Highly regio- and stereoselective palladium-catalyzed allene bifunctionalization cascade via π-allyl intermediate

Article abstract of DOI:10.1016/j.tet.2017.08.021

We report a palladium-catalyzed allene bifunctionalization reaction that forms C–C and either C–O or C–N bonds in one pot with excellent regio- and stereoselectivity. Carboxylic acids, amides, and hydroxide are all suitable nucleophiles. Organoboronic acid acts as hydroxide transfer reagent. An intermediate π-allyl palladium complex was isolated, which yields improved catalytic performance as well as evidence of the origin of stereoselectivity. A derivatization study emphasizes the utility of the functionalized allylic products.

Full text of DOI:10.1016/j.tet.2017.08.021

Tetrahedron 73 (2017) 5784e5793
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Highly regio- and stereoselective palladium-catalyzed allene
bifunctionalization cascade via
p-allyl intermediate
a
,
*
a
b
b
c
Tao Bai , Yanhui Yang , Trevor Janes , Datong Song , Zhiqiang Guo
a
College of Chemistry and Chemical Engineering, Shanxi University, #92 Wucheng Road, Taiyuan, Shanxi, 030006, People's Republic of China
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada
Scientific Instrument Center, Shanxi University, Taiyuan, 030006, People's Republic of China
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 12 June 2017
Received in revised form
We report a palladium-catalyzed allene bifunctionalization reaction that forms CeC and either CeO or
CeN bonds in one pot with excellent regio- and stereoselectivity. Carboxylic acids, amides, and hydroxide
are all suitable nucleophiles. Organoboronic acid acts as hydroxide transfer reagent. An intermediate p-
allyl palladium complex was isolated, which yields improved catalytic performance as well as evidence of
the origin of stereoselectivity. A derivatization study emphasizes the utility of the functionalized allylic
products.
8
August 2017
Accepted 14 August 2017
Available online 19 August 2017
©
2017 Elsevier Ltd. All rights reserved.
Keywords:
Allenes
Palladium
Allylic compounds
Multicomponent reactions
1
. Introduction
yielding allyl acetate products9b (eq. 2, Scheme 1). However,
selectivity problems hampered further applications of this method.
Reports of nucleophilic substitution reactions utilizing allenes
bearing strong EWG (such as sulfone, phosphonate and phosphine
Polysubstituted allyl compounds are important building blocks
in organic synthesis, and are common structural motifs in natural
products. Transition metal-catalyzed nucleophilic allylic substitu-
1
6
oxide) are still scarce. Boronic acids are commonly used to
tion is a rapid process to construct polysubstituted allyl com-
pounds. The palladium catalyzed TsujieTrost reaction has been
construct CeC bonds via the transmetallation step in Suzuki-
Miyaura coupling reactions. However, examples of boronic acid
2
7,8
developed into a powerful tool for this transformation in recent
employed as hydroxide source to construct CeO bonds are un-
common. Herein we report a new series of palladium-catalyzed
3
9
years. The
p
-allyl palladium intermediates are essential to the
-allyl palladium
formation of allylic substitution products; such
p
allene bifunctionalization reactions which generate substituted
allylic alcohols, esters and amides employing boronic acid, car-
boxylic acids and amides, respectively as nucleophiles (eq. 3,
Scheme 1). We observe good regioselective control and pure (Z)-
selectivity of the double bond geometry. We isolated a possible
species have been thoroughly studied and reviewed by organo-
metallic chemists.4 Allenes possess two adjacent C]C double
bonds, and can be used to construct p-allyl metal complexes with
participation of electrophiles such as aryl halides. Subsequent
5
nucleophilic substitution yields the polysubstituted allyl products.
intermediate p-allyl palladium complex and used it as catalyst,
In most reports of palladium-catalyzed allene bifunctionaliza-
tion reactions, the allene substituent R is an electron donating
group such as alkyl/aryl, or a weak electron withdrawing group
which improved the efficiency of the reaction.
5
c,5d
2. Results and discussion
(
EWG) such as carboxylic acid, ester or amide (eq. 1, Scheme 1).
Savic et al. demonstrated that heteroatom-based nucleophiles such
as acetate could be employed in the bifunctionalization cascade,
In the cascade reaction involving phenylsulfonyl allene 1a and
phenyl iodide 2a, different palladium sources, boronic acids,
phosphine ligands, and bases were screened in order to find
optimal reaction conditions (Table 1). For purification purposes, the
allyl alcohol product was protected using imidazole/TBSCl.
Optimal conditions (entry 1, Table 1) resulted in a 64% isolated
10
*
Corresponding author.
E-mail address: baitaostersioc@163.com (T. Bai).
http://dx.doi.org/10.1016/j.tet.2017.08.021
040-4020/© 2017 Elsevier Ltd. All rights reserved.
0

T. Bai et al. / Tetrahedron 73 (2017) 5784e5793
5785
Scheme 1. Cascade reaction pathway involving allenes.
Scheme 2. Substrate scope.
yield of desired product 4a, but we were unable to completely
suppress the biphenyl product 4aa formed by the direct C-C
coupling of phenyl iodide 2a and boronic acid 3a. For the palladium
Table 1). The optimal boronic acid was p-n-butylphenylboronic acid
3a). Screening different phosphine ligands (entries 12e17, Table 1)
(
source, [Pd(MeCN)
4
](OTf)
2
outperformed its counterparts
revealed Xantphos to be the preferred choice. The success of
Xantphos may be attributed to its wide bite angle and rigid carbon
skeleton, which can help to increase the ability of Pd to bind the
Pd (dba) and Pd(OAc)
2
3
2
(entries 1e3, Table 1). Arylboronic acids of
varying structure were also screened (entries 4e9, Table 1); use of
ortho methyl-substituted phenyl boronic acid (3h) yielded only a
trace amount of desired product 4a, and meta-methylphenyl
boronic acid (3i) gave 26% isolated yield of 4a (entries 10e11,
11
CeC double bond of the functionalized allene substrates. Chang-
ing the base from potassium carbonate to KF or K
3
PO
4
did not lead
to improved yields (entries 18e19, Table 1).
Table 1
Optimization of palladium catalyzed cascade reaction.
Entry
[Pd]/5 mol%
Pd]/[P] ¼ 1:2
[P]/10 mol%
Boronic acids 3
Base
4aa (%)
4aa (%)
[
1
2
3
4
5
6
7
8
9
[Pd(MeCN)
Pd (dba)
Pd(OAc)
4
](OTf)
2
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
3a
3a
3a
3b
3c
3d
3e
3f
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
64
28
9
46
26
49
trace
25
trace
trace
26
trace
trace
trace
trace
trace
trace
26
26
e
2
3
2
e
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
[Pd(MeCN)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
4
](OTf)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
e
e
e
e
e
3g
3h
3i
e
10
11
12
13
14
15
16
17
18
19
20
e
e
PPh
3
3a
3a
3a
3a
3a
3a
3a
3a
34
trace
18
6
trace
25
e
dppe
dppp
dppf
dppbz
DPEphos
Xantphos
Xantphos
Xantphos
KF
K
K
3
PO
4
trace
Complicated
e
THF/H
2
O (3:0.1/mL)
2
CO
3
e
THF was dried by sodium/benzophenone and used in glove box (O
2
< 0.1 ppm and H
2
O < 0.1 ppm).
a
t
There is no need to purify the allyl alcohol precursor. Isolated yield of two steps were shown. -TBS ¼ -SiMe
2
( Bu); -OTf ¼ -SO
2 3
CF ;

5786
T. Bai et al. / Tetrahedron 73 (2017) 5784e5793
nucleophilic substitution reaction of the OH group (formed in the
first step of cascade reaction) with the phosphonate substituent
due to their mutually cis orientation. However, when the phos-
phonate group was replaced by a phosphine oxide group (1g), the
cyclization was inhibited, and allylic alcohol 4p forms in 67% yield
(eq. 3). The solid-state structure of 4p was confirmed by X-ray
crystallography (see full detail in SI).
Fig. 1. ORTEP drawing of 4d with 50% thermal ellipsoids. Hydrogen atoms are omitted
for clarity.
(
(
1)
2)
(
3)
In all cases, the allene's EWG and the aryl halide's aryl group are
oriented trans to each other in the olefin products, which is similar
to the orientation of
before.
p-allyl palladium complexes we isolated
1
5,16
Therefore, we hypothesized that the reaction pathway involves
p-allyl palladium intermediate. To investigate this hypothesis, the
a
17
complex (Xantphos)PdPhI, 7, was reacted with allene 1a (Scheme
). After iodide abstraction with AgBF was carried out in CH Cl
the cis- -allyl palladium complex 8 was isolated as light yellow
3
4
2
2
,
p
Scheme 3. The ORTEP drawing of complex 8 with 50% thermal ellipsoids. Hydrogen
atoms and co-crystallized solvent are omitted for clarity. There is one disordered
solid in 70% yield. The structure of 8 was confirmed by X-ray
crystallography (Scheme 3). The coordination geometry at palla-
component of BF
4
counter anion shown in the crystal structure. Selected bond lengths
ꢀ
(
Å) and angles ( ): Pd(1)eP(1) 2.3779(6), Pd(1)eP(2) 2.3733(6), Pd(1)eC(40) 2.212(3),
dium is best described as distorted square planar, with the two
Pd(1)eC(41) 2.193(2), Pd(1)eC(48) 2.154(2); P(1)ePd(1)eP(2) 106.88(2); P(1)ePd(1)e
C(41) 126.75(6), P(2)ePd(1)eC(41) 125.52(6), C(14)-P(1)-Pd(1) 125.68(8), C(26)-P(2)-
Pd(1) 119.15(8).
3
phosphorus donors and the
h
-allyl fragment comprising the co-
ordination sphere. The two phosphorus atoms are cis to each other
ꢀ
with a bite angle (P-Pd-P) of 106.9 , which occurs within the
ꢀ
17
calculated flexible bite angle range of Xantphos (97-135 ). The
distances between the two phosphorus atoms and the palladium
center are 2.378 and 2.373 Å. The distance between the metal
To address the origin of the hydroxide nucleophile, we per-
formed control experiments using either water or boroxine12 in
place of organoboronic acid. These experiments did not result in
product formation (entry 20, Table 1 and see SI for further detail).
With the optimized reaction conditions in hand, we studied the
scope with respect to the aryl iodide 2 (Scheme 2). For the para (2b-
center and the allyl moiety is in the range of 2.15e2.21 Å, which is
17c
similar to analogues in the literature.
The trans configuration
between the sulfone substituent on the terminal carbon of the
allene and the phenyl group on the central carbon of the allene is
2
f) and meta (2g-2i) substituted phenyl iodide substrates, the
15
evident in the crystal structure. This trans orientation is main-
cascade reaction furnishes the desired products (4b-4i) with
moderate to good combined isolated yields. Carbon-halogen func-
tionalities on the phenyl ring remained intact (4d, 4e), which in-
dicates the potential to build more complicated molecules via cross
coupling reactions. The (Z) geometry of the CeC double bond of 4d
was confirmed by X-ray crystallography (Fig. 1). The highest yield
tained after nucleophilic substitution in the final coupling product.
Complex 8 can be used as an effective catalyst in the cascade
(
73%) can be reached when 4-t-butyl phenyl iodide is used as
0
substrate (4f). We also tested other substituents R on the sulfone
(
4
4k-4m, Scheme 3). For R’ ¼ Me, the yield of corresponding product
k is similar to 4a; the electron donating group R’ ¼ OMe decreased
the yield (4l), and when the electron withdrawing group R’ ¼ Br
was used, the yield dropped to 35% (4m).
Allenes containing other types of functional groups were used,
such as the phosphonate 1e and the ester 1f. The cascade reaction
13
14
afforded the cyclic products 4n (61%) and 4o (75%) (eqs. 1 and
). Their formation can be rationalized as the intramolecular
Scheme 4. Catalyst screening for the multicomponent reaction using KOAc as
nucleophile.
2

T. Bai et al. / Tetrahedron 73 (2017) 5784e5793
5787
reaction with higher isolated yield (80%) and lower catalyst loading
2.5 mol%, eq. 4) compared to [Pd(MeCN) ](OTf) , which suggests
that the -allyl palladium complex 8 is a possible intermediate in
(
4
2
p
this cascade reaction. The stoichiometric reaction of complex 8
with boronic acid and potassium carbonate was also conducted,
and yielded the desired product 4a with 36% yield in the presence
18
of phenyl iodide. (see SI for full detail).
Fig. 2. ORTEP drawing of 6ai with 50% thermal ellipsoids. Hydrogen atoms are omitted
for clarity.
(4)
In order to expand the nucleophile scope in the cascade reac-
tion, we investigated the viability of carboxylates as coupling
partners. When potassium acetate was reacted with sulfonyl allene
1
4 2
a and phenyl iodide 2a under our [Pd(MeCN) ](OTf) /Xantphos
coupling conditions, desired allylic acetate 6a formed in 39% iso-
lated yield (Scheme 4). Improvement of the yield to 64% or 66% was
achieved by employing precatalysts 7 or 8, respectively. Given the
similar catalytic performance of 7 and 8, we used the more stable
and easily available complex 7 as catalyst to study the substrate
scope of aryl iodides and nucleophiles (Scheme 5).
Alkyl and aryl carboxylic acids are successful nucleophiles in the
cascade; in the presence of a variety of aryl halides, the catalytic
cascade reaction yields products 6aa-6ag with 57e73% isolated
yields. Commonly used Tosyl- and Phth-protected amide
(
TsNH(BOC), PhthNH) were also employed as nitrogen-containing
Scheme 6. Derivatization studies of allylic silyl ether 4a.
nucleophiles to produce allylic amides 6ah-6aj with moderate
yields. Single crystals of 6ai were obtained and analyzed by X-ray
crystallography, which confirmed that the sulfonyl group and the
aryl group are oriented trans to each other in the allylic amide
product (Fig. 2). Removal of the Phth-group allows access to the free
allylic amine.19
To demonstrate the utility of our allene bifunctionalization
method, we subjected one of the products to a derivatization study,
namely allylic silyl ether 4a (Scheme 6). The free alcohol 5a can be
obtained with 91% isolated yield under KF-promoted Si-O cleavage
2
0
with the assistance of TMSCl as Lewis acid. The allylic halide
3
compound 5b was formed with 83% isolated yield under PPh /DDQ
assisted C-O cleavage.2 Allylic acetate 6a can be obtained as well
from alcohol 5a with 95% yield via a standard acetylation pathway.
The allylic acetate 6a can be employed as a useful building block to
form CeC, CeN or CeC double bonds under different conditions.
Reaction with C-nucleophilic reagent di-tert-butyl propanedioate
1
Scheme 7. Proposed catalytic cycle.
2
2
yields the C-C coupling product 6b in 68% isolated yield. When 6a
was subjected to catalytic borylation, unexpected CeC double bond
migration occurred to yield product 6c instead of the desired allylic
boronate.23 C-N coupling of 6a with aniline proceeded smoothly
under the influence of Pd/dppf cocatalysts: product 6d formed in
69%.
24
Based on the observations above, the reaction mechanism is
proposed in Scheme 7. Pd(0) reacts with aryl iodide via oxidative
addition to produce Pd(II) intermediate A. Subsequently, carbo-
metallation of the allene occurs to form the
p-allyl palladium(II)
intermediate B, which can be trapped by different Nus via nucle-
ophilic attack on the terminal allene carbon, which results in
release of the coupling product D and regeneration of Pd(0). Hy-
-
droxide delivery from organoboronic acid (Nu ¼ OH) can be
explained by nucleophilic attack of the “ate complex” C, which is
9
a
produced by the reaction of boronic acid with base. The exclusive
trans orientation between the allene substituent and the aryl group
on the central carbon can be attributed to the strong electron
15
withdrawing ability of the functional group on the allene.
Scheme 5. Substrate scope for different nucleophiles containing carboxylic acids and
amides.

5788
T. Bai et al. / Tetrahedron 73 (2017) 5784e5793
3
. Conclusion
monitored by TLC (Hexane/Ethyl acetate ¼ 7:1) as well to confirm
that the formation of TBS protected allyl alcohol 4a was complete.
Then product was isolated and purified by short column chroma-
tography (Hexane/Ethyl acetate ¼ 20:1) to yield pure 4.
In summary, the palladium-catalyzed cascade reaction of aryl
iodides and functionalized allenes was demonstrated, which pro-
duced (Z)-allylic alcohol compounds with pure steroselectivity. The
putative intermediate p-allyl palladium complex can be trapped by
4.2.1. {[(2Z)-3-(benzenesulfonyl)-2-phenylprop-2-en-1-yl]
several kinds of nucleophiles to form CeO or CeN bonds. Organo-
boronic acids were used to form the CeOH bond and promote the
completion of the catalytic cycle. The utility of the allylic acetate
products was shown in a derivatization study. Our results show that
useful building blocks can be easily produced by this cascade
methodology. We would like to expand this reactivity to other
sensitive substrates. The corresponding research is under devel-
opment in our lab.
oxy}(tert-butyl)dimethylsilane (4a)
Eluent: Hexane/Ethyl acetate. White solid (50 mg, 64%), Melting
ꢀ
1
point 48e49 C, H NMR (600 MHz, C
6
D
6
)
d
7.93 (2H, d, J ¼ 6 Hz),
7
.11e6.95 (8H, m), 6.41 (1H, s), 5.27 (2H, s), 0.79 (9H, s), 0.03 (6H, s);
13
C NMR (150 MHz, C D ) d 155.69, 143.27, 138.14, 133.38, 129.80,
6 6
1
29.64, 128.95, 128.70, 128.43, 127.93, 58.89, 26.18, 18.60, ꢁ4.87; IR
ꢁ1
(film, cm ): 2924, 1470, 1303, 1287, 1174, 1144, 1082, 837; HRMS
þ
(
3
ESIþ): Calcd for
C
21
H
29
O
3
SSi [MþH] : 389.16012; Found:
89.15999.
4
. Experimental section
4
.2.2. {[(2Z)-3-(benzenesulfonyl)-2-(4-methylphenyl)prop-2-en-1-
4.1. General information
yl]oxy}(tert-butyl)dimethylsilane (4b)
Eluent Hexane/Ethyl acetate. White solid (46 mg, 57%), Melting
Analytical thin layer chromatography (TLC) was performed on
ꢀ
1
point 64e66 C, H NMR (600 MHz, C
6 6
D ) d 7.97e7.92 (2H, m), 7.09
precoated silica gel 60 F254 plates, glass. Visualization on TLC was
achieved by the use of UV light (254 nm). Flash column chroma-
tography was undertaken on silica gel (300e400 mesh). The purity
of nitrogen gas is 99.999%. Air sensitive liquid and solutions were
manipulated by using glove box and dry solvents. The catalytic
reactions were performed under a nitrogen atmosphere either in a
glove box (Delix, China) or in sealed thick glass tubes purchased
from Synthware Company (BeiJing). THF, benzene and deuterated
benzene were distilled from Na metal under nitrogen protected
solvent purification system obtained from Synthware Company.
Unless otherwise stated, all commercial reagents were used
without additional purification. Proton nuclear magnetic resonance
spectra were recorded on Brucker Avance 600 MHz, Chemical shifts
were quoted in parts per million (ppm) referenced to the appro-
(
2H, d, J ¼ 6 Hz), 6.98e6.93 (3H, m), 6.85 (2H, d, J ¼ 6 Hz), 6.49 (1H,
13
s), 5.30 (2H, s), 2.03 (3H, s), 0.83 (9H, s), 0.07 (6H, s); C NMR
150 MHz, C 155.49, 143.48, 139.99, 135.26, 133.28, 129.61,
29.48, 128.68, 128.43, 127.90, 58.81, 26.24, 21.46, 18.65, ꢁ4.82; IR
(
1
(
6 6
D ) d
ꢁ
1
þ
film, cm ): 2929, 1316, 1140, 1106, 812, 788, 688; HRMS (ESI ):
þ
þ
Calcd for C22
H
31
O
3
SSi [MþH] : 403.17577; Found: 403.17579.
4
.2.3. {[(2Z)-3-(benzenesulfonyl)-2-(4-fluorophenyl)prop-2-en-1-
yl]oxy}(tert-butyl)dim-ethylsilane (4c)
Eluent Hexane/Ethyl acetate. White solid (44 mg, 54%), Melting
ꢀ
1
point 82e83 C, H NMR (600 MHz, C
6 6
D ) d 7.95e7.91 (2H, m),
6
.99e6.93 (3H, m), 6.89e6.84 (2H, m), 6.67e6.62 (2H, m), 6.30 (1H,
13
s), 5.20 (2H, s), 0.79 (9H, s), 0.02 (6H, s); C NMR (150 MHz, C
6 6
D )
priate solvent peak (CHCl
.16 ppm). Carbon 13 nuclear magnetic resonance spectroscopy (
3 3 6 6 6 6
in CDCl : 7.24 ppm; C H in C D :
d
(
2
(
(
4
164.90, 163.25, 154.38, 143.20, 133.95 (d, J ¼ 3 Hz), 133.44, 130.42
13
7
C
d, J ¼ 7.5 Hz), 129.65, 128.84, 127.93, 115.67 (d, J ¼ 7.5 Hz), 58.76,
NMR) was recorded on Brucker Avance 151 MHz and was fully
decoupled by broad band decoupling. Chemical shifts were re-
ported in ppm referenced to the center line of a triplet at 77.23 ppm
19
6.14, 18.56, ꢁ4.90; F NMR (564.6 MHz, C
6
D
6
)
d
ꢁ111.47 (s); IR
ꢁ1
film, cm ): 2850, 1599, 1507, 1305, 1163, 1142, 829, 772; HRMS
þ
þ
þ
ESI ): Calcd for
C
21
H28FO
3
SSi [MþH] : 407.15070; Found:
6 6
of chloroform-d and 128.39 ppm of C D . Phosphorus 31 nuclear
07.15066.
31
magnetic resonance spectroscopy ( P NMR) was recorded on
Brucker Avance 243 MHz and phosphoric acid was used as external
standard. Infrared (IR) spectra were recorded on Thermo Scientific
4
.2.4. {[(2Z)-3-(benzenesulfonyl)-2-(4-chlorophenyl)prop-2-en-1-
yl]oxy}(tert-butyl)di-methylsilane (4d)
ꢁ1
Nicolet iS50. Frequencies are given in reciprocal centimeters (cm
)
Eluent Hexane/Ethyl acetate. White solid (45 mg, 53%), Melting
and only selected absorptions are reported. High resolution mass
spectra were obtained by using Thermo Scientific Q Exactive (API or
ESI as ion source) Melting points was measured using RD-II man-
ufactured by Tianjin optical instrument factory.
ꢀ
1
point 112e113 C; H NMR (600 MHz, C
6
D
6
)
d
7.92 (2H, d, J ¼ 6 Hz),
6
0
1
.99e6.94 (5H, m), 6.81 (2H, d, J ¼ 6 Hz), 6.30 (1H, s), 5.18 (2H, s),
13
6 6
.79 (9H, s), 0.02 (6H, s); C NMR (150 MHz, C D ) d 154.20, 143.06,
36.43, 135.93, 133.51, 129.80, 129.68, 129.24, 128.91, 128.68, 127.95,
ꢁ
1
5
8.69, 26.14, 18.64, ꢁ4.90; IR (film, cm ): 2855, 1597, 1489, 1142,
4
.2. General procedure for the palladium catalyzed cascade
reaction to produce compounds 4 (Scheme 2)
þ
þ
þ
1
4
4
082, 809, 687; HRMS (ESI ): Calcd for C21
H28ClO
3
SSi [MþH] :
35
3
5
37
23.12114 [Cl ], 425.11819 [Cl ]; Found: 423.12084 [Cl ],
25.11727 [Cl37].
In an N
ꢂ0.1 ppm, to an oven-dried screw-capped vial was added
Pd(MeCN) ](OTf) (5.3 mg, 5 mol%), Xantphos (5.5 mg, 5 mol%),
CO (55 mg, 2 eq.), boronic acids 3a (53 mg, 1.5 eq.) and THF
2
-filled glove box with oxygen and water levels
[
K
4
2
4.2.5. {[(2Z)-3-(benzenesulfonyl)-2-(4-bromophenyl)prop-2-en-1-
yl]oxy}(tert-butyl)di-methylsilane (4e)
2
3
(
(
3 mL), then allene 1a (36 mg, 0.2 mmol) and aryl iodide 2
0.24 mmol, 1.2 eq.) were also added to the suspension. The joint
Eluent Hexane/Ethyl acetate. White solid (48 mg, 52%), Melting
ꢀ
1
point 83e85 C; H NMR (600 MHz, C
7.13 (2H, d, J ¼ 6 Hz), 6.95e6.93 (3H, m), 6.73 (2H, d, J ¼ 6 Hz), 6.29
6
D
6
)
d
7.91 (2H, d, J ¼ 6 Hz),
position between the vial and cap was sealed with electrical tape to
and the vial was heated to 70 C with stirring using an aluminum
ꢀ
13
(1H, s), 5.18 (2H, s), 0.79 (9H, s), 0.01 (6H, s); C NMR (150 MHz,
heating plate outside of the glove box for 13e15 h. The reaction was
monitored by TLC (Hexane/Ethyl acetate ¼ 2:1) to show that the
allyl alcohol precursor had formed completely. Then, imidazole (8
eq. 108 mg) and TBSCl (3 eq. 90 mg) were added into the vial under
air and stirred for another 2 h at room temperature, which was
6 6
C D ) d 154.26, 143.05, 136.90, 133.49, 131.89, 130.01, 129.66, 129.25,
ꢁ
1
128.68, 127.95, 124.24, 58.66, 26.07, 18.58, ꢁ4.91; IR (film, cm ):
þ
2855, 1598, 1485, 1141, 1125, 853, 790; HRMS (ESI ): Calcd for
þ
þ
79
81
C
21
H
28BrO
3
SSi [MþH] : 467.07063 [Br ], 469.06858 [Br ];
79 81
Found: 467.07039 [Br ], 469.06806 [Br ].

T. Bai et al. / Tetrahedron 73 (2017) 5784e5793
5789
þ
SSi [MþH]þ: 403.17577; Found:
þ
4
1
.2.6. {[(2Z)-3-(benzenesulfonyl)-2-(4-tert-butylphenyl)prop-2-en-
-yl]oxy}(tert-butyl)-dimethylsilane (4f)
Eluent Hexane/Ethyl acetate. Colorless oil (65 mg, 73%); H NMR
600 MHz, C 7.98e7.95 (2H, m), 7.18e7.12 (4H, m), 7.01e6.97
3H, m), 6.51 (1H, s), 5.30 (2H, s), 1.15 (9H, s), 0.82 (9H, s), 0.06 (6H,
(ESI ): Calcd for
403.17565.
22 31 3
C H O
1
(
(
6
D
6
)
d
4.2.12. {[(2Z)-3-(4-methoxybenzenesulfonyl)-2-phenylprop-2-en-
1-yl]oxy}tert-butyldi-methylsilane (4l)
Eluent Hexane/Ethyl acetate; White solid (48 mg, 57%), Melting
point 56e58 C; H NMR (600 MHz, C
13
s); C NMR (150 MHz, C
6
D
6
)
d
155.47, 153.13, 143.47, 135.37, 133.32,
ꢀ
1
129.63, 128.68, 128.30, 127.92, 125.72, 58.92, 34.95, 31.53, 26.22,
6
D
6
)
d
7.91 (2H, d, J ¼ 6 Hz),
ꢁ
1
1
8.66, ꢁ4.81; IR (neat, cm ): 2961, 1598, 1300, 1148, 1112, 857, 755;
7.14 (2H, d, J ¼ 6 Hz), 7.05e6.98 (3H, m), 6.56 (2H, d, J ¼ 6 Hz), 6.48
þ
þ
þ
13
HRMS (ESI ): Calcd for C25
H
37
O
3
SSi [MþH] : 445.22272; Found:
(1H, s), 5.33 (2H, s), 3.11 (3H, s), 0.81 (9H, s), 0.07 (6H, s); C NMR
4
45.22280.
(150 MHz, C
6 6
D ) d 163.94, 154.55, 138.55, 134.97, 130.25, 129.76,
1
29.67, 128.70, 128.44, 114.97, 58.89, 55.40, 26.21, 18.62, ꢁ4.82; IR
ꢁ1
4.2.7. {[(2Z)-3-(benzenesulfonyl)-2-(3-methylphenyl)prop-2-en-1-
(neat, cm ): 2928, 1594, 1497, 1257, 1141, 1084, 831, 776; HRMS
(ESI ): Calcd for
419.17058.
þ
þ
þ
yl]oxy}(tert-butyl)di-methylsilane (4g)
Eluent Hexane/Ethyl acetate. Colorless oil (48 mg, 59%); H NMR
600 MHz, C 7.96e7.93 (2H, m), 7.04e6.94 (6H, m), 6,90e6.86
1H, m), 6.48 (1H, s), 5.28 (2H, s), 2.02 (3H, s), 0.81 (9H, s), 0.04 (6H,
C
22
H
31
O
4
SSi [MþH] : 419.17068; Found:
1
(
(
6 6
D ) d
4.2.13. {[(2Z)-3-(4-bromobenzenesulfonyl)-2-phenylprop-2-en-1-
yl]oxy}(tert-butyl)dime-thylsilane (4m)
13
s); C NMR (150 MHz, C
6 6
D ) d 155.84, 143.35, 138.21, 138.19, 133.37,
1
30.62, 129.63, 129.11, 128.86, 128.69, 127.93, 125.60, 59.00, 26.20,
Eluent Hexane/Ethyl acetate; White solid (33 mg, 35%), Melting
ꢁ
1
ꢀ
1
2
1.54, 18.63, ꢁ4.86; IR (neat, cm ): 2855, 1599, 1305, 1254, 1147,
point 52e53 C; H NMR (600 MHz, C
6
D
6
)
d
7.56 (2H, d, J ¼ 6 Hz),
þ
þ
þ
1083, 834, 811; HRMS (ESI ): Calcd for C22
H
31
O
3
SSi [MþH] :
7.11 (2H, d, J ¼ 6 Hz), 7.06 (2H, d, J ¼ 6 Hz), 7.03e6.98 (3H, m), 6.31
13
4
03.17577; Found: 403.17595.
(1H, s), 5.20 (2H, s), 0.79 (9H, s), 0.02 (6H, s); C NMR (150 MHz,
156.15, 142.03, 138.13, 132.91, 129.98, 129.45, 128.77, 128.68,
6 6
C D ) d
ꢁ1
4.2.8. {[(2Z)-3-(benzenesulfonyl)-2-(3-chlorophenyl)prop-2-en-1-
58.85, 26.15, 18.59, ꢁ4.90; IR (neat, cm ): 2932, 1601, 1574, 1306,
þ
þ
þ
79
yl]oxy}(tert-butyl)di-methylsilane (4h)
Eluent Hexane/Ethyl acetate. Colorless oil (42 mg, 50%); H NMR
600 MHz, C
7.90 (2H, d, J ¼ 6 Hz), 7.25 (1H, s), 7.01e6.93 (4H,
m), 6.76 (1H, d, J ¼ 6 Hz), 6.68 (1H, t, J ¼ 6 Hz), 6.30 (1H, s), 5.15 (2H,
1146, 1084, 1009; HRMS (ESI ): Calcd for C21
H28BrO
3
SSi [MþH] :
1
79
81
467.07063 [Br ], 469.06858 [Br ]; Found: 467.07063 [Br ],
(
6 6
D ) d
469.06832 [Br81].
13
s), 0.79 (9H, s), 0.00 (6H, s); C NMR (150 MHz, C
6
D
6
)
d
154.07,
4.2.14. 2-Ethoxy-4-phenyl-2,5-dihydro-1,2-oxaphosphole 2-oxide
13
142.90, 139.96, 134.71, 133.54, 129.98, 129.82, 129.68, 128.71, 127.96,
(4n, eq. 1)
ꢁ
1
1
1
26.44, 58.85, 26.13, 18.54, ꢁ4.97; IR (neat, cm ): 2855, 1471, 1446,
The title compound was prepared according to the general
procedure and there is no need to add imidazole/TBSCl for the
þ
306, 1254, 1147, 1083, 775, 686; HRMS (ESI ): Calcd for
þ
þ
35
37
C
21
H28ClO
3
SSi [MþH] : 423.12114 [Cl ], 425.11819 [Cl ]; Found:
synthesis of cyclic products. Eluent Hexane/Ethyl acetate; White
35
37
1
4
23.12107 [Cl ], 425.11755 [Cl ].
solid (27 mg, 61%); H NMR (600 MHz, CDCl
3
)
d
7.43e7.38 (m, 5H),
6
.34 (1H, d, J (PH) ¼ 30 Hz), 5.13e5.02 (2H, m), 4.13 (2H, q, J ¼ 6 Hz),
13
4
1
.2.9. {[(2Z)-3-(benzenesulfonyl)-2-(3-methoxyphenyl)prop-2-en-
1.33 (3H, t, J ¼ 6 Hz); C NMR (150 MHz, CDCl
3
) d 158.35 (d,
-yl]oxy}(tert-butyl)di-methylsilane (4i)
J(PC) ¼ 21 Hz), 131.53 (d, J(PC) ¼ 21 Hz), 131.19, 129.30, 126.05,
1
Eluent Hexane/Ethyl acetate. Colorless oil (42 mg, 50%); H NMR
108.84 (d, J(PC) ¼ 171 Hz), 70.27 (d, J(PC) ¼ 9 Hz), 63.34 (d,
3
1
(
(
(
600 MHz, C
6
D
6
)
d
7.93 (2H, d, J ¼ 6 Hz), 6.98e6.91 (5H, m), 6.75
J(PC) ¼ 6 Hz), 16.63; P NMR (243 MHz, CDCl
3
) d 43.72 (s).
1H, d, J ¼ 6 Hz), 6.70 (1H, d, J ¼ 6 Hz), 6.50 (1H, s), 5.26 (2H, s), 3.26
1
3
4.2.15. 4-Phenyl-2,5-dihydrofuran-2-one (4o, eq. 2)14
3H, s), 0.82 (9H, s), 0.05 (6H, s); C NMR (150 MHz, C
6 6
D ) d 160.32,
1
55.43, 143.22, 139.78, 133.37, 129.82, 129.63, 129.25, 127.94, 120.70,
The title compound was prepared according to the general
procedure and there is no need to add imidazole/TBSCl for the
synthesis of cyclic products. Eluent: Hexane/Ethyl acetate; White
ꢁ1
1
15.69, 114.04, 59.05, 55.17, 26.23, 18.56, ꢁ4.86; IR (neat, cm ):
þ
2
928, 1575, 1485, 1289, 1170, 835, 776; HRMS (ESI ): Calcd for
þ
þ
1
C
22 31
H O
4
SSi [MþH] : 419.17068; Found: 419.17075.
Solid (27 mg, 75%); H NMR (600 MHz, CDCl
6
3
)
d
7.51e7.42 (5H, m),
174.05, 164.11,
13
.35 (1H, s), 5.20 (2H, s); C NMR (150 MHz, CDCl
131.96, 129.80, 129.47, 126.62, 113.18, 71.19; IR (neat, cm ): 3500,
3
)
d
ꢁ1
4.2.10. {[(2Z)-3-(benzenesulfonyl)-2-(3,5-dimethylphenyl)prop-2-
þ
en-1-yl]oxy}(tert-butyl)-dimethylsilane (4j)
Eluent Hexane/Ethyl acetate; Colorless oil (47 mg, 56%); H NMR
600 MHz, C 7.98e7.94 (2H, m), 6.96 (3H, s), 6.88 (2H, s), 6.71
1H, s), 6.54 (1H, s), 5.30 (2H, s), 2.04 (6H, s), 0.77 (9H, s), 0.05 (6H,
1597, 1443, 1301, 1174, 1082, 1033, 836, 771; HRMS (ESI ): Calcd for
1
þ
þ
C
15
H
15
O
3
S
[MþH] : 275.07364; Found: 275.07338.
(
(
6 6
D ) d
4.2.16. (2Z)-3-(diphenylphosphoroso)-2-phenylprop-2-en-1-ol (4p,
eq. 3)
13
s); C NMR (150 MHz, C
6
D
6
)
d
155.99, 143.45, 138.23, 138.08,
1
33.29, 131.59, 129.62, 128.74, 127.92, 126.31, 59.11, 26.21, 21.48,
ꢁ
1
1
8.65, ꢁ4.85; IR (neat, cm ): 2885, 1595, 1306, 1254, 1147, 1101,
þ
þ
þ
1083, 835, 776; HRMS (ESI ): Calcd for C23
H O
33 3
SSi [MþH] :
417.19142; Found: 417.19104.
4.2.11. {[(2Z)-3-(4-methylbenzenesulfonyl)-2-phenylprop-2-en-1-
yl]oxy}tert-butyldi-methyl silane (4k)
Eluent Hexane/Ethyl acetate; White solid (53 mg, 66%), Melting
ꢀ
1
point 92e93 C; H NMR (600 MHz, C
7
(
6
D
6
)
d
7.88 (2H, d, J ¼ 6 Hz),
The procedure was the same as the general procedure above.
.12 (2H, d, J ¼ 6 Hz), 7.05e6.97 (3H, m), 6.83 (2H, d, J ¼ 6 Hz), 6.46
The amount of boronic acid 3a was increased to 2 eq. and the re-
13
ꢀ
1H, s), 5.30 (2H, s), 1.90 (3H, s), 0.80 (9H, s), 0.04 (6H, s); C NMR
150 MHz, C 155.14, 144.34, 140.46, 138.23, 130.34, 129.74,
29.38, 128.71, 128.43, 128.08, 58.88, 26.20, 21.54, 18.61, ꢁ4.85; IR
action temperature was decreased to 65 C to obtain higher yield.
(
6
D
6
)
d
The solid phase of product contains 4p confirmed by X-ray crys-
tallography (see SI for detail), however, both 4p and 4p’ exist in the
solution phase, the ratio of them is confirmed as 6.43:1 (4p/4p’) by
1
(
ꢁ
1
neat, cm ): 2854, 1598, 1313, 1299, 1139, 1078, 809, 781; HRMS

5790
T. Bai et al. / Tetrahedron 73 (2017) 5784e5793
the integration of 31P NMR in CDCl
White Solid (47 mg, 67%); Melting Point: 122e123 C; H NMR
600 MHz, CDCl
. Eluent: Hexane/Ethyl acetate;
suspension. The joint position between the vial and cap was sealed
with electrical tape and the vial was heated to 70 C with stirring
3
ꢀ
1
ꢀ
(
3
)
d
7.75 (4H, t, J(PH) ¼ 12 Hz), 7.55e7.43 (6H, m),
using an aluminum heating plate outside of the glove box for 13 h.
The reaction was monitored by TLC (Hexane/Ethyl acetate ¼ 2:1).
Upon completion of the reaction, imidazole (8 eq. 108 mg) and
TBSCl (3 eq. 90 mg) were added into the vial under air and stirred
for another 2 h at room temperature. This protection step was also
monitored by TLC (Hexane/Ethyl acetate ¼ 7:1) to confirm
completion of the formation of the TBS-protected allyl alcohol 4a.
The product was isolated and purified by short column chroma-
tography (Hexane/Ethyl acetate ¼ 20:1) to yield pure product of 4a
(62 mg, 80%). NMR data for this material was the same as above.
7
0
4
.36 (2H, d, J ¼ 6 Hz), 7.15 (2H, d, J ¼ 6 Hz), 6.31 (minor isomer,
.09 H, d, J(PH) ¼ 24 Hz), 6.29 (1H, d, J(PH) ¼ 24 Hz), 5.75 (1H, br s),
13
3
.72 (2H, s), 2.33 (3H, s); C NMR (150 MHz, CDCl ) d 164.38 (minor
isomer), 164.25, 140.99 (minor isomer, d, J(PC) ¼ 16.5 Hz), 139.67,
38.00 (d, J(PC) ¼ 16.5 Hz), 133.88, 133.73 (minor isomer), 133.17,
33.02 (minor isomer), 132.18 (minor isomer, d, J(PC) ¼ 3.0 Hz),
32.12 (d, J(PC) ¼ 3.0 Hz), 131.30, 131.24, 129.49, 129.44 (minor
isomer), 128.96 (minor isomer), 128.93, 128.88 (minor isomer),
28.85, 128.81 (minor isomer), 126.64 (minor isomer), 126.57,
19.50 (minor isomer, d, J(PC) 100.5 Hz), 118.44 (d,
J(PC) ¼ 100.5 Hz), 63.54 (minor isomer, d, J(PC) ¼ 6.0 Hz), 63.45 (d,
1
1
1
1
1
¼
4.4. General procedure for substrate scope employing different
nucleophiles containing carboxylic acids and amides (Schemes 4
and 5)
3
1
J(PC) ¼ 6.0 Hz), 21.37; P NMR (243 MHz, CDCl
3
) d 23.99 (major
isomer, s), 23.86 (minor isomer, s), the ratio of major isomer and
minor isomer is confirmed by the integration of P NMR as 6.43:1; IR
film, cm ): 3365, 1594, 1456, 1170, 1071, 851, 822, 751; HRMS
31
ꢁ
1
(
(
In an N
ꢂ0.1 ppm, to an oven-dried screw-capped vial were added (Xant-
phos)Pd(Ph)I (8.8 mg, 5 mol%), K CO (55 mg, 0.4 mmol, 2.0 eq.),
2
-filled glove box with oxygen and water levels
þ
þ
ESI ): Calcd for
C
22
H
22
O
2
Pþ [MþH] : 349.13519; Found:
3
49.13530.
2
3
carboxylic acid or amide (0.4 mmol, 2.0 eq.) and THF (3 mL), then
allene 1a (36 mg, 0.2 mmol) and Aryl iodide 2 (0.24 mmol, 1.2 eq.)
were also added to the suspension. The joint position between the
vial and cap was sealed with electrical tape and the reaction vial
4
.3. Procedure for isolation of complex 8 and its catalytic reactivity
(Scheme 3 and eq. 4)
ꢀ
4
.3.1. Procedure for isolation of complex 8 (Scheme 3)
was heated to 70 C with stirring using an aluminum heating plate
In glove box, to an oven-dried screw-capped vial was added
outside of the glove box for 13 h. The reaction was monitored by
complex 7 (0.033 mmol, 30 mg), CH
lution. Then allene compound 1a (7.2 mg, 1.2 eq.) dissolved in 1 mL
of CH Cl was added slowly into the stirred solution above. The
2
Cl
2
(3 mL) to get yellow so-
TLC (Hexane/Ethyl acetate ¼ 5:1) The product was isolated and
purified
by
column
chromatography
(Hexane/Ethyl
2
2
acetate ¼ 20:1e10:1) to yield pure product.
color of the reaction mixture changed to deep red immediately.
After 4 h, silver tetrafluoroborate (6.4 mg, 1 eq.) was added into the
reaction solution and the color changed to yellow slowly with
brown precipitate generated at the same time. After stirring for
another 5 h at room temperature, the suspension was worked up
first by filtration The filtrate was concentrated to ca. 0.5 mL, then
diethyl ether (5 mL) was added to afford the yellow precipitate. The
solid was collected and was washed with diethyl ether (2 mL ꢃ 3).
4.4.1. (2Z)-3-(benzenesulfonyl)-2-phenylprop-2-en-1-yl acetate
(6a)
The KOAc (39 mg, 0.4 mmol, 2 eq.) was used directly; Eluent:
Hexane/Ethyl acetate (10:1); Colorless oil (41 mg, 64%); The NMR
data is matched with above.
4.4.2. (2Z)-3-(benzenesulfonyl)-2-phenylprop-2-en-1-yl-2,2-
dimethyl-propanoate (6aa)
After drying, light yellow solid was obtained. Yellow solid (25 mg,
1
7
(
7
6
(
(
0%); H NMR (600 MHz, CDCl
3
)
d
7.69 (d, 1H, J(PH) ¼ 12 Hz), 7.64
Eluent: Hexane/Ethyl acetate (20:1); White solid (42 mg, 59%);
ꢀ
1
d, 1H, J(PH) ¼ 12 Hz), 7.60e7.49 (m, 8H), 7.48e7.43 (m, 7H),
.42e7.34 (m, 5H), 7.31 (t, 2H, J ¼ 6 Hz), 7.23e7.14 (m, 6H),
.92e6.85 (m, 4H), 6.65 (t, 2H, J ¼ 6 Hz), 5.32 (d, 1H, J ¼ 6 Hz), 4.98
Melting Point: 90e91 C; H NMR (600 MHz, CDCl
3
) d 8.00 (2H, d,
J ¼ 6 Hz), 7.63 (1H, t, J ¼ 6 Hz), 7.56 (2H, t, J ¼ 6 Hz), 7.35e7.29 (3H,
1
3
m), 7.25 (2H, d, J ¼ 6 Hz), 6.50 (1H, s), 5.63 (2H, s), 0.90 (9H, s);
NMR (151 MHz, CDCl 177.76, 152.15, 141.42, 136.54, 133.83,
130.05, 129.62, 129.61, 128.73, 127.69, 127.46, 59.11, 38.73, 26.94; IR
C
13
br s, 1H), 3.97 (br s, 1H), 1.81 (s, 3H), 1.44 (s, 3H); C NMR
150 MHz, CDCl
155.26 (d, J(PC) ¼ 7.6 Hz), 154.98 (d,
3
) d
3
) d
ꢁ1
J(PC) ¼ 7.6 Hz), 140.67 (d, J(PC) ¼ 3.0 Hz), 134.86 (d, J(PC) ¼ 3.0 Hz),
(film, cm ): 3037, 1730, 1601, 1306, 1133, 1081763, 746; HRMS
þ
þ
þ
4
1
(
34.66, 134.56 (d, J(PC) ¼ 3.0 Hz), 133.57 (d, J(PC) ¼ 13.6 Hz), 132.96
(ESI ): Calcd for C20
H26NO
4
S
[MþNH
] : 376.15771; Found:
d, J(PC) ¼ 13.6 Hz), 132.8 (d, J(PC) ¼ 9.0 Hz), 132.73, 132.62 (d,
376.15770.
J(PC) ¼ 24.1 Hz), 132.81 (d, J(PC) ¼ 12.1 Hz), 132.01, 131.73, 131.31 (d,
J(PC) ¼ 3.0 Hz), 130.13 (d, J(PC) ¼ 9.0 Hz), 129.80 (d, J(PC) ¼ 12.1 Hz),
4.4.3. (2Z)-3-(benzenesulfonyl)-2-(4-tert-butylphenyl)prop-2-en-
1
1
(
29.65 (d, J(PC) ¼ 9.0 Hz), 129.66, 129.15, 129.00 (d, J(PC) ¼ 7.6 Hz),
1-yl benzoate (6ab)
1
28.93 (d, J(PC) ¼ 7.6 Hz), 127.92 (d, J(PC) ¼ 43.8 Hz), 126.96, 126.67
Eluent: Hexane/Ethyl acetate (20:1); Oil (49 mg, 57%); H NMR
d, J(PC) ¼ 43.8 Hz), 125.72 (d, J(PC) ¼ 7.6 Hz), 125.39 (d,
(600 MHz, CDCl
3
)
d
8.00 (2H, d, J ¼ 6 Hz), 7.79 (2H, d, J ¼ 6 Hz), 7.56
J(PC) ¼ 7.6 Hz),118.16 (d, J(PC) ¼ 45.3 Hz),115.79 (d, J(PC) ¼ 45.3 Hz),
(1H, t, J ¼ 6 Hz), 7.50e7.47 (3H, m), 7.35 (4H, s), 7.33 (2H, t, J ¼ 6 Hz),
13
9
2
0.61 (d, J(PC) ¼ 40.77 Hz), 77.66 (t, J(PC) ¼ 33.22 Hz), 36.39, 30.85,
6.71 (1H, s), 5.81 (2H, s), 1.25 (9H, s); C NMR (151 MHz, CDCl
166.02, 153.90, 150.04, 141.60, 133.76, 133.70, 133.26, 130.22,
129.83, 129.66, 129.54, 128.41, 127.63, 126.97, 125.96, 59.52, 34.91,
3
)
3
1
5.11; P NMR (243 MHz, CDCl
29.2 Hz); Elemental analysis calcd for
PdSþ2 CH Cl ]: C, 56.10; H, 4.12. Found: C, 56.63; H,
3
)
d
5.03 (d, J (PP) ¼ 29.2 Hz), ꢁ0.15
d
(
[
d, J(PP)
¼
ꢁ1
C
54
H45BF
4
O
3
P
2
2
2
31.23; IR (film, cm ): 2961, 1717, 1265, 1146, 1025, 997; HRMS
þ
þ
þ
4
4
.41.
(ESI ): Calcd for C26
4
H30NO S
[MþNH
] : 452.18901; Found:
452.18888.
4
.3.2. Procedure for catalytic reactivity of complex 8 (eq. 4)
In an N -filled glove box with oxygen and water levels
ꢂ0.1 ppm, to an oven-dried screw-capped vial was added complex
(5.4 mg, 2.5 mol%), K CO (55 mg, 2 eq.), boronic acid 3a (53 mg,
.5 eq.) and THF (3 mL), then allene 1a (36 mg, 0.2 mmol) and
phenyl iodide 2a (0.24 mmol, 49 mg, 1.2 eq.) were also added to the
2
4.4.4. (2Z)-3-(Benzenesulfonyl)-2-(4-chlorophenyl)prop-2-en-1-yl-
4-tert-butylbenzoate (6ac)
8
1
2
3
Eluent: Hexane/Ethyl acetate (15:1); White solid (63 mg, 67%);
ꢀ
1
Melting Point: 61e62 C; H NMR (600 MHz, CDCl
3
) d 8.02 (2H, d,
J ¼ 6 Hz), 7.72 (2H, d, J ¼ 6 Hz), 7.61 (1H, t, J ¼ 6 Hz), 7.55 (2H, t,

T. Bai et al. / Tetrahedron 73 (2017) 5784e5793
5791
J ¼ 6 Hz), 7.35 (2H, d, J ¼ 6 Hz), 7.32 (2H, d, J ¼ 6 Hz), 7.29 (2H, d,
139.76, 136.99, 133.65, 129.43, 129.37, 129.21, 128.50, 128.04, 127.92,
13
ꢁ1
J ¼ 6 Hz), 6.62 (1H, s), 5.81 (2H, s), 1.28 (9H, s); C NMR (151 MHz,
CDCl 165.96,157.21, 149.74,141.22,136.42,135.15,133.96,130.93,
29.70, 129.69, 129.22, 128.68, 127.79, 126.61, 125.56, 59.26, 35.28,
127.79, 127.48, 84.92, 44.8, 27.85, 21.77, 21.48; IR (film, cm ): 2979,
þ
þ
2
3
)
d
1723, 1292, 1144, 1084; HRMS (ESI ): Calcd for C28
35
H N
2
O
6
S
þ
1
[MþNH
4
] : 559.19310; Found: 559.19346.
ꢁ
1
31.24; IR (film, cm ): 2962, 1717, 1307, 1266, 1147, 1083, 1012;
þ
þ
þ
HRMS (ESI ): Calcd for C26
H29ClNO
4
S
[MþNH
4
] : 486.15003
4.4.10. tert-Butyl-N-[(2Z)-3-(Benzenesulfonyl)-2-(3,5-
dimethylphenyl) prop-2-en-1-yl]-N-(4-methylbenzenesulfonyl)
3
5
37
35
37
[Cl ], 488.14708 [Cl ]; Found: 486.15019 [Cl ], 488.14643 [Cl ].
carbamate (6ai)
4
.4.5. (2Z)-3-(Benzenesulfonyl)-2-(4-bromophenyl)prop-2-en-1-
Eluent: Hexane/Ethyl acetate (20:1); White solid (58 mg, 52%);
ꢀ
1
yl-4-tert-butylbenzoate (6ad)
Melting Point: 163e165 C; H NMR (600 MHz, CDCl ) d 8.06 (2H, d,
3
Eluent: Hexane/Ethyl acetate (15:1); White solid (64 mg, 62%);
Melting Point: 62e64 C; H NMR (600 MHz, CDCl ) d 8.01 (2H, d,
3
J ¼ 6 Hz), 7.61 (1H, t, J ¼ 6 Hz), 7.55 (2H, t, J ¼ 6 Hz), 7.47 (2H, t,
J ¼ 6 Hz), 7.16 (2H, d, J ¼ 6 Hz), 6.98 (1H, s), 6.91 (2H, s), 6.26 (1H, s),
ꢀ
1
13
J ¼ 6 Hz), 7.72 (2H, d, J ¼ 6 Hz), 7.61 (1H, t, J ¼ 6 Hz), 7.54 (2H, t,
5.62 (2H, s), 2.38 (3H, s), 2.24 (6H, s), 1.20 (9H, s); C NMR
J ¼ 6 Hz), 7.44 (2H, d, J ¼ 6 Hz), 7.35 (2H, d, J ¼ 6 Hz), 7.24 (2H, d,
3
(151 MHz, CDCl ) d 155.40, 150.89, 144.42, 141.50, 138.18, 137.15,
13
J ¼ 6 Hz), 6.63 (1H, s), 5.81 (2H, s), 1.28 (9H, s); C NMR (151 MHz,
136.92, 133.67, 131.18, 129.46, 129.37, 128.04, 127.83, 127.54, 125.73,
ꢁ1
CDCl
3
)
d
165.94, 157.19, 149.77, 141.17, 135.61, 133.96, 132.16, 130.94,
84.83, 44.81, 27.85, 21.79, 21.36; IR (film, cm ): 2917, 1734, 1347,
þ
þ
þ
4
1
3
(
5
29.69, 129.68, 128.88, 127.78, 126.58, 125.55, 124.71, 59.20, 35.26,
1161, 1083; HRMS (ESI ): Calcd for C29
H
37
N
2
O
6
S
2
[MþNH
] :
ꢁ1
1.23; IR (film, cm ): 2961, 1716, 1608, 1266, 773, 721; HRMS
573.20875; Found: 573.20906.
þ
þ
þ
79
ESI ): Calcd for C26
H
29BrNO
4
S
[MþNH
4
] : 530.09952 [Br ],
32.09747 [Br81]; Found: 530.09878 [Br ], 532.09643 [Br ].
79
81
4.4.11. 2-[(2Z)-3-(Benzenesulfonyl)-2-(3,5-dimethylphenyl)prop-2-
en-1-yl]-2,3-dihydro-1H-isoindole-1,3-dione (6aj)
4
4
.4.6. (2Z)-3-(Benzenesulfonyl)-2-(3-chlorophenyl)prop-2-en-1-yl-
Eluent: Hexane/Ethyl acetate (20:1); White solid (40 mg, 46%);
ꢀ
1
-tert-butylbenzoate (6ae)
Eluent: Hexane/Ethyl acetate (15:1); Oil (56 mg, 60%); H NMR
Melting Point: 168e170 C; H NMR (600 MHz, CDCl
3
) d 8.14 (2H, d,
1
J ¼ 6 Hz), 7.70e7.67 (2H, m), 7.61 (1H, t, J ¼ 6 Hz), 7.63e7.58 (4H, m),
13
(
(
(
600 MHz, CDCl
3
)
d
8.02 (2H, d, J ¼ 6 Hz), 7.72 (2H, d, J ¼ 6 Hz), 7.62
6.83 (2H, s), 6.81 (1H, s), 6.44 (1H, s), 5.47 (2H, s), 2.14 (6H, s);
NMR (151 MHz, CDCl 167.73, 152.24, 141.32, 138.32, 136.40,
134.14, 133.78, 131.81, 131.68, 129.52, 129.16, 127.90, 124.86, 123.41,
C
1H, t, J ¼ 6 Hz), 7.55 (2H, t, J ¼ 6 Hz), 7.38e7.29 (4H, m), 7.27e7.25
3
) d
13
2H, m), 6.63 (1H, s), 5.81 (2H, s), 1.28 (9H, s); C NMR (151 MHz,
165.93,157.16,149.50,140.06,138.58,134.91,134.01,131.55,
30.19, 129.70, 127.82, 127.45, 126.61, 125.53, 59.39, 35.26, 31.23; IR
ꢁ1
CDCl
1
3
)
d
35.85, 21.23; IR (film, cm ): 3017, 1770, 1715, 751, 715; HRMS
þ
þ
þ
4
(ESI ): Calcd for C25
25
H N
2
O
4
S
[MþNH
] : 449.15295; Found:
ꢁ
1
þ
(film, cm ): 2962, 1717, 1608, 853, 719; HRMS (ESI ): Calcd for
449.15215.
þ
þ
35
37
C
26
H
29ClNO
4
S
[MþNH
4
] : 486.15003 [Cl ], 488.14708 [Cl ];
3
5
37
Found: 486.15022 [Cl ], 488.14635 [Cl ].
4.5. General procedure for the study of allylic alcohol derivation to
synthesize compounds (5a-5b, 6a-6d, Scheme 6)
4
1
.4.7. (2Z)-3-(Benzenesulfonyl)-2-(3,5-dimethylphenyl)prop-2-en-
-yl benzoate (6af)
Eluent: Hexane/Ethyl acetate (20:1); Oil (57 mg, 70%); H NMR
4.5.1. (2Z)-3-(benzenesulfonyl)-2-phenylprop-2-en-1-ol (5a)
1
To an oven-dried screw-capped vial was added 4a (0.2 mmol,
77 mg), KF (23 mg, 2 eq.) and MeCN (3 mL), then TMSCl (21 mg, 1
eq.) was added into the white suspension. The mixture was stirred
at room temperature and monitored by TLC (Hexane/Ethyl
acetate ¼ 2/1). After completion of the reaction, all of the volatiles
were removed by rotary evaporation and the residue was purified
by column chromatography to yield pure product 5a as white solid
(
600 MHz, CDCl
3
)
d
8.00 (2H, d, J ¼ 6 Hz), 7.80 (2H, d, J ¼ 6 Hz), 7.58
(
6
1H, t, J ¼ 6 Hz), 7.54e7.46 (3H, m), 7.34 (2H, t, J ¼ 6 Hz), 6.99 (2H, s),
13
.97 (1H, s), 6.65 (1H, s), 5.79 (2H, s), 2.25 (6H, s); C NMR
166.06, 150.88, 141.56, 138.55, 136.74, 133.74,
33.27, 132.00, 130.38, 129.82, 129.71, 129.57, 128.45, 127.69, 125.04,
(
3
151 MHz, CDCl ) d
1
5
ꢁ1
9.8, 21.39; IR (film, cm ): 2918, 1717, 1599, 1308, 1263, 1146;
þ
þ
þ
ꢀ
1
HRMS (ESI ): Calcd for C24
Found: 424.15760.
H26NO
4
S
[MþNH
4
] : 424.15771;
(50 mg, 91%). Melting point: 82e83 C; H NMR (600 MHz, C
6
D
6
)
d
7.86e7.82 (2H, m), 7.05e7.03 (2H, m), 7.01e6.88 (6H, m), 6.40 (1H,
13
s), 4.76 (2H, d, J ¼ 6 Hz), 2.98 (1H, br s); C NMR (150 MHz, C
6
D
6
)
4
1
.4.8. (2Z)-3-(Benzenesulfonyl)-2-(3,5-dimethylphenyl)prop-2-en-
d 156.04, 142.71, 138.87, 133.52, 130.09, 130.07, 129.69, 129.13,
ꢁ
1
-yl-4-methoxybenzo-ate (6ag)
Eluent: Hexane/Ethyl acetate (20:1); Oil (64 mg, 73%); H NMR
128.68, 127.92, 127.63, 60.29; IR (neat, cm ): 3500, 1597, 1443,
1301, 1174, 1082, 1033, 836, 771; HRMS (ESI ): Calcd for C15
[MþH] : 275.07364; Found: 275.07338.
1
þ
þ
3
H
15
O
S
þ
(
(
(
600 MHz, CDCl
3
)
d
8.00 (2H, d, J ¼ 6 Hz), 7.75 (2H, d, J ¼ 6 Hz), 7.58
1H, t, J ¼ 6 Hz), 7.51 (2H, t, J ¼ 6 Hz), 6.98 (2H, s), 6.97 (1H, s), 6.81
2H, d, J ¼ 6 Hz), 6.64 (1H, s), 5.75 (2H, s), 3.80 (3H, s), 2.24 (6H, s);
4.5.2. [(1Z)-1-(benzenesulfonyl)-3-bromoprop-1-en-2-yl] benzene
(5b)
13
C NMR (151 MHz, CDCl
3
)
d
165.76, 163.64, 151.17, 141.60, 138.50,
1
36.80, 133.70, 131.95, 131.89, 130.24, 129.55, 127.68, 125.05, 122.06,
To an oven-dried screw-capped vial was added 5a (0.1 mmol,
27 mg), PPh (52 mg, 2 eq.), DDQ (45 mg, 2 eq.) and CH Cl (3 mL)
followed by addition of TBAB (96 mg, 1.5 eq.). The mixture was
stirred at room temperature and monitored by TLC (Hexane/Ethyl
acetate ¼ 2/1). After completion of the reaction, volatiles were
removed by rotary evaporation and the residue was purified by
ꢁ1
113.70, 59.53, 55.57, 21.39; IR (film, cm ): 2918, 1711, 1604, 1252,
3
2
2
þ
þ
þ
4
1146, 1025; HRMS (ESI ): Calcd for C25
H28NO
5
S
[MþNH
] :
4
54.16827; Found: 454.16823.
4.4.9. tert-Butyl-N-[(2Z)-3-(benzenesulfonyl)-2-(4-methylphenyl)-
prop -2-en-1-yl]-N-(4-methylbenzenesulfonyl) carbamate (6ah)
column chromatography to yield pure product 5b as colorless oil
1
Eluent: Hexane/Ethyl acetate (20:1); White solid (54 mg, 50%);
(28 mg, 83%). H NMR (600 MHz, C
6
D
6
)
d
8.00e7.97 (2H, m),
ꢀ
1
13
Melting Point: 69e70 C; H NMR (600 MHz, CDCl
3
)
d
8.06 (2H, d,
6.99e6.92 (4H, m), 6.91e6.84 (4H, m), 6.34 (1H, s), 4.79 (2H, s);
NMR (150 MHz, C 150.32, 142.28, 137.73, 133.71, 130.40,
130.24, 129.71, 129.19, 128.68, 127.40, 25.09; IR (neat, cm ): 1597,
C
J ¼ 6 Hz), 7.61 (1H, t, J ¼ 6 Hz), 7.54 (2H, t, J ¼ 6 Hz), 7.52 (2H, t,
J ¼ 6 Hz), 7.21 (2H, t, J ¼ 6 Hz), 7.18 (2H, t, J ¼ 6 Hz), 7.11 (2H, t,
J ¼ 6 Hz), 6.25 (1H, s), 5.63 (2H, s), 2.39 (3H, s), 2.33 (3H, s), 1.21 (9H,
6 6
D ) d
ꢁ1
þ
þ
2
S
1445, 1304, 1083, 806; HRMS (ESI ): Calcd for C15
H14BrO
13
þ
79
81
3
s); C NMR (151 MHz, CDCl ) d 155.09, 150.85, 144.48, 141.43,
[MþH] : 336.98924[Br ], 338.98719[Br ]; Found: 336.98928

5792
T. Bai et al. / Tetrahedron 73 (2017) 5784e5793
[
Br79], 338.98725[Br81].
(1H, t, J ¼ 6 Hz), 7.54 (2H, t, J ¼ 6 Hz), 7.37e7.30 (5H, m), 7.11 (2H, t,
J ¼ 6 Hz), 6.71 (1H, t, J ¼ 6 Hz), 6.63 (1H, s), 6.54 (2H, d, J ¼ 6 Hz),
13
4
(
.5.3. (2Z)-3-(benzenesulfonyl)-2-phenylprop-2-en-1-yl acetate
6a)
To an oven-dried screw-capped vial was added 5a (0.35 mmol,
7 mg), Et N (42 mg, 1.2 eq.) and CH Cl (3 mL) followed by slow
4.67 (2H, s), 3.82 (1H, br, s); C NMR (150 MHz, CDCl
3
) d 154.50,
147.40, 141.72, 138.03, 133.78, 130.23, 130.16, 129.62, 129.36, 129.06,
ꢁ
1
127.59, 127.07, 118.47, 113.75, 42.65; IR (film, cm ): 3383, 1601,
þ
þ
þ
9
3
2
2
1506, 1297, 1133; HRMS (ESI ): Calcd for C21
H20NO
2
S
[MþH] :
addition of AcCl (30 mg, 1.1 eq.). The mixture was stirred at room
temperature and monitored by TLC (Hexane/Ethyl acetate ¼ 2/1).
After completion of the reaction, volatiles were removed by rotary
evaporation and the residue was purified by column chromatog-
350.12093; Found: 350.12115.
Acknowledgements
1
raphy to yield pure product 6a as colorless oil (108 mg, 98%). H
We would like to acknowledge the overseas high-level talents
program of Shanxi University (112545005 and 112545012) and
Shanxi Scholarship Council of China (112639901001) for financial
support of this research. We also thank Dr. Cao Wei and Prof. Chao
Jianbin in Scientific Instrument Centre, Shanxi University for crystal
structure analysis and running of NMR samples.
NMR (600 MHz, CDCl
.56 (2H, t, J ¼ 6 Hz), 7.39e7.28 (5H, m), 6.57 (2H, s), 5.58 (2H, s),
.86 (3H, s); 13C NMR (150 MHz, C
170.47, 150.85, 141.38,
3
)
d
7.99 (2H, d, J ¼ 6 Hz), 7.63 (1H, t, J ¼ 6 Hz),
7
1
1
2
6 6
D ) d
36.61, 133.86, 130.47, 130.27, 129.60, 128.91, 127.69, 127.28, 59.20,
ꢁ1
þ
0.74; IR (neat, cm ): 1738, 1604, 1445, 1306, 1227; HRMS (ESI ):
þ
þ
Calcd for C17
H16NaO
4
S
[MþNa] : 339.06615; Found: 339.06637.
Appendix A. Supplementary data
4.5.4. 2-[(2E)-3-(benzenesulfonyl)-2-phenylprop-2-en-1-yl]-1,3-di-
tert-butyl propanedioate (6b)
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2017.08.021.
2 3
To an oven-dried screw-capped vial was added Pd (dba)
(
0.0025 mmol, 2.5 mol%, 2.8 mg), PPh
3
(0.015 mmol, 15 mol%,
3
.9 mg), 6a (0.10 mmol, 31 mg), K PO (53 mg, 2.5 eq.), and dry THF
3
4
References
(
2 mL) followed by slow addition of di-tert-butyl propanedioate
(
52 mg, 1.2 eq.) solution in dry THF (1 mL). The mixture was stirred
1
. a) Chen YK, Lurain AE, Walsh PJ. J Am Chem Soc. 2002;49:12225e12231;
b) Yang Y, Zhu SF, Zhou CY, Zhou QL. J Am Chem Soc. 2008;49:14052e14053;
c) Kinoshita H, Uemura R, Fukuda D, Miura K. Org Lett. 2013;15:5538e5541;
d) Kurosawa F, Nakano T, Soeta T, Endo K, Ukaji U. J Org Chem. 2015;80:
ꢀ
at 45 C and monitored by TLC (Hexane/Ethyl acetate ¼ 7/1). After
completion of the reaction, all of the volatiles were removed by
rotary evaporation and the residue was purified by column chro-
matography to yield pure product 6b as white solid (32 mg, 68%).
5696e5703.
2
. a) Thiery E, Aouf C, Belloy J, Harakat D, Bras JL, Muzart J. J Org Chem. 2010;75:
1771e1774;
b) Kiyokawa K, Yahata S, Kojima T, Minakata S. Org Lett. 2014;16:4646e4649;
c) Li J, Tan C, Gong J, Yang Z. Org Lett. 2014;16:5370e5373;
d) Cannon JS, Kirsch SF, Overman LE. J Am Chem Soc. 2010;132:15185e15191.
ꢀ
1
3
Melting point 91e92 C; H NMR (600 MHz, CDCl ) d 7.97 (2H, d,
J ¼ 6 Hz), 7.59 (1H, t, J ¼ 6 Hz), 7.52 (2H, t, J ¼ 6 Hz), 7.35e7.27 (5H,
m), 6.39 (1H, s), 3.60 (2H, d, J ¼ 6 Hz), 3.31 (1H, t, J ¼ 6 Hz), 1.31
(
1
2
18H, s); 13C NMR (150 MHz, CDCl
3
)
d
167.78, 154.95, 141.97, 139.02,
3. a) Trost BM. Chem Rev. 1996;96:395;
b) Leitner A, Shu C, Hartwig JF. Org Lett. 2005;7:1093e1096;
c) Ibrahem I, C
33.53, 129.99, 129.86, 129.47, 128.94, 127.66, 127.34, 81.99, 53.33,
oꢀ rdova A. Angew Chem Int Ed. 2006;45:1952e1956;
ꢁ1
8.71, 27.91; IR (film, cm ): 1740, 1718, 1366, 1274, 1146; HRMS
d) Jellerich BG, Kong J, Krische MJ. J Am Chem Soc. 2003;125:7758e7759.
4. Tsuji J. In: Palladium Reagents and Catalysts: New Perspectives for the 21st Cen-
tury. Weinheim, Germany: Wiley-VCH; 2004.
þ
þ
þ
(
ESI ): Calcd for
C
26
H
32NaO
6
S
[MþH] : 495.18118; Found:
4
95.18149.
5. a) Ma S. Chem Rev. 2005;105:2829;
b) Chang K, Rayabarapu DK, Yang F, Cheng C. J Am Chem Soc. 2005;127:
126e131;
c) Shimizu I, Tsuji J. Chem Lett. 1984:233;
d) Jeganmohan M, Cheng C. Chem Commun. 2008;27:3101e3117.
. a) Yang Z, Hao W, Wang S, et al. J Org Chem. 2015;80:9224e9230;
b) Tsukamoto H, Kondo Y. Org Lett. 2008;10:2633e2636;
c) Chakravarty M, Swamy KC. J Org Chem. 2006;71:9128e9138;
d) Fu C, Ma S. Org Lett. 2005;7:1605e1607.
. a) Pasquale RJL. J Organomet Chem. 1971;32:381e393;
b) Cazes B. Pure Appl Chem. 1990;62:1867;
c) Zimmer R, Dinesh C, Nandanan E, Khan F. Chem Rev. 2000;100:3067.
. a) Miyaura N, Suzuki A. Chem Rev. 1995;95:2457e2483;
b) Suzuki A. Pure Appl Chem. 1991;63:419e422;
4
.5.5. [3-(Benzenesulfonyl)prop-1-en-2-yl]benzene (6c)20
To an oven-dried screw-capped vial was added Pd(OAc)
2
(
(
2
0.005 mmol, 5 mol%, 1.1 mg), 6a (0.10 mmol, 31 mg), B (pin)
0.22 mmol, 2.2 eq., 56 mg) and degassed DMSO (2 mL). The
2
6
ꢀ
mixture was stirred at 60 C and monitored by TLC (Hexane/Ethyl
acetate ¼ 7/1). After completion of the reaction, water (3 mL) was
added into the mixture and extracted with ether (3 mL ꢃ 3), the
organic phase was collected and washed with brine (5 mL). Ether
was removed by rotary evaporation and the residue was purified by
column chromatography to yield pure product 6c as white solid
7
8
c) Lu Z, Wilsily A, Fu GC. J Am Chem Soc. 2011;133:8154e8157.
(
7
19 mg, 74%). 1H NMR (600 MHz, C
.11e7.07 (2H, m), 7.01e6.96 (3H, m), 6.87 (1H, t, J ¼ 6 Hz), 6.79 (2H,
6
D
6
)
d
7.64 (2H, d, J ¼ 6 Hz),
9. a) Bouziane A, Helou M, Carboni B, et al. Chem Eur J. 2008;14:5630e5637;
b) Husinec S, Jadranin M, Markovic R, Petkovic M, Savic V, Todorovic N. Tet-
rahedron Lett. 2010;51:4066e4068;
c) Kobayashi Y, Ikeda E. J Chem Soc Chem Comm. 1994:1789e1790.
10. Porto RS, Vasconcellos MLAA, Ventura E, Coelho F. Synthesis. 2005:2297e2306.
13
t, J ¼ 6 Hz), 5.28 (1H, s), 4.93 (1H, s), 3.86 (2H, s); C NMR (150 MHz,
139.97, 139.76, 137.63, 133.35, 129.27, 129.03, 128.83, 126.96,
21.62, 62.18.
6 6
C D ) d
1
1. a) Kranenburg M, Van der Burgt YEM, Kamer PCJ, Van Leeuwen PWNM. Or-
ganometallics. 1995;14:3081e3089;
1
b) Van Leeuwen PWNM, Kamer PCJ, Reek JNH, Dierkes P. Chem Rev. 2000;100:
2741e2769.
12. Hall DG. Boronic Acids e Preparation and Applications in Organic Synthesis and
Medicine. John Wiley & Sons; 2005.
3. Lv Y, Hu G, Ma D, Liu L, Gao Y, Zhao Y. J Org Chem. 2015;80:6908e6914.
14. Colombe G, Søren K, Yann O, Fabien G. J Am Chem Soc. 2012;134:828e831.
15. Bai T, Xue L, Xue P, et al. Organometallics. 2008;27:2614e2626.
4
(
.5.6. N-[(2Z)-3-(benzenesulfonyl)-2-phenylprop-2-en-1-yl]aniline
6d)
To an oven-dried screw-capped vial was added Pd
0.00375 mmol, 2.5 mol%, 4.3 mg), dppf (0.0075 mmol, 5 mol%,
2
(dba)
3
1
(
4
.0 mg), 6a (0.15 mmol, 48 mg), aniline (0.165 mmol, 1.1 eq.,
ꢀ
16. a) Estrada J, Woen DH, Tham FS, Miyake GM, Lavallo V. Inorg Chem. 2015;54:
15.4 mg) and dry toluene (2 mL). The mixture was stirred at 70 C
5142e5144;
and monitored by TLC (Hexane/Ethyl acetate
¼
7/1). After
b) Yamaguchi Y, Yamanishi K, Kondo M, Tsukada N. Organometallics. 2013;32:
4837e4842;
c) Szab oꢀ KJ. Chem Soc Rev. 2001;30:136e143;
d) Bai T, Ma S, Jia G. Coor Chem Rev. 2009;253:423e448.
7. a) Andersen TL, Friis SD, Audrain H, Nordeman P, Antoni G, Skrydstrup T. J Am
Chem Soc. 2015;137:1548e1555;
completion of the reaction, volatiles were removed by rotary
evaporation and the residue was purified by column chromatog-
raphy to yield pure product 6d as solid (36 mg, 69%). Melting point
1
ꢀ
1
137e138 C; H NMR (600 MHz, CDCl
3
)
d
7.97 (2H, d, J ¼ 6 Hz), 7.63

T. Bai et al. / Tetrahedron 73 (2017) 5784e5793
5793
b) Yin J, Buchwald SL. J Am Chem Soc. 2002;124:6043e6048;
19. Sen SE, Roach SL. Synthesis. 1995:756e758.
c) Mora G, Deschamps B, van Zutphen S, Le Goff XFL, Le Floch RP. Organome-
tallics. 2007;26:1846e1855;
d) Kamer PCJ, Van Leeuwen PWNM, Reek JNH. Acc Chem Res. 2001;34:
20. Peng Y, Li W. Synlett. 2006:1165e1168.
21. Firouzabadi H, Iranpoor N, Sobhani S. Tetrahedron. 2004;60:203e210.
22. Lara MJ, Jonathan W. Adv Synth Catal. 2001;343:75e77.
23. Li X, Xu X, Zhou C. Chem Commun. 2012;48:12240e12242.
24. a) Fors BP, Buchwald SL. J Am Chem Soc. 2010;132:15914e15917;
b) Green RA, Hartwig JF. Org Lett. 2014;16:4388e4392.
895e904.
1
8. There was biphenyl compound 4aa formed as well with 15% yield and there
was no reaction occur without the participation of phenyl iodide. (see SI for full
detail).