyl acetate)
to give the pure target product
arylation of allyl derivatives.15
Based on our experimental results and previous reports,8-11
a
plausible mechanism is proposed in Scheme 3. First, coordination
of the aryl carboxylic acid 1 to the palladium (II) complex led to
the formation of intermediate A. The subsequent decarboxylation
yielded intermediate B, which underwent migratory insertion of
the olefin 2 to give intermediate C. The following β-H
elimination furnished the desired product 3. Finally oxidation of
the Pd(0) species to the Pd(II) complex by the silver salt
completed the catalytic cycle.
4.2.1
(E)-N,N-bis(tert-butoxycarbonyl)-3-(2,6-
dimethoxyphenyl)prop-2-en-1-amine (3aa). White solid, mp: 70-
71 °C; 1H NMR (400 MHz, CDCl3) δ 1.53 (s, 18H ), 3.82 (s, 6H ),
4.33 (dd, J = 1.0, 6.5 Hz, 2H), 6.54 (d, J = 8.4 Hz, 2H), 6.61 (dt,
J = 6.5, 16.1 Hz, 1 H), 6.85 (d, J = 16.2 Hz, 1H), 7.14 (t, J = 8.4
Hz, 1H); 13C NMR (100.6 MHz, CDCl3) δ 28.0, 49.9, 55.6, 82.0,
103.9, 114.1, 123.1, 128.0, 128.8, 152.3, 158.5; HRMS (ESI)
calcd. for C21H31NNaO6 [M+Na]+: 416.2044, found: 416.2033.
4.2.2 (E)-2-(3-(2,6-dimethoxyphenyl)allyl)isoindoline-1,3-dione
(3ab). Yellow solid, mp: 115-116 °C; 1H NMR (400 MHz,
CDCl3) δ 3.83 (s, 6H), 4.47 (dd, J = 1.0, 6.7 Hz, 2H), 6.53 (d, J =
8.4 Hz, 2H), 6.72 (dt, J = 6.7, 16.1 Hz, 1H), 7.06 (d, J = 16.1 Hz,
1H), 7.14 (t, J = 8.3 Hz, 1H), 7.71 (dd, J = 3.0, 5.4 Hz, 2H), 7.86
(dd, J = 3.1, 4.6 Hz, 2H); 13C NMR (100.6MHz, CDCl3) δ 41.7,
55.7, 103.8, 113.5, 123.2, 124.6, 126.4, 128.4, 132.4, 133.8,
158.6, 168.1; HRMS (ESI) calcd. for C19H17NNaO4 [M+Na]+:
346.1050, found: 346.1029.
Scheme 3. Proposed reaction mechanism.
3. Conclusions
In conclusion, we have developed a general and efficient
decarboxylative coupling reaction of aryl carboxylic acids with
unactivated olefins under Pd(II) catalysis. This method allows for
highly regioselective and stereoselective arylation of a diverse of
unactivated olefins with differently substituted aryl carboxylic
acids to essentially furnish the linear products in good to
excellent yields with good functional group tolerance. This
methodology offers a valuable complement to the existing
decarboxylative olefination of arene carboxylic acids. Further
studies to expand the substrate scope and synthetic application of
this catalytic process are currently underway in this lab, and will
be reported in due course.
4.2.3 (E)-2-(4-(2,6-dimethoxyphenyl)but-3-en-2-yl)isoindoline-
1,3-dione (3ac). Yellow solid, mp: 91-92 °C; 1H NMR (400
MHz, CDCl3) δ 1.68 (d, J = 7.0 Hz, 3H), 3.84 (s, 6H), 5.05-5.13
(m, 1H), 6.53 (d, J = 8.4 Hz, 2H), 6.97 (d, J = 16.2 Hz, 1H),
7.10-7.16 (m, 2H), 7.68 (dd, J = 3.1, 5.4 Hz, 2H), 7.82 (dd, J =
3.0, 5.4 Hz, 2H); 13C NMR (100.6 MHz, CDCl3) δ 19.4, 51.0,
55.7, 103.9, 113.6, 122.6, 123.0, 128.3, 131.8, 132.3, 133.7,
158.6, 168.0; HRMS (ESI) calcd. for C20H19NNaO4 [M+Na]+:
360.1206, found: 360.1195.
4.2.4 (E)-2-(1-(2,6-dimethoxyphenyl)pent-1-en-3-yl)isoindoline-
1,3-dione (3ad). White solid, mp: 69-70 °C; 1H NMR (400 MHz,
CDCl3) δ 0.96 (t, J = 7.4 Hz, 3H), 2.02-2.09 (m, 1H), 2.11-2.20
(m, 1H), 3.85 (s, 6H), 4.76-4.82 (m, 1H), 6.54 (d, J = 8.4 Hz, 2H),
6.96 (d, J = 16.2 Hz, 1H), 7.08-7.16 (m, 2H), 7.69 (dd, J = 3.0,
5.4 Hz, 2H), 7.83 (dd, J = 3.1, 5.4 Hz, 2H); 13C NMR (100.6
MHz, CDCl3) δ 11.2, 26.1, 55.7, 57.7, 103.9, 113.7, 123.0, 123.6,
128.3, 130.8, 132.2, 133.7, 158.6, 168.3; HRMS (ESI) calcd. for
C21H21NNaO4 [M+Na]+: 374.1363, found: 374.1351.
4. Experimental section
4.1. General
All experiments were carried out under an atmosphere of
1
nitrogen. H NMR and 13C NMR spectra were recorded on a
Bruker Model Avance DMX 400 Spectrometer (1H 400 MHz and
13C 100.6 MHz, respectively). Chemical shifts (δ) are given in
ppm and are referenced to residual solvent peaks. 3-Chloro-2,6-
dimethoxybenzoic acid (1c),16 3-bromo-2,6-dimethoxybenzoic
acid (1d),16 N,N-(Boc)2-allylamine (2a),17a 2-allylisoindoline-1,3-
dione (2b),17b 2-(but-3-en-2-yl)isoindoline-1,3-dione (2c),17c 2-
4.2.5
(E)-tert-butyl
(3-(2,6-
dimethoxyphenyl)allyl)(methyl)carbamate (3ae). Colorless oil; 1H
NMR (400 MHz, CDCl3) δ 1.48 (s, 9H), 2.87 (s, 3H), 3.83 (s,
6H), 3.98 (d, J = 8.5 Hz, 2H), 6.50 (m, 1H), 6.55 (d, J = 8.4 Hz,
2H), 6.75 (d, J = 16.1 Hz, 1H), 7.14 (t, J = 8.4 Hz, 1H); 13C NMR
(100.6 MHz, CDCl3) δ 28.5, 43.2, 55.3, 55.7, 79.3, 106.2, 114.1,
128.0, 129.2, 129.9, 155.9, 158.4; HRMS (ESI) calcd. for
C17H25NNaO4 [M+Na]+: 330.1676, found: 330.1673.
(pent-1-en-3-yl)isoindoline-1,3-dione
(2d),17d
(2g)17f,
tert-butyl
allyl(methyl)carbamate (2e),17e N-Boc-allylamine (2f),17e 2-(but-
3-en-1-yl)isoindoline-1,3-dione
yl)isoindoline-1,3-dione
(2h)17g
2-(pent-4-en-1-
2-(but-3-en-1-
,
diethyl
yl)malonate (2i)17h and methyl 2-methylpent-4-enoate (2j)17i were
prepared according to the previous reports. All other chemicals
were used as received from Aldrich or Acros without further
purification.
4.2.6 (E)-tert-butyl (3-(2,6-dimethoxyphenyl)allyl)carbamate
(3af). Colorless oil; 1H NMR (400 MHz, CDCl3) δ 1.46 (s , 9H),
3.83 (s, 6H), 3.91 (d, J = 7.3 Hz, 2H), 4.64 (s, 1H), 6.54 (d, J =
8.3 Hz, 2H), 6.60 (m, 1H), 6.77 (d, J = 16.2 Hz, 1H), 7.14 (t, J =
8.4 Hz, 1H); 13C NMR (100.6 MHz, CDCl3) δ 28.4, 44.4, 55.7,
103.7, 103.9, 113.9, 122.1, 128.1, 130.1, 158.4; HRMS (ESI)
calcd. for C16H23NNaO4 [M+Na]+: 316.1519, found: 316.1515.
4.2. General procedure for the decarboxylative arylation
of olefins with aryl carboxylic acids

5
4.2.7(E)-2-(4-(2,6-dimethoxyphenyl)but-3-en-1-yl)isoindoline-
1,3-dione (3ag). White solid, mp: 58-59 °C; 1H NMR (400 MHz,
CDCl3) δ 2.62-2.68 (m, 2H), 3.78 (s, 6H), 3.86 (t, J = 7.2 Hz, 2H),
6.51 (d, J = 8.3 Hz, 3H), 6.67 (d, J = 16.1 Hz, 1H), 7.10 (t, J =
6.8 Hz, 1H), 7.70 (dd, J = 3.0, 5.4 Hz, 2H), 7.84 (dd, J = 3.0, 5.4
Hz, 2H); 13C NMR (100.6 MHz, CDCl3) δ 33.7, 37.9, 55.6, 103.8,
114.5, 123.1, 127.6, 130.3, 132.2, 133.7, 133.8, 158.2, 168.3;
HRMS (ESI) calcd. for C20H19NNaO4 [M+Na]+: 360.1206, found:
360.1215.
4.2.14 (E)-1,3-dimethoxy-2-(3-(4-methoxyphenyl)prop-1-en-
1
ACCEPTED MANUSCRIPT
1-yl)benzene (3an). Colorless oil; H NMR (400 MHz, CDCl3) δ
3.54 (dd, J = 1.1, 6.4 Hz, 2H), 3.78 (s, 3H), 3.83 (s, 6H), 6.19 (m,
1H), 6.33 (d, J = 15.9 Hz, 1H), 6.57 (d, J = 6.8 Hz, 2H), 6.79 (d,
J = 8.7 Hz, 2H), 7.21 (m, 2H), 7.16 (m, 1H); 13C NMR (100.6
MHz, CDCl3) δ 26.4, 55.3, 55.9, 103.9, 113.7, 116.8, 126.8,
127.1, 128.8, 129.6, 131.0, 158.3, 158.5; HRMS (ESI) calcd. for
C18H20NaO3 [M+Na]+: 307.1305, found: 307.1293.
4.2.15 (E)-2-(2-cyclohexylvinyl)-1,3-dimethoxybenzene (3ao).
Yellow oil; H NMR (400 MHz, CDCl3) δ 1.29 (m , 6H), 1.70
1
4.2.8 (E)-2-(5-(2,6-dimethoxyphenyl)pent-4-en-1-yl)isoindoline-
1
1,3-dione (3ah). Colorless oil; H NMR (400 MHz, CDCl3) δ
(m, 4H), 2.16 (m, 1H), 3.85 (s, 6H), 6.56 (d, J = 8.4 Hz, 2H),
6.61 (m, 1H), 6.67 (d, J = 16.4 Hz, 1H), 7.12 (t, J = 8.3 Hz, 1H);
13C NMR (100.6 MHz, CDCl3) δ 26.2, 26.3, 33.3, 43.0, 55.8,
104.1, 117.6, 127.1, 141.3, 158.2; HRMS (ESI) calcd. for
C16H23O2 [M+H]+: 247.1693, found: 247.1689.
1.88-1.94 (m, 2H), 2.31-2.36 (m, 2H), 3.76-3.77 (m, 2H), 3.84 (s,
6H), 6.52-6.60 (m, 3H), 6.67 (d, J = 16.2 Hz, 1H), 7.10 (t, J = 8.3
Hz, 1H), 7.69 (dd, J = 3.0, 5.4 Hz, 2H), 7.83 (dd, J = 3.0, 5.4 Hz,
2H); 13C NMR (100.6 MHz, CDCl3) δ 28.4, 32.2, 37.9, 55.7,
103.7, 103.9, 114.8, 120.8, 123.1, 127.3, 132.2, 133.8, 158.1,
168.4; HRMS (ESI) calcd. for C21H21NNaO4 [M+Na]+: 374.1363,
found: 374.1339.
4.2.16 (E)-2-(hex-1-en-1-yl)-1,3-dimethoxybenzene (3ap)
and (E)-2-(hex-2-en-1-yl)-1,3-dimethoxybenzene (3ap’) (ratio=
5/2). Colorless oil; 1H NMR (400 MHz, CDCl3) δ 0.84 (t, J = 7.3,
7.4 Hz, 1.2H) (3ap’), 0.92 (t, J = 7.2 Hz, 3H) (3ap), 1.35 (m, 2H)
(3ap), 1.46 (m, 2.8H) (3ap+3ap’), 1.94 (m , 0.8H) (3ap’), 2.23
(m, 2H) (3ap), 3.34 (s, 0.8H) (3ap’), 3.80 (s, 2.4H) (3ap’), 3.84
(s, 6H) (3ap), 5.38 (m, 0.4H) (3ap’), 5.49 (m, 0.4H) (3ap’), 6.55
(m, 2.8H) (3ap+3ap’), 6.60 (m, 1H) (3ap), 6.63 (d, J = 16.1 Hz,
1H) (3ap), 7.09 (t, J = 8.3 Hz, 1.4H) (3ap+3ap’); 13C NMR
(100.6 MHz, CDCl3) δ 14.0, 22.4, 31.9, 34.5, 55.8, 104.1, 115.2,
119.8, 127.1, 135.9, 158.1; HRMS (ESI) calcd. for C14H21O2
[M+H]+: 221.1536, found: 221.1528.
4.2.9 (E)-diethyl 2-(3-(2,6-dimethoxyphenyl)allyl)malonate
(3ai).11 Yellow oil; 1H NMR (400 MHz, CDCl3) δ 1.29 (t, J = 7.1
Hz, 6H), 2.84 (td, J = 1.2, 7.5, Hz, 2H ), 3.52 (t, J = 7.7 Hz, 1H),
3.83 (s, 6H), 4.22 (dd, J = 2.5, 7.2 Hz, 4H), 6.54-6.56 (m, 3H),
6.75 (d, J = 16.1 Hz, 1H), 7.13 (t, J = 8.4 Hz, 1H); 13C NMR
(100.6 MHz, CDCl3) δ 4.1, 34.0, 52.5, 55.7, 61.3, 103.9, 114.4,
123.1, 127.7, 129.8, 158.3, 169.1; HRMS (ESI) calcd. for
C18H24NaO6 [M+Na]+: 359.1465, found: 359.1457.
4.2.10 (E)-methyl 5-(2,6-dimethoxyphenyl)-2-methylpent-4-
enoate (3aj). Colorless oil; 1H NMR (400 MHz, CDCl3) δ1.21 (d,
J = 6.8 Hz, 3H), 2.34 (m, 1H), 2.60 (m, 2H), 3.68 (s, 3H), 3.82 (s,
6H), 6.48 (m, 1H), 6.54 (d, J = 8.4 Hz, 2H), 6.65 (d, J = 16.0 Hz,
1H), 7.11 (t, J = 8.3 Hz, 1H); 13C NMR (100.6 MHz, CDCl3) δ
16.5, 38.8, 39.9, 51.5, 55.7, 104.0, 114.8, 122.3, 127.5, 129.9,
131.6, 158.2; HRMS (ESI) calcd. for C15H20NaO4 [M+Na]+:
287.1254, found: 287.1248.
4.2.17
(E)-N,N-bis(tert-butoxycarbonyl)-3-(2,4,6-
trimethoxyphenyl)prop-2-en-1-amine (3ba). Colorleess oil; 1H
NMR (400 MHz, CDCl3) δ 1.52 (s, 18H), 3.79 (s, 3H), 3.80 (s,
6H), 4.30 (d, J = 6.6 Hz, 2H), 6.11 (s, 2H), 6.49 (dt, J = 6.6, 16.0
Hz, 1H), 6.77 (d, J = 16.0 Hz, 1H); 13C NMR (100.6 MHz,
CDCl3) δ 28.0, 50.1, 55.2, 55.5, 81.9, 90.6, 107.3, 123.2, 126.2,
152.3, 159.3, 160.1; HRMS (ESI) calcd. for C22H33NNaO7
[M+Na]+: 446.2149, found: 446.2138.
4.2.11(E)-6-(2,6-dimethoxyphenyl)hex-5-en-2-one (3ak)/(Z)-6-
(2,6-dimethoxyphenyl)hex-5-en-2-one
dimethoxyphenyl)hex-5-en-2-one
(3ak’)/5-(2,6-
(E/Z=100/19,
4.2.18 (E)-2-(3-(2,4,6-trimethoxyphenyl)allyl)isoindoline-1,3-
dione (3bb). Yellow oil; H NMR (400 MHz, CDCl3) δ 3.80 (s,
1
(3ak’’)
linear/branched=119/14). Colorless oil; 1H NMR (400 MHz,
CDCl3) δ 2.09 (s, 0.57H) (3ak’), 2.10 (s, 0.42H) (3ak’’), 2.17 (s,
3H) (3ak), 2.51 (m, 2.64H) (3ak+3ak’+3ak’’), 2.62 (m, 2.30H)
(3ak+3ak’), 3.78 (s, 0.84H) (3ak’’), 3.83 (s, 1.19H) (3ak’), 3.83
(s, 6H) (3ak), 4.90 (m, 0.14H) (3ak’’), 5.31 (m, 0.14H) (3ak’’),
6.21 (m, 0.19H) (3ak’), 6.54 (m, 2.72H) (3ak+3ak’+3ak’’) , 6.58
(m, 1.20H) (3ak+3ak’), 6.66 (d, J = 16.2 Hz, 1H) (3ak), 7.11 (t,
J = 8.3 Hz, 1H) (3ak), 7.20 (m, 0.34H) (3ak’+3ak’’); 13C NMR
(100.6 MHz, CDCl3) δ 29.0, 30.0, 43.7, 55.7, 104.0, 114.6, 121.0,
127.5, 133.1, 158.2, 208.7; HRMS (ESI) calcd. for C14H19O3
[M+H]+: 235.1329, found: 235.1320.
3H ), 3.81 (s, 6H ), 4.44 (dd, J = 0.9, 6.8 Hz, 2H), 6.10 (s, 2H),
6.57 (dt, J = 6.8, 16.0 Hz, 1H), 6.98 (d, J = 16.0 Hz, 1H), 7.70
(dd, J = 3.0, 5.4 Hz, 2H), 7.85 (dd, J = 3.0, 5.4 Hz, 2H); 13C
NMR (100.6 MHz, CDCl3) δ 41.8, 55.3, 55.7, 90.6, 106.8, 123.1,
123.7, 124.5, 132.4, 133.7, 159.5, 160.4, 168.1; HRMS (ESI)
calcd. for C20H19NNaO5 [M+Na]+: 376.1155, found: 376.1148.
4.2.19
(E)-2-(4-(2,4,6-trimethoxyphenyl)but-3-en-2-
1
yl)isoindoline-1,3-dione (3bc). Yellow oil; H NMR (400 MHz,
CDCl3) δ 1.67 (d, J = 7.0 Hz, 3H), 3.81 (s, 3H), 3.83 (s, 6H),
5.02-5.09 (m, 1H), 6.11 (s, 2H), 6.89 (d, J = 16.2 Hz, 1H), 6.99
(dd, J = 8.0, 16.1 Hz, 1H), 7.68 (dd, J = 3.1, 5.4 Hz, 2H), 7.82
(dd, J = 3.0, 5.4 Hz, 2H); 13C NMR (100.6 MHz, CDCl3) δ 19.5,
51.2, 55.3, 55.7, 90.6, 106.8, 122.5, 123.0, 129.2, 132.3, 133.6,
159.5, 160.3, 168.1; HRMS (ESI) calcd. for C21H21NNaO5
[M+Na]+: 390.1312, found: 390.1298.
4.2.12 (E)-ethyl 5-(2,6-dimethoxyphenyl)pent-4-enoate (3al).
1
Colorless oil; H NMR (400 MHz, CDCl3) δ 1.29 (t, J = 7.1 Hz,
3H), 2.49-2.53 (m, 2H), 2.56-2.62 (m, 2H), 3.85 (s, 6H), 4.17 (q,
J = 7.2 Hz, 2H), 6.54-6.59 (m, 3H), 6.72 (d, J = 16.1 Hz, 1H),
7.14 (t, J = 8.4 Hz, 1H); 13C NMR (100.6 MHz, CDCl3) δ 14.3,
30.1, 34.5, 55.7, 60.3, 104.0, 114.6, 121.1, 127.5, 132.8, 158.2,
173.3; HRMS (ESI) calcd. for C15H20NaO4 [M+Na]+: 287.1254,
found: 287.1260.
4.2.20 (E)-diethyl 2-(3-(2,4,6-trimethoxyphenyl)allyl)malonate
(3bi). Colorless oil; 1H NMR (400 MHz, CDCl3) δ 1.28 (t, J = 7.2
Hz, 6H), 2.80 (td, J = 1.3, 7.6 Hz, 2H), 3.49 (t, J = 7.7 Hz, 1H),
3.82 (s, 6H), 3.82 (s, 3H), 4.19-4.24 (m, 4H), 6.13 (s, 2H), 6.41
(dt, J = 7.2, 16.0 Hz, 1H), 6.67 (d, J = 16.1 Hz, 1H); 13C NMR
(100.6 MHz, CDCl3) δ 14.1, 34.0, 52.7, 55.3, 55.6, 61.3, 90.7,
107.7, 122.9, 127.2, 159.1, 159.8, 169.2; HRMS (ESI) calcd. for
C19H26NaO7 [M+Na]+: 389.1571, found: 389.1575.
4.2.13
(E)-1,3-dimethoxy-2-(3-phenylprop-1-en-1-yl)benzene
1
(3am). Colorless oil; H NMR (400 MHz, CDCl3) δ 3.57 (d, J =
5.3 Hz, 2H), 3.84 (s, 6H), 6.35 (m, 1H), 6.40 (d, J = 15.9 Hz, 1H),
6.58 (d, J = 8.3 Hz, 2H), 7.16 (m, 2H), 7.25 (m, 2H), 7.33 (m,
2H); 13C NMR (100.6 MHz, CDCl3) δ 26.5, 55.9, 103.9, 116.5,
126.0, 126.6, 127.2, 128.3 129.0, 129.5, 138.2 158.3; HRMS
(ESI) calcd. for C17H19O2 [M+H]+: 255.1380, found: 255.1369.
4.2.21 (E)-1,3,5-trimethoxy-2-(3-phenylprop-1-en-1-yl)benzene
(3bm). Colorless oil; 1H NMR (400 MHz, CDCl3) δ 3.48 (dd, J =

6
Tetrahedron
1.2, 6.3 Hz, 2H), 3.84 (s, 9H), 6.14-6.24 (m, 4H), 6.33 (d, J =
6.93 (s, 1H), 6.98 (d, J = 15.9 Hz, 1H), 7.73 (dd, J = 3.0, 5.4 Hz,
ACCEPTED MANUSCRIPT
15.8 Hz, 1H), 6.82 (d, J = 8.8 Hz, 2H), 7.28 (d, J = 8.7 Hz, 2H);
13C NMR (100.6 MHz, CDCl3) δ 26.1, 55.3, 55.8, 90.7, 109.3,
113.7, 127.1, 127.3, 128.5, 131.1, 158.4, 158.8, 159.6; HRMS
(ESI) calcd. for C18H20NaO3 [M+Na]+: 307.1305, found:
307.1310.
2H), 7.87 (dd, J = 3.0, 5.48 Hz, 2H); 13C NMR (100.6 MHz,
CDCl3) δ 40.3, 56.0, 56.4, 56.6, 97.6, 109.9, 117.0, 120.9, 123.3,
128.5, 132.3, 133.9, 143.3, 149.7, 151.6, 168.1; HRMS (ESI)
calcd. for C20H19NNaO5 [M+Na]+: 376.1155, found: 376.1142.
4.2.29
(E)-2-(4-(2,4,5-trimethoxyphenyl)but-3-en-2-
1
4.2.22 (E)-1,3,5-trimethoxy-2-(3-(4-methoxyphenyl)prop-1-en-
1-yl)benzene (3bn). Colorless oil; H NMR (400 MHz, CDCl3) δ
yl)isoindoline-1,3-dione (3ec). Yellow oil ; H NMR (400 MHz,
CDCl3) δ 1.67 (d, J = 7.0 Hz, 3H), 3.81 (s, 3H), 3.87 (s, 3H), 3.88
(s, 3H), 5.07-5.14 (m, 1H), 6.48 (s, 1H), 6.53 (dd, J = 8.1, 16.0
Hz, 1H), 6.92 (d, J = 15.5 Hz, 1H), 6.98 (s, 1H), 7.69 (dd, J = 3.0,
5.44 Hz, 2H), 7.81 (dd, J = 3.0, 5.4 Hz, 2H); 13C NMR (100.6
MHz, CDCl3) δ 19.3, 49.6, 56.0, 56.5, 56.6, 97.6, 109.7, 117.1,
123.1, 126.1, 126.3, 132.1, 133.8, 143.3, 149.7, 151.5, 168.0;
HRMS (ESI) calcd. for C21H21NNaO5 [M+Na]+: 390.1312, found:
390.1294.
1
3.49 (dd, J = 0.9, 6.3 Hz, 2H), 3.81 (s, 3H), 3.85 (s, 9H), 6.20 (s,
2H), 6.21-6.24 (m, 1H), 6.33 (d, J = 15.8 Hz, 1H), 6.82 (d, J =
8.8 Hz, 2H), 7.27-7.29 (m, 2H); 13C NMR (100.6 MHz, CDCl3) δ
26.1, 55.3, 55.3, 55.8, 90.7, 109.2, 113.7, 127.1, 127.3, 128.5,
131.1, 158.4, 158.8, 159.4; HRMS (ESI) calcd. for C19H22NaO4
[M+Na]+: 337.1410, found: 337.1419.
4.2.23
(E)-N,N-bis(tert-butoxycarbonyl)-3-(3-chloro-2,6-
dimethoxyphenyl)prop-2-en-1-amine (3ca). Colorless oil; 1H
NMR (400 MHz, CDCl3) δ 1.51 (s, 18H), 3.75 (s, 3H), 3.81 (s,
3H), 4.34 (d, J = 4.1 Hz, 2H), 6.60 (d, J = 8.9 Hz, 1H), 6.67 (m,
2H), 7.18 (d, J = 8.9 Hz, 1H); 13C NMR (100.6 MHz, CDCl3) δ
28.1, 49.3, 55.8, 60.2, 82.3, 107.5, 120.1, 120.9, 122.1, 128.3,
4.2.30
(E)-N,N-bis(tert-butoxycarbonyl)-3-(2,6-
1
diethoxyphenyl)prop-2-en-1-amine (3fa). Colorless oil; H NMR
(400 MHz, CDCl3) δ 1.39 (m , 6H), 1.51 (s , 18H), 4.00 (m, 4H),
4.32 (d, J = 6.5 Hz, 2H), 6.51 (d, J = 8.2 Hz, 2H), 6.72 (m, 1H),
6.88 (d, J = 16.2 Hz, 1H), 7.08 (t, J = 8.3 Hz 1H); 13C NMR
(100.6 MHz, CDCl3) δ 14.1, 28.1, 48.5, 64.1, 82.3, 104.8, 116.2,
128.6, 133.8, 152.4, 158.0; HRMS (ESI) calcd. for C23H35NNaO6
[M+Na]+: 444.2357, found: 444.2345.
131.0, 152.3, 154.5,
157.2; HRMS (ESI) calcd. for
C21H30ClNNaO6 [M+Na]+: 450.1654, found: 450.1643.
4.2.24
(E)-N,N-bis(tert-butoxycarbonyl)-3-(3-bromo-2,6-
dimethoxyphenyl)prop-2-en-1-amine (3da). Colorless oil; 1H
NMR (400 MHz, CDCl3) δ 1.53 (s, 18H), 3.75 (s, 3H), 3.82 (s,
3H), 4.37 (dd, J = 1.5, 2.9 Hz, 2H), 6.58 (d, J = 8.9 Hz, 1H),
6.67-6.69 (m, 2H), 7.36 (d, J = 8.9 Hz, 1H); 13C NMR (100.6
MHz, CDCl3) δ 28.1, 49.3, 55.8, 60.2, 82.3, 108.2, 108.8, 121.0,
122.2, 131.1, 131.2, 152.3, 155.5, 157.9; HRMS (ESI) calcd. for
C21H30BrNNaO6 [M+Na]+: 494.1149, found: 494.1142.
4.2.31 (E)-N,N-bis(tert-butoxycarbonyl)-3-(3-methylthiophen-
2-yl)prop-2-en-1-amine (3ga).12e Yellow oil; 1H NMR (400 MHz,
CDCl3) δ 1.51 (s, 18H), 2.21 (s, 3H), 4.29 (m, 2H), 5.98 (dt, J =
6.4, 15.5 Hz, 1H), 6.66 (d, J = 15.8 Hz, 1H), 6.77 (d, J = 5.1 Hz,
1H), 7.03 (d, J = 5.0 Hz, 1H); 13C NMR (100.6 MHz, CDCl3) δ
13.7, 28.1, 48.1, 82.4, 122.6, 124.1, 124.2, 125.5 130.5, 135.3,
152.3; HRMS (ESI) calcd. for C18H27NNaO4S [M+Na]+:
376.1553, found: 376.1540.
4.2.25
(E)-2-(4-(3-bromo-2,6-dimethoxyphenyl)but-3-en-2-
1
yl)isoindoline-1,3-dione (3dc). Brown oil; H NMR (400 MHz,
CDCl3) δ 1.70 (d, J = 7.0 Hz, 3H), 3.75 (s, 3H), 3.84 (s, 3H),
5.10-5.17 (m, 1H), 6.57 (d, J = 8.9 Hz, 1H), 6.77 (d, J = 16.3 Hz,
1H), 7.08 (dd, J = 7.3, 16.2 Hz, 1H), 7.35 (d, J = 8.9 Hz, 1H),
7.72 (dd, J = 3.0, 5.4 Hz, 2H), 7.85 (dd, J =3.1, 5.3 Hz, 2H); 13C
NMR (100.6 MHz, CDCl3) δ 18.8, 19.2, 49.9, 55.9, 60.5, 108.2,
108.8, 121.9, 123.1, 131.5, 132.1, 133.9, 134.0, 158.0, 168.0;
HRMS (ESI) calcd. for C20H18BrNNaO4 [M+Na]+: 438.0311,
found: 438.0296.
4.2.32
(E)-2-(3-(3-methylthiophen-2-yl)allyl)isoindoline-1,3-
1
dione (3gb). White solid, mp: 84-85 °C; H NMR (400 MHz,
CDCl3) δ 2.23 (s, 3H), 4.41 (dd, J = 1.1, 7.9 Hz, 2H), 6.00 (dt, J
= 6.8, 15.5 Hz, 1H), 6.75 (d, J = 5.0 Hz, 1H), 6.83 (d, J = 15.5
Hz, 1H), 7.02 (d, J = 5.0 Hz, 1H), 7.71 (dd, J = 3.1, 5.5 Hz, 2H),
7.85 (dd, J = 3.1, 5.5 Hz, 2H); 13C NMR (100.6 MHz, CDCl3) δ
13.8, 39.7, 121.6, 123.1, 123.3, 125.9, 130.5, 132.2, 133.9, 134.7,
167.9; HRMS (ESI) calcd. for C16H13NNaO2S [M+Na]+:
306.0559, found: 306.0563.
4.2.26
(E)-diethyl
2-(3-(3-bromo-2,6-
4.2.33
(E)-N,N-bis(tert-butoxycarbonyl)-3-(3,4,5-
1
1
dimethoxyphenyl)allyl)malonate (3di). Brown oil; H NMR (400
MHz, CDCl3) δ 1.29 (t, J = 7.1 Hz, 6H), 2.84-2.88 (m, 2H), 3.53
(t, J = 7.6 Hz, 1H), 3.74 (s, 3H), 3.83 (s, 3H), 4.18-4.27 (m, 4H),
6.57 (d, J = 8.9 Hz, 1H), 6.61-6.63 (m, 2H), 7.35 (d, J = 8.9 Hz,
1H); 13C NMR (100.6 MHz, CDCl3) δ 14.1, 33.7, 52.1, 55.9, 60.2,
61.4, 108.2, 108.9, 121.3, 122.9, 131.0, 131.8, 155.4, 157.8,
168.9; HRMS (ESI) calcd. for C18H23BrNaO6 [M+Na]+: 437.0570,
found: 437.0565.
trichlorothiophen-2-yl)prop-2-en-1-amine (3ha). Yellow oil; H
NMR (400 MHz, CDCl3) δ 1.53 (s, 18H ), 4.32 (dd, J = 1.4, 6.2
Hz, 2H ), 6.06 (dt, J = 6.2, 15.8 Hz,1H), 6.68 (dt, J = 1.4, 15.8 Hz,
1H); 13C NMR (100.6 MHz, CDCl3) δ 28.1, 47.6, 82.8, 121.3,
121.7, 122.5, 123.6, 127.9, 132.1, 152.1; HRMS (ESI) calcd. for
C17H22Cl3NNaO4S [M+Na]+: 464.0227, found: 464.0216.
4.2.34 (E)-2-(3-(3,4,5-trichlorothiophen-2-yl)allyl)isoindoline-
1
1,3-dione (3hb). Yellow oil; H NMR (400 MHz, CDCl3) δ 4.45
4.2.27
(E)-N,N-bis(tert-butoxycarbonyl)-3-(2',4',5'-
(dd, J =1.4, 6.5 Hz, 2H), 6.08 (dt, J = 6.5, 15.8 Hz, 1H), 6.82 (dt,
J = 1.4, 15.8 Hz, 1H), 7.76 (dd, J = 3.0, 5.5 Hz, 2H), 7.89 (dd, J
= 3.0, 5.5 Hz, 2H); 13C NMR (100.6 MHz, CDCl3) δ 39.2, 123.0,
123.3, 123.5, 123.7, 125.4, 131.5, 132.0, 134.0, 134.2, 167.7;
HRMS (ESI) calcd. for C15H8Cl3NNaO2S [M+Na]+: 393.9234,
found: 393.9228.
trimethoxyphenyl)prop-2-en-1-amine (3ea). Colorless oil; 1H
NMR (400 MHz, CDCl3) δ 1.52 (s, 18H), 3.80 (s, 3H), 3.86 (s,
3H), 3.89 (s, 3H), 4.32 (dd, J = 1.2, 6.5 Hz, 2H), 6.08 (dt, J = 6.5,
15.9 Hz, 1H), 6.49 (s, 1H), 6.83 (d, J = 16.0 Hz, 1H), 6.94 (s, 1H);
13C NMR (100.6 MHz, CDCl3) δ 28.1, 48.7, 56.0, 56.5, 56.5,
82.3, 97.6, 109.9, 117.6, 123.1, 127.1, 143.3, 149.5, 151.3, 152.4;
HRMS (ESI) calcd. for C22H33NNaO7 [M+Na]+: 446.2149, found:
446.2135.
4.2.35
(E)-N,N-bis(tert-butoxycarbonyl)-3-(3-
methylbenzo[b]thiophen-2-yl)prop-2-en-1-amine (3ia).12e Yellow
1
oil; H NMR (400 MHz, CDCl3) δ 1.55 (s, 18H ), 2.41 (s, 3H),
4.2.28 (E)-2-(3-(2,4,5-trimethoxyphenyl)allyl)isoindoline-1,3-
dione (3eb). Yellow solid, mp: 101-102 °C; 1H NMR (400 MHz,
CDCl3) δ 3.83 (s, 3H), 3.85 (s, 3H), 3.90 (s, 3H), 4.46 (dd, J =
1.2, 6.7 Hz, 2H), 6.16 (dt, J = 6.8, 15.9 Hz, 1H), 6.49 (s, 1H),
4.38 (dd, J = 1.2, 6.3 Hz, 2H), 6.13 (dt, J = 6.3, 15.5 Hz, 1H),
6.88 (dt, J = 1.3, 15.5 Hz, 1H), 7.30-7.38 (m, 2H), 7.63-7.65 (m,
1H), 7.74-7.76 (m, 1H); 13C NMR (100.6 MHz, CDCl3) δ 11.7,
28.1, 48.1, 82.6, 121.7, 122.1, 124.1, 124.3, 124.9, 127.0, 129.4,

7
135.6, 138.0, 141.0, 152.3; HRMS (ESI) calcd. for
Acknowledgments
ACCEPTED MANUSCRIPT
C22H29NNaO4S [M+Na]+: 426.1710, found: 426.1693.
Financial support from the National Natural Science
Foundation of China (21372258) is greatly acknowledged.
4.2.36 (E)-2-(3-(3-methylbenzo[b]thiophen-2-
1
yl)allyl)isoindoline-1,3-dione (3ib). Yellow oil; H NMR (400
MHz, CDCl3) δ 2.39 (s, 3H ), 4.48 (dd, J = 0.7, 4.4 Hz, 2H ), 6.13
(dt, J = 4.5, 10.3 Hz, 1H), 7.02 (dt, J = 0.8, 10.3 Hz, 1H), 7.28-
7.33 (m, 2H), 7.61 (dd, J = 0.7, 5.6 Hz, 1H), 7.71 (dd, J = 0.8, 4.7
Hz, 1H), 7.73 (dd, J = 2.0, 3.6 Hz, 2H), 7.87 (dd, J = 2.0, 3.6 Hz,
2H); 13C NMR (100.6 MHz, CDCl3) δ 11.9, 39.8, 121.9, 122.2,
123.4, 124.1, 124.4, 125.1, 126.2, 130.3, 132.3, 134.1, 135.1,
138.2, 141.0, 168.0; HRMS (ESI) calcd. for C20H15NNaO2S
[M+Na]+: 356.0716, found: 356.0708.
References and notes
1. For recent reviews, see: (a) Cartney, D. M.; Guiry, P. J. Chem. Soc.
Rev. 2011, 40, 5122; (b) Oestreich, M. The Mizoroki-Heck
reaction, Wiley: Chichester, 2009; (c) Torborg, C.; Beller, M.; Adv.
Synth. Catal. 2009, 351, 3027; (d) Knowles, J. P.; Whiting, A. Org.
Biomol. Chem. 2007, 5, 31; (e) Phan, N. T. S.; Van Der Sluys, M.;
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Beletskaya, I. P.; Yus, M. Tetrahedron 2005, 61, 11771; (g)
Oestreich, M. Eur. J. Org. Chem. 2005, 783.
4.2.37
(E)-N,N-bis(tert-butoxycarbonyl)-3-(3-
2. For applications of Heck reaction, see: (a) Felpin, F.-X.; Nassar-
Hardy, L.; Le Callonnec, F.; Fouquet, E. Tetrahedron 2011, 67,
2815; (b) Taylor, J. G.; Moro, A. V.; Correia, C. R. D. Eur. J. Org.
Chem. 2011, 1403; (c) Nicolaou, K. C.; Bulger, P. G.; Sarlah, D.
Angew. Chem. Int. Ed. 2005, 44, 4442; (d) Farina, V. Adv. Synth.
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(f) Zapf, A.; Beller, M. Top. Catal. 2002, 19, 101; (g) de Vries, J.
G. Can. J. Chem. 2001, 79, 1086.
methylbenzo[b]furan-2-yl)prop-2-en-1-amine (3ja). Colorless oil;
1H NMR (400 MHz, CDCl3) δ 1.52 (s, 18H), 2.23 (s, 3H), 4.38 (d,
J = 6.1 Hz, 2H), 6.37 (m, 1H), 6.52 (d, J = 16.0 Hz, 1H), 7.19 (m,
2H), 7.38 (d, J = 8.1 Hz, 1H), 7.44 (d, J = 7.6 Hz, 1H); 13C NMR
(100.6 MHz, CDCl3) δ 7.9, 28.1, 48.1, 82.3, 110.7, 116.2, 118.7,
119.2, 122.3, 124.6, 125.9, 133.8, 149.6, 152.4; HRMS (ESI)
calcd. for C22H29NNaO5 [M+Na]+: 410.1938, found: 410.1927.
3.
For recent reviews, see: (a) Baudoin, O. Angew. Chem. Int. Ed.
2007, 46, 1373; (b) Goossen, L. J.; Rodriguez, N.; Goossen, K.
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Synthesis 2010, 3395; (d) Rodriguez, N.; Goossen, L. J. Chem.
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2671.
4.2.38
(E)-N,N-bis(tert-butoxycarbonyl)-3-(2,6-
1
difluorophenyl)prop-2-en-1-amine (3ka). Colorless oil; H NMR
(400 MHz, CDCl3) δ 1.51 (s, 18H), 4.34 (d, J = 3.7 Hz, 2H), 6.52
(m, 2H), 6.86 (m, 2H), 7.13 (m, 1H); 13C NMR (100.6 MHz,
CDCl3) δ 28.0, 48.9, 82.5, 111.6, 116.2, 118.3, 128.0, 132.4,
133.8, 152.2; HRMS (ESI) calcd. for C19H25F2NNaO4 [M+Na]+:
392.1644, found: 392.1630.
4. (a) Goosen, L. J.; Deng, G.; Levy, L. M. Science 2006, 313, 662; (b)
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4.2.39
(E)-N,N-bis(tert-butoxycarbonyl)-3-(2-chloro-6-
fluorophenyl)prop-2-en-1-amine (3la). Colorless oil; 1H NMR
(400 MHz, CDCl3) δ 1.51 (s, 18H), 4.37 (d, J = 5.8 Hz, 2H), 6.45
(m, 1H), 6.61(d, J = 16.2 Hz, 1H), 6.97 (m, 1H), 7.10 (m, 1H),
7.16 (m, 1H); 13C NMR (100.6 MHz, CDCl3) δ 28.1, 48.7, 82.5,
114.7, 116.2, 122.1, 125.5, 128.1, 128.2, 129.9, 133.4, 152.3;
HRMS (ESI) calcd. for C19H25ClFNNaO4 [M+Na]+: 408.1348,
found: 408.1333.
4.2.40
(E)-N,N-bis(tert-butoxycarbonyl)-3-(2,4,6-
1
trifluorophenyl)prop-2-en-1-amine (3ma). Yellow oil; H NMR
(400 MHz, CDCl3) δ 1.53 (s, 18H), 4.30 (dd, J = 0.8, 6.6 Hz, 2H),
6.13 (s, 2H), 6.50 (dt, J = 6.6, 16.1 Hz, 1H), 6.78 (d, J = 16.2 Hz,
1H); 13C NMR (100.6 MHz, CDCl3) δ 28.1, 50.1, 81.9, 90.7,
107.4, 123.2, 126.3, 152.3, 159.3, 160.1; HRMS (ESI) calcd. for
C19H24F3NNaO4 [M+Na]+: 410.1550, found: 410.1538.
4.2.41
(E)-N,N-bis(tert-butoxycarbonyl)-3-(2,3,4,5,6-
5.
Dai, J.-J.; Liu, J.-H.; Luo, D.-F.; Liu, L. Chem. Commun. 2011, 47,
pentafluorophenyl)prop-2-en-1-amine (3na).12e Yellow oil; 1H
NMR (400 MHz, CDCl3) δ 1.50 (s, 18H), 4.35 (d, J = 4.6 Hz,
2H), 6.39 (d, J = 16.4 Hz, 1H), 6.54 (dt, J = 16.4, 5.6 Hz, 1H);
13C NMR (100.6 MHz, CDCl3) δ 28.0, 48.5, 82.8, 115.8, 116.2,
133.8, 135.0, 152.1; 19F NMR (376.5 MHz, CDCl3): -163.0 (dt, J
= 5.5, 14.9 Hz, 2F), -156.4 (t, J = 14.8 Hz, 1F). -143.0 (dd, J =
5.6, 14.9 Hz, 2F); HRMS (ESI) calcd. for C19H22F5NNaO4
[M+Na]+: 446.1361, found: 446.1348
677.
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4.2.42
(E)-2-(3-(perfluorophenyl)allyl)isoindoline-1,3-dione
(3nb).12e White solid, mp: 114-115 °C; 1H NMR (400 MHz,
CDCl3) δ 4.49 (d, J = 4.84 Hz, 2H), 6.54 (d, J = 16.4 Hz, 1H),
6.60 (dd, J = 5.2, 16.4 Hz, 1H), 7.74 (dd, J = 3.0, 5.5 Hz, 2H),
7.88 (dd, J = 3.0, 5.4 Hz, 2H); 13C NMR (100.6 MHz, CDCl3) δ
40.1, 117.6, 123.5, 123.6, 132.0, 132.3, 134.2, 134.3, 167,7; 19F
NMR (376.5 MHz, CDCl3): δ -142.4 (dd, J = 5.1, 14.4 Hz, 2F), -
155.6 (t, J = 14.0 Hz, 1F), -162.8 (td, J = 4.7, 19.2 Hz, 2F);
HRMS (ESI) calcd. for C17H8F5NNaO2 [M+Na]+: 376.0367,
found: 376.0355.
8.
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