Palladium-catalyzed cross-couplings of allylic carbonates with triarylbismuths as multi-coupling atom-efficient organometallic nucleophiles

Article abstract of DOI:10.1016/j.jorganchem.2010.03.010

Allylic carbonates were efficiently cross-coupled with triarylbismuths under palladium catalysis. Using the optimized protocol, arylations of various allylic carbonates were carried out with triarylbismuths to afford high yields of 1,3-disubstituted prope

Full text of DOI:10.1016/j.jorganchem.2010.03.010

Journal of Organometallic Chemistry 695 (2010) 1518–1525
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Palladium-catalyzed cross-couplings of allylic carbonates with triarylbismuths
as multi-coupling atom-efficient organometallic nucleophiles
*
Maddali L.N. Rao , Debasis Banerjee, Somnath Giri
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208 016, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 6 January 2010
Received in revised form 27 February 2010
Accepted 4 March 2010
Available online 10 March 2010
Allylic carbonates were efficiently cross-coupled with triarylbismuths under palladium catalysis. Using
the optimized protocol, arylations of various allylic carbonates were carried out with triarylbismuths
to afford high yields of 1,3-disubstituted propenes in regio- and chemo-selective manner. Triarylbis-
muths were employed as multi-coupling atom-efficient organometallic nucleophiles in sub-stoichiome-
tric amounts in all the reactions.
Ó 2010 Elsevier B.V. All rights reserved.
Keywords:
Triarylbismuths
Palladium
Allylic carbonates
Arylation
Atom-efficient
Cross-coupling
1. Introduction
with triarylbismuths under palladium catalysis [39]. During this
study, a more facile cross-coupling reactivity of allylic acetates in
The metal catalyzed reactions of allylic substrates are useful for
a variety of synthetic transformations [1–10]. The reactivity profile
of allylic carbonates differ from other allylic substrates in coupling
reactions [11–22]. The coupling reaction of allylic carbonate in the
comparison with allylic bromides was observed. This prompted
us to extend this study to allylic carbonate substrates. Herein, we
report the cross-coupling study of allylic carbonates with triaryl-
bismuth under palladium-catalyzed conditions.
presence of palladium catalyst usually involves
p-allylpalla-
dium(II) intermediate species [17] through the initial oxidative
addition of allylic carbonate to Pd(0) with subsequent loss of car-
2. Results and discussion
bon dioxide. The transmetallation of
p-allylpalladium(II) with
The initial studies were carried out using cinnamyl carbonate
and triphenylbismuth as model substrates under different condi-
tions and these studies are summarized in Table 1. The coupling
reaction with cinnamyl carbonate was found to be facile to furnish
the corresponding allylic arylation product, 5.12 as major one
along with minor regio-isomeric compound, 4.12. However, biphe-
nyl was also formed as homo-coupling product from triphenylbis-
muth in minor amounts (Table 1). This was expected as
triarylbismuths were known to give bi-aryls in the presence of pal-
ladium catalyst [36].
The screening carried out with different palladium precursors
using K3PO4 base in N,N-dimethylformamide (DMF) provided mod-
erate conversion to 5.12 (Table 1, entries 1–3). However, the reac-
tion with NEt3 as base delivered somewhat better conversion in
comparison with pyridine (Table 1, entries 4 and 5). Reaction at
90 °C with 1 equiv. of NEt3 furnished 5.12 in 74% isolated yield (Ta-
ble 1, entry 6). This reaction was further tried in different solvents
to improve the cross-coupling yield (Table 1, entries 7–11). From
this, N-Methyl-2-pyrrolidone (NMP) solvent was found to be more
organometallic nucleophile followed by reductive elimination
delivers the cross-coupled product. Here, the utilization of allylic
carbonate as coupling partner is advantageous from the view point
that the in situ formed alkoxide is expected to activate the organo-
metallic reagent during transmetallation step [17]. Thus, allylic
carbonates serve as facile substrates in coupling reactions with
organometallic nucleophiles. The cross-coupling reactions of vari-
ous allylic substrates with organo-boron, -tin, -silicon, -indium,
etc. reagents were reported under palladium-catalyzed conditions
[11–22]. However, recently triarylbismuths have been demon-
strated to be useful as multi-coupling organometallic nucleophiles
for atom-efficient couplings with organic electrophiles [23–36]. In
particular, the palladium-catalyzed cross-couplings of allyl bro-
mide [37,38] with triarylbismuths were reported earlier. Recently,
we have also demonstrated the arylation of various allylic acetates
* Corresponding author. Tel./fax: +91 512 259 7532.
E-mail address: maddali@iitk.ac.in (M.L.N. Rao).
0022-328X/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.03.010

M.L.N. Rao et al. / Journal of Organometallic Chemistry 695 (2010) 1518–1525
1519
Table 1
Screening with cinnamyl carbonate.a–c
Ph
[Pd]
+ BiPh3
OCO2Et
Ph
+
+
Ph
Ph-Ph
Ph
Ph
5.12
1
2
4.12
3
(1 equiv)
(3 equiv)
Entry
Catalytic conditions
1 (%)
2 (%)
3 (%)
4.12 (%)
5.12 (%)
1
2
3
4
5
6
7
8
PdCl2(MeCN)2, K3PO4 (4), DMF, 60 °C, 2.5 h
Pd(PPh3)4, K3PO4(4), DMF, 60 °C, 2.5 h
PdCl2(PPh3)2, K3PO4(4), DMF, 60 °C, 2.5 h
PdCl2(PPh3)2, Et3N (1), DMF, 60 °C, 1 h
PdCl2(PPh3)2, Pyridine (1) DMF, 90 °C, 1 h
PdCl2(PPh3)2, Et3N (1), DMF, 90 °C, 1 h
PdCl2(PPh3)2, Et3N (1), DME, 90 °C, 1 h
PdCl2(PPh3)2, Et3N (1), THF, 90 °C, 1 h
PdCl2(PPh3)2, Et3N (1), MeCN, 90 °C, 1 h
PdCl2(PPh3)2, Et3N (1), DMA, 90 °C, 1 h
PdCl2(PPh3)2, Et3N (1), NMP, 90 °C, 1 h
PdCl2(PPh3)2, Et3N (2), NMP, 90 °C, 1 h
PdCl2(PPh3)2, Et3N (3), NMP, 90 °C, 1 h
No catalyst, Et3N (1), DMF, 90 °C, 1 h
PdCl2(PPh3)2, no base, DMF, 90 °C, 1 h
67
3
23
15
22
–
68
60
19
18
10
5
18
–
–
–
–
9
0
0
0
0
0
2
0
0
4
4
2
3
2
0
0
0
26
66
71
62
78 (74)
0
0
64
32
11
13
16
6
12
7
12
12
5
–
17
30
–
–
–
1
1
–
–
9
10
11
12
13
14
15
65
81(76)
78(71)
79(71)
0
6
8
4
6
4
96
32
43
a
Conditions: BiPh3 (1 equiv., 0.50 mmol), Cinnamyl carbonate (3.5 equiv., 1.75 mmol), base (1–4 equiv.), palladium catalyst (0.09 equiv., 0.045 mmol), solvent (6 mL).
Conversions are based on GC analysis of the crude reaction mixture with respect to triphenylbismuth. Isolated yields are given in parentheses and, considering 3 equiv. of
b
cross-coupling product (1.5 mmol) as 100% yield.
effective in comparison with 1,2-dimethoxyethane (DME), tetrahy-
drofuran (THF), acetonitrile and N,N-dimethylacetamide (DMA)
solvents. At this stage, increase in the amount of NEt3 to 2 or
3 equiv. did not improve the product yield further (Table 1, entries
12 and 13). A control reaction without palladium catalyst did not
furnish allylic arylation product (Table 1, entry 14). Another reac-
tion without NEt3 also furnished lower conversion to 5.12 (Table 1,
entry 15). From the above screening it was found that the reaction
is facile in polar aprotic solvents such as DMF and NMP. Formation
of 4.12 as regio-isomer was also observed under certain conditions
in minor amounts. Overall this investigation revealed that the pro-
tocol involving PdCl2(PPh3)2 catalyst, NEt3 base (1 equiv.) in NMP
solvent at 90 °C is very effective for the facile coupling of cinnamyl
carbonate with triphenylbismuth. Notably, the coupling reaction
was completed in short reaction time affording high yield of aryla-
tion product. Out of DMF and NMP solvents we have chosen NMP
as our choice for further study. In these reactions 3.5 equiv. of cin-
namyl carbonate was employed although 3 equiv. of cinnamyl car-
bonate is sufficient to react with three phenyl groups of
triphenylbismuth. It was also gratifying that triphenylbismuth
was effectively coupled with 3 equiv. of allylic carbonates under
the established protocol.
Table 3. This study revealed an efficient coupling reactivity of var-
ious functionalized allylic carbonates. Importantly, cinnamyl car-
bonates substituted with bromo- and chloro- groups provided
chemo-selective allylic arylations in high yields. The cross-cou-
pling of 3-cyclohexylallyl carbonate also furnished the regio-selec-
tive arylation with different triarylbismuth reagents.
The above results revealed us the following: (i) facile cross-cou-
plings of allylic carbonates with triarylbismuths; (ii) the high reac-
tivity of electronically divergent triarylbismuths with allylic
carbonates; (iii) the atom-efficient reactivity of triarylbismuths
as multi-coupling organometallic nucleophiles with allylic carbon-
ates; (iv) fast reactivity of couplings in 1 h involving three C–C cou-
plings using 3 equiv. of allylic carbonates; and (v) novel multi-
coupling ability of triarylbismuths in comparison with other orga-
nometallic nucleophiles in allylic aryaltion. Overall, the high reac-
tivity of triarylbismuths for cross-coupling with allylic carbonate
was established under the established conditions. The products ob-
tained in these reactions, i.e. 1,3-disubstituted propenes are impor-
tant skeletons found in natural products [40–43]. These
compounds are also useful for a variety of synthetic transforma-
tions [44–49].
A tentative catalytic cycle proposed for this reaction is given in
Fig. 1. This is similar to the earlier mechanism proposed by Hiyama
and co-workers with allylic carbonates [17]. As noted before in the
To elaborate the scope, coupling reactions of a variety of triaryl-
bismuths with (E)-3-p-tolylallyl carbonate were conducted under
the optimized conditions (Table 2).
introduction, the catalytic cycle is expected to go through
p-allyl-
The arylations using electronically divergent triarylbismuths as
organometallic nucleophiles were found to furnish high yields of
products. The regio-selectivities at the allylic position were high
in all cases with the formation of corresponding 1,3-disubstituted
propenes as major products. However in some reactions, the other
regio-isomer was also formed in minor amounts. Noteworthy is
that the novel reactivity of functionalized triarylbismuths and their
facile reactivity under the coupling conditions (Table 2, entries 8
and 9). Importantly, trithiophen-2-ylbismuth as multi-coupling
atom-efficient reagents also furnished high yield of arylation prod-
uct (Table 2, entry 11).
palladium alkoxide intermediate, A.
This intermediate upon transmetallation with triarylbismuth
provides allylpalladium intermediates and which upon
B
C
reductive elimination delivers arylated products D and E. The
alkoxide as counter anion in A was proposed to activate arylbis-
muth species during transmetallation, as we have not used extra
base to activate the Ar–Bi bond of triarylbismuths [28]. As the
coupling sequence involves three aryl transfers from triarylbis-
muth, the in situ generated species such as Ar2BiOEt/ArBi(OEt)2
are proposed to involve in the transmetallation steps of subse-
quent catalytic cycles. This is in tune with the facile coupling
reactivity of organobismuth alkoxide under palladium catalysis
[50,51]. Thus, triarylbismuths were involved as multi-coupling
The versatility of the coupling reaction was also assessed with a
variety of allylic carbonates and the results are summarized in

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M.L.N. Rao et al. / Journal of Organometallic Chemistry 695 (2010) 1518–1525
Table 2
Couplings with different triarylbismuths.a–c
Ar
[Pd]
OCO2Et
Ar
BiAr3
+
+
Me
Me
Me
5
(3 equiv)
(1 equiv)
4
(major)
(minor)
Entry
1
Triarylbismuth
GC ratio
94/4
1,3-Diarylpropene, 5
Yield (%)
80
Bi
5.1
3
Me
2
3
4
5
6
85/15
91/9
70
64
76
74
67
Bi
Bi
Bi
Bi
Bi
Me
5.2
3
Me
Me
OMe
5.3
3
Me
OMe
F
94/6
F
3
5.4
Me
95/5
Cl
5.5
3
Me
Cl
OMe
79/21
5.6
3
Me
OMe
7
8
100/0
100/0
78
90
Me
Bi
Bi
5.7
3
Me
Me
O
5.8
O
3
3
O
O
Me
9
100/0
70
O
Bi
5.9
O
O
O
Me
10
11
100/0
100/0
70
80
Bi
Bi
5.10
OMe
3
Me
OMe
S
S
5.11
3
Me
a
Conditions: BiAr3 (1 equiv., 0.50 mmol), allylic carbonate (3.5 equiv., 1.75 mmol), PdCl2(PPh3)2(0.09 equiv., 0.045 mmol), NEt3 (1 equiv., 0.50 mmol); NMP (6 mL), 90 °C,
Isolated yields of 5 based on three couplings from triarylbismuth, i.e. 3 equiv. of cross-coupling product (3 Â 0.5 = 1.5 mmol) as 100% yield. All products were charac-
1 h
b
terized by 1H, 13C NMR, IR, HRMS and in comparison with the literature data.
c
In general, homo-coupling bi-aryls from triarylbismuths are formed in all the reactions and the amount varied with respect to the degree of the cross-coupling reaction.
Minor isomer 4 was not isolated as it is formed in small amounts.
organometallic nucleophiles in these coupling reactions with
allylic carbonates for three C–C couplings. However, homo-cou-
pling reactivity of triarylbismuths under palladium-catalyzed
conditions [36] is an unavoidable side pathway leading to forma-
tion of bi-aryls as minor products.
In conclusion, we have demonstrated an atom-efficient cross-
coupling reactivity of triarylbismuths as multi-coupling organome-
tallic nucleophiles with allylic carbonate under palladium-cata-
lyzed conditions.
3. Experimental
3.1. General
All the reactions have been conducted under nitrogen atmo-
sphere using an oven dried Schlenk tube using anhydrous solvent
conditions. Allylic carbonates were prepared using standard meth-
ods [52–54]. Triarylbismuths were made following the literature
procedure [55]. Anhydrous solvents such as N,N-dimethylformam-

M.L.N. Rao et al. / Journal of Organometallic Chemistry 695 (2010) 1518–1525
1521
Table 3
Couplings of allylic carbonates with triarylbismuths.a–c
Ar
[Pd]
R1
OCO2Et
(3 equiv)
R1 = Ar, cylohexyl
BiAr3
+
R1
+
R1
Ar
(1 equiv)
4
5
(minor)
(major)
Entry
12
Allylic carbonate
Triarylbismuth
GC ratio
90/10
1,3-diarylpropene, 5
Yield (%)
76
OCO2Et
Bi
5.12
3
13
14
85/15
83/17
74
OCO2Et
Bi
Bi
Me
5.13
3
Me
72
OCO2Et
OMe
5.14
3
OMe
Br
Br
Br
15
16
93/7
75
72
OCO2Et
Bi
Bi
5.15
5.16
3
Br
Br
90/10
OCO2Et
Me
3
Me
Br
17
18
19
20
21
22
23
24
88/12
92/8
73
73
71
70
70
64
70
75
OCO2Et
OCO2Et
OCO2Et
OCO2Et
OCO2Et
OCO2Et
OCO2Et
Bi
Bi
Bi
Bi
Bi
Bi
Bi
Bi
OMe
5.17
5.18
3
OMe
3
Br
Br
Br
Cl
Cl
Cl
Br
Br
Br
Cl
Cl
87/13
86/14
90/10
86/14
87/13
98/2
Me
5.19
5.20
3
Me
OMe
3
OMe
5.21
5.22
5.23
3
Me
3
Me
OMe
3
OMe
Cl
Cl
OCO2Et
5.24
5.25
5.26
3
Cl
Cl
Cl
25
26
88/12
89/11
71
70
OCO2Et
OCO2Et
Bi
Bi
Me
3
Me
Cl
Cl
OMe
3
OMe
27
28
29
30
94/6
85
80
77
70
OCO2Et
OCO2Et
OCO2Et
OCO2Et
Bi
Bi
Bi
Bi
5.27
Cl
3
Cl
Cl
Cl
90/10
90/10
88/12
Me
5.28
Cl
3
Me
OMe
5.29
Cl
3
OMe
MeO
5.30
3
OMe
31
32
91/9
91/9
68
71
OCO2Et
OCO2Et
Bi
Bi
5.31
5.32
3
Me
3
Me
33
90/10
77
OCO2Et
Bi
OMe
5.33
3
OMe
a
Conditions: BiAr3 (1 equiv., 0.50 mmol), allylic carbonate (3.5 equiv., 1.75 mmol), PdCl2(PPh3)2(0.09 equiv., 0.045 mmol), NEt3 (1 equiv., 0.50 mmol); NMP (6 mL), 90 °C,
Isolated yields of 5 based on three couplings from triarylbismuth, i.e. 3 equiv. of cross-coupling product (3 Â 0.5 = 1.5 mmol) as 100% yield. All products were charac-
1 h.
b
terized by 1H, 13C NMR, IR, HRMS and in comparison with literature data.
c
In general, homo-coupling bi-aryls from triarylbismuths are formed in all the reactions and the amount varied with respect to the degree of the cross-coupling reaction.
Minor isomer 4 was not isolated as it is formed in small amounts.
ide (DMF) and N-methylpyrrolidone (NMP) were distilled using
standard drying procedures. Column chromatography was per-
formed using silica gel (100–200 mesh). NMR spectra were re-
corded in CDCl3 using JEOL 400 MHz spectrometer. IR spectra

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M.L.N. Rao et al. / Journal of Organometallic Chemistry 695 (2010) 1518–1525
OCO2Et
R
R
R
Ar
+
O
C
Ar
2
Pd0L
(E)
(D)
R
_
Pd+
OEt
L
(A)
BiAr3
R
R
Pd
Pd
Ar
(B)
L
EtO-BiAr2
L
Ar
(C)
Fig. 1. Proposed mechanism.
were recorded using Bruker FT-IR spectrometer and HRMS were
measured using WATERS LCMS spectrometer.
(d, 2H, J = 6.84 Hz), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3) d
161.47 (d, J = 243.00 Hz), 136.94, 135.91, 134.56, 131.09, 130.01,
129.19, 127.91, 126.01, 115.15 (d, J = 22.00 Hz), 38.45, 21.10. IR
(KBr) 3024, 2920, 1602, 1508, 1221, 1156, 967, 798, 704 cmÀ1
.
3.2. Representative procedure for cross-coupling of allylic carbonate
with triarylbismuth
HRMS (ESI) calcd. for C16H15F [M+H]+, 227.1236; found, 227.1236.
5.5, (E)-1-(4-Methylphenyl)-3-(4-chlorophenyl)propene [56]:
Colourless oil. Yield, 74%. 1H NMR (400 MHz, CDCl3) d 7.24–7.28
(m, 4H), 7.16 (d, 2H, J = 8.32 Hz), 7.10 (d, 2H, J = 8.40 Hz), 6.41 (d,
1H, J = 15.84 Hz), 6.21–6.29 (m, 1H), 3.50 (d, 2H, J = 6.60 Hz), 2.32
(s, 3H). 13C NMR (100 MHz, CDCl3) d 138.77, 137.02, 134.50,
131.91, 131.37, 129.98, 129.22, 128.54, 127.48, 126.04, 38.59,
21.12. IR (KBr) 3023, 2921, 1726, 1489, 1089, 1014, 966,
803 cmÀ1. HRMS (ESI) calcd. for C16H15Cl [M+H]+, 243.0941; found,
243.0940.
To an oven dried Schlenk tube, cinnamyl carbonate (1.75 mmol,
361 mg) was charged followed by Et3N (0.5 mmol, 51 mg), triphe-
nylbismuth (0.5 mmol, 220 mg), PdCl2(PPh3)2 (0.045 mmol,
31.5 mg) and NMP (6 mL) under nitrogen atmosphere. The reaction
mixture was stirred in an oil bath at 90 °C for 1 h. After the reaction
time, the contents were cooled to room temperature, quenched
with 10 mL water and extracted with ethyl acetate (3 Â 20 mL).
The combined organic extract was washed with water
(2 Â 10 mL), brine (20 mL) and dried over anhydrous MgSO4. The
organic extract was concentrated under reduced pressure. The
crude product was purified by column chromatography using
petroleum ether as eluent to afford 1,3-diphenylpropene, 5.12
(221 mg, 76%).
5.6,
(E)-1-(4-Methylphenyl)-3-(3-methoxyphenyl)propene:
Colourless oil. Yield, 67%. 1H NMR (400 MHz, CDCl3) d 7.24–7.30
(m, 3H), 7.13 (d, 1H, J = 8.08 Hz), 6.88 (d, 2H, J = 7.56 Hz), 6.79–
6.83 (m, 2H), 6.47 (d, 1H, J = 15.80 Hz), 6.29–6.39 (m, 1H), 3.83
(s, 3H), 3.55 (d, 2H, J = 6.60 Hz), 2.36 (s, 3H). 13C NMR (100 MHz,
CDCl3) d 159.78, 141.97, 136.80, 134.70, 131.01, 129.16, 127.94,
126.02, 121.03, 114.35, 111.51, 55.13, 39.34, 21.10. IR (KBr) 3023,
2919, 2833, 1598, 1511, 1261, 1148, 1045, 967, 775 cmÀ1. HRMS
(ESI) calcd. for C17H18O [M+H]+, 239.1436; found, 239.1436.
5.7, (E)-1-(3-Methylphenyl)-3-(4-methylphenyl)propene: Col-
ourless oil. Yield, 78%. 1H NMR (400 MHz, CDCl3) d 7.29 (d, 2H,
J = 8.28 Hz), 7.08–7.22 (m, 6H), 6.30–6.47 (m, 2H), 3.53 (d, 2H,
J = 6.84 Hz), 2.36 (s, 3H), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 140.23, 138.02, 136.76, 134.71, 130.77, 129.15, 128.32, 126.83,
125.99, 125.63, 39.27, 21.36, 21.11. IR (KBr) 3023, 2922, 2855,
1702, 1607, 1488, 1452, 1094, 813 cmÀ1. HRMS (ESI) calcd. for
C17H18 [M–H]+, 221.1336; found, 221.1336.
5.1, (E)-1-(4-Methylphenyl)-3-phenylpropene [56]: Colourless
oil, Yield, 80%. 1H NMR (400 MHz, CDCl3) d 7.18–7.36 (m, 7H),
7.14 (d, 2H, J = 8.04 Hz), 6.47 (d, 1H, J = 15.84 Hz), 6.30–6.38 (m,
1H), 3.57 (d, 2H, J = 6.60 Hz), 2.36 (s, 3H); 13C NMR (100 MHz,
CDCl3) d 140.32, 136.80, 134.67, 130.90, 129.17, 128.64, 128.43,
128.14, 126.10, 125.99, 39.32, 21.13. IR (KBr) 3026, 2920, 1723,
1452, 1270, 1177, 816, 750, 699 cmÀ1
.
5.2, (E)-1,3-bis(4-Methylphenyl)propene [57]: White solid. M.P
42–43 °C. Yield, 70%. 1H NMR (400 MHz, CDCl3) d 7.09–7.29 (m,
8H), 6.42 (d, 1H, J = 15.88 Hz), 6.26–6.33 (m, 1H), 3.50 (d, 2H,
J = 6.60 Hz), 2.34 (s, 3H), 2.33 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 137.22, 136.72, 135.57, 134.75, 130.67, 129.12, 128.51, 128.45,
125.96, 38.90, 21.11, 20.99. IR (KBr) 3022, 2920, 1723, 1514,
1271, 1177, 1109, 1039, 810, 698 cmÀ1. HRMS (ESI) calcd. for
C17H18 [MÀH]+, 221.1336; found, 221.1330.
5.8, (E)-2-Methyl-2-[4-(3-p-tolyl-allyl)-phenyl]-[1,3]dioxolane:
Yellow oil. Yield, 90%. 1H NMR (400 MHz, CDCl3) d 7.44 (d, 2H,
J = 8.08 Hz), 7.28 (d, 2H, J = 7.56 Hz), 7.25 (d, 2H, J = 7.80 Hz), 7.13
(d, 2H, J = 7.80 Hz), 6.46 (d, 1H, J = 15.88 Hz), 6.28–6.33 (m, 1H),
4.06 (t, 2H, J = 6.60 Hz), 3.81 (t, 2H, J = 6.60 Hz), 3.56 (d, 2H,
J = 6.84 Hz), 2.35 (s, 3H), 1.68 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 141.23, 139.97, 136.83, 134.70, 131.02, 129.17, 128.40, 128.01,
126.01, 125.40, 108.86, 64.42, 39.00, 27.60, 21.09. IR (KBr) 3024,
2987, 2888, 1704, 1609, 1410, 1255, 1198, 1039, 1212, 871,
757 cmÀ1. HRMS (ESI) calcd. for C20H22O2 [MÀH]+, 293.1547;
found, 293.1547.
5.3,
(E)-1-(4-Methylphenyl)-3-(4-methyoxyphenyl)propene
[56]: Colourless oil. Yield, 64%. 1H NMR (400 MHz, CDCl3) d 7.27
(d, 2H, J = 8.04 Hz), 7.11–7.19 (m, 4H), 6.88 (d, 2H, J = 8.52 Hz),
6.43 (d, 1H, J = 15.60 Hz), 6.27–6.34 (m, 1H), 3.82 (s, 3H), 3.50 (d,
2H, J = 6.60 Hz), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3) d 158.00,
136.74, 134.71, 132.33, 130.58, 129.59, 129.19, 128.62, 125.99,
113.88, 55.26, 38.41, 21.12. IR (KBr) 3063, 2939, 2853, 1598,
1511, 1267, 1149, 1045, 967, 775 cmÀ1. HRMS (ESI) calcd. for
C17H18O [M]+, 238.1358; found, 238.1355.
5.9, (E)-2-[4-(3-p-Tolyl-allyl)-phenyl]-[1,3]dioxolane: Yellow
oil. Yield, 70%. 1H NMR (400 MHz, CDCl3)
d 7.43 (d, 2H,
5.4, (E)-1-(4-Methylphenyl)-3-(4-fluorophenyl)propene [56]:
Light yellow oil. Yield, 76%. 1H NMR(400 MHz, CDCl3) d 7.28 (d,
2H, J = 8.00 Hz), 7.20–7.23 (m, 2H), 7.13 (d, 2H, J = 7.84 Hz), 6.99–
7.04 (m, 2H), 6.43 (d, 1H, J = 15.88 Hz), 6.26–6.33 (m, 1H), 3.53
J = 7.80 Hz), 7.24–7.27 (m, 4H), 7.11 (d, 2H, J = 7.80 Hz), 6.43 (d,
1H, J = 16.36 Hz), 6.24–6.32 (m, 1H), 5.81 (s, 1H), 4.14 (t, 2H,
J = 6.84 Hz), 4.02–4.05 (m, 2H), 3.54 (d, 2H, J = 6.60 Hz), 2.32 (s,

M.L.N. Rao et al. / Journal of Organometallic Chemistry 695 (2010) 1518–1525
1523
3H). 13C NMR (100 MHz, CDCl3) d 141.42, 136.84, 134.69, 131.07,
130.01, 129.18, 128.67, 127.92, 126.57, 126.01, 103.75, 65.26,
39.06, 21.09. IR (KBr) 3024, 2921, 2853, 1697, 1605, 1261, 1272,
135.64, 132.72, 132.55, 131.85, 129.57, 128.05, 127.01, 126.73,
113.98, 55.28, 38.65. IR (KBr) 2999, 2954, 2930, 1606, 1511,
1176, 995 cmÀ1. HRMS (ESI) calcd. for C16H15BrO [M]+, 302.0306;
found, 302.0306.
5.18, (E)-1-(4-Bromophenyl)-3-phenylpropene [12]: Light yel-
low oil, Yield, 73%. 1H NMR (400 MHz, CDCl3) d 7.42 (d, 2H,
J = 6.84 Hz), 7.32 (d, 2H, J = 7.32 Hz), 7.21–7.27 (m, 5H), 6.32–
6.42 (m, 2H), 3.54 (d, 2H, J = 4.64 Hz). 13C NMR (100 MHz, CDCl3)
d 139.77, 136.38, 131.53, 130.13, 129.84, 128.64, 128.51, 127.63,
126.26, 120.73, 39.29. IR (KBr) 3061, 3028, 2923, 1722, 1591,
1045, 1212, 967, 816 cmÀ1
. HRMS (ESI) calcd. for C19H20O2
[M+H]+, 281.1547; found, 281.1542.
5.10, (E)-2-Methoxy-6-(3-p-tolyl-allyl)-naphthalene: Light yel-
low oil. Yield, 70%. 1H NMR (400 MHz, CDCl3) d 7.68 (d, 2H,
J = 8.28 Hz), 7.60 (s, 1H), 7.33 (dd, 2H, J = 1.68, 8.28 Hz), 7.27 (d,
2H, J = 8.04 Hz), 7.09–7.14 (m, 3H), 6.45 (d, 1H, J = 15.88 Hz),
6.33–6.40 (m, 1H), 3.90 (s, 3H), 3.66 (d, 2H, J = 6.60 Hz), 2.32 (s,
3H); 13C NMR (100 MHz, CDCl3) d 157.33, 136.82, 135.49, 134.79,
133.22, 131.02, 129.19, 128.97, 128.27, 127.95, 126.87, 126.57,
126.05, 118.70, 105.78, 55.26, 39.26, 21.09. IR(KBr) 3054, 3020,
2961, 1631, 1508, 1421, 1228, 1195, 1033, 855, 816 cmÀ1. HRMS
(ESI) calcd. for C21H20O [M + H]+, 289.1598; found, 289.1594.
5.11, (E)-2-(3-p-Tolyl-allyl)-thiophene: Light brown oil, Yield,
80%. 1H NMR (400 MHz, CDCl3) d 7.29 (d, 2H, J = 8.08 Hz), 7.18
(dd, 1H, J = 1.20, 5.12 Hz), 7.14 (d, 2H, J = 7.80 Hz), 6.98 (dd, 1H,
J = 3.40, 5.12 Hz), 6.88 (dd, 1H, J = 1.00, 3.40 Hz), 6.32–6.52 (m,
2H), 3.75 (d, 2H, J = 6.60 Hz), 2.36 (s, 3H). 13C NMR (100 MHz,
CDCl3) d 143.33, 137.03, 134.39, 131.21, 129.19, 127.10, 126.87,
126.11, 124.57, 123.65, 33.31, 21.13. IR (KBr) 3023, 2919, 1512,
1489, 1266, 1070, 1029, 796, 700 cmÀ1
5.19,
.
(E)-1-(4-Bromophenyl)-3-(4-methylphenyl)propene:
Light yellow solid, Yield, 71%. M.P 47–49 °C. 1H NMR (400 MHz,
CDCl3) d 7.50 (d, 2H, J = 8.08 Hz), 7.42 (d, 2H, J = 8.52 Hz), 7.13–
7.27 (m, 4H), 6.31–6.41 (m, 2H), 3.52 (d, 2H, J = 5.12 Hz), 2.35
(s, 3H). 13C NMR (100 MHz, CDCl3) d 136.66, 136.45, 135.78,
131.51, 130.45, 129.61, 129.19, 128.51, 127.61, 120.66, 38.87,
21.00. IR (KBr) 3020, 2888, 1901, 1510, 1482, 1397, 1069 cmÀ1
.
HRMS (ESI) calcd. for C16H15Br [MÀH]+, 285.0284; found,
285.0267.
5.20,
(E)-1-(4-Bromophenyl)-3-(4-methoxyphenyl)propene:
Light yellow oil, Yield, 70%. 1H NMR (400 MHz, CDCl3) d 7.42 (d,
2H, J = 8.52 Hz), 7.23 (d, 2H, J = 8.56 Hz), 7.16 (d, 2H, J = 8.80 Hz),
6.88 (d, 2H, J = 8.76 Hz), 6.31–6.40 (m, 2H), 3.82 (s, 3H), 3.49 (d,
2H, J = 4.88 Hz). 13C NMR (100 MHz, CDCl3) d 158.16, 136.50,
131.81, 131.53, 130.63, 129.56, 127.63, 120.68, 113.99, 55.33,
38.41. IR (KBr) 3026, 2953, 2833, 1701, 1607, 1510, 1486, 1245,
1176, 1071, 1035, 967, 827 cmÀ1. HRMS (ESI) calcd. for C16H15BrO
[M ]+, 302.0306; found, 302.0304.
1438, 1180, 966, 847, 817 cmÀ1. HRMS (ESI) calcd. for C14H14
S
[MÀH]+, 213.0743; found, 213.0727.
5.12, (E)-1,3-Diphenyl propene [12]: Colourless oil, Yield, 76%.
1H NMR (400 MHz, CDCl3) d 7.25–7.42 (m, 10H), 6.51 (d, 1H,
J = 15.88 Hz), 6.37–6.45 (m, 1H), 3.60 (d, 2H, J = 6.56 Hz). 13C
NMR (100 MHz, CDCl3) d 140.14, 137.45, 131.05, 129.19, 128.64,
128.47, 127.07, 126.15, 126.10, 39.32. IR (KBr) 3060, 3026, 1600,
1494, 1452, 1428, 965, 741, 697 cmÀ1
.
5.21, (E)-1-(4-Chlorophenyl)-3-phenylpropene [12]: Pale yel-
low oil, Yield, 70%. 1H NMR (400 MHz, CDCl3) d 7.24–7.35 (m,
9H), 6.41 (d, 1H, J = 15.84 Hz), 6.31–6.38 (m, 1H), 3.56 (d, 2H,
J = 6.08 Hz). 13C NMR (100 MHz, CDCl3) d 139.86, 136.00, 132.67,
130.03, 129.85, 128.62, 128.53, 127.31, 126.26, 39.29. IR (KBr)
5.13, (E)-3-(4-methylphenyl)-1-phenyl propene [58]: Colour-
less oil, Yield, 74%. 1H NMR (400 MHz, CDCl3) d 7.15–7.39 (m,
9H), 6.47 (d, 1H, J = 15.64 Hz), 6.33–6.40 (m, 1H), 3.53 (d, 2H,
J = 6.36 Hz), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3) d 137.46,
135.64, 130.77, 129.47, 129.14, 128.51, 128.45, 127.01, 126.06,
125.53, 38.89, 21.00. IR (KBr) 3024, 2921, 1600, 1513, 1495,
1449, 1022 cmÀ1. HRMS (ESI) calcd. for C16H16 [M]+, 208.1252;
found, 208.1258.
3026, 2926, 1600, 1452, 1429, 1093 cmÀ1
.
5.22,
(E)-1-(4-Chlorophenyl)-3-(4-methylphenyl)propene:
White solid. M.P. 43–45 °C. Yield, 64%. 1H NMR (400 MHz, CDCl3)
d 7.34–7.50 (m, 4H), 7.13–7.26 (m, 4H), 6.39 (d, 1H, J = 15.88 Hz),
6.29–6.36 (m, 1H), 3.51 (d, 2H, J = 6.08 Hz), 2.34 (s, 3H). 13C NMR
5.14, (E)-1-phenyl-3-(4-methoxyphenyl)propene [12]: Light
yellow oil, Yield, 72%. 1H NMR (400 MHz, CDCl3) d 7.21–7.40 (m,
5H), 7.20 (d, 2H, J = 8.52 Hz), 6.89 (d, 2H, J = 8.56 Hz), 6.47 (d, 1H,
J = 15.88 Hz), 6.34–6.41 (m, 1H), 3.83 (s, 3H), 3.53 (d, 2H,
J = 6.36 Hz). 13C NMR (100 MHz, CDCl3) d 158.03, 137.50, 132.14,
130.69, 129.64, 129.56, 128.45, 127.01, 126.07, 113.87, 55.25,
38.42. IR (KBr) 3001, 2955, 2835, 1606, 1512, 1248, 1176, 1033,
(100 MHz, CDCl3)
d 136.72, 136.00, 135.77, 132.54, 130.29,
129.56, 129.20, 128.57, 128.52, 127.27, 38.86, 21.00. IR (KBr)
3020, 2920, 2888, 1487, 1450, 1332, 1091 cmÀ1. HRMS (ESI) calcd.
for C16H15Cl [MÀH]+, 241.0790; found, 241.0794.
5.23,
(E)-1-(4-Chlorophenyl)-3-(4-methoxyphenyl)propene
[12]: Colourless oil. Yield, 70%. 1H NMR (400 MHz, CDCl3) d 7.22–
7.35 (m, 4H), 7.18 (d, 2H, J = 8.56 Hz), 6.89 (d, 2H, J = 8.56 Hz),
6.41 (d, 1H, J = 15.88 Hz), 6.31–6.38 (m, 1H), 3.83 (s, 3H), 3.50 (d,
2H, J = 5.84 Hz). 13C NMR (100 MHz, CDCl3) d 158.10, 136.01,
132.55, 131.83, 130.45, 129.57, 129.47, 128.58, 127.27, 113.93,
55.26, 38.39. IR (KBr) 2999, 2995, 2835, 1606, 1511, 1301, 1248,
829, 698 cmÀ1
.
5.15, (E)-1-(3-Bromophenyl)-3-phenylpropene: Light yellow
oil. Yield, 75%. 1H NMR (400 MHz, CDCl3) d 7.14–7.52 (m, 9H),
6.38–6.39 (m, 2H), 3.56 (d, 2H, J = 4.16 Hz). 13C NMR (100 MHz,
CDCl3) d 139.67, 130.96, 129.97, 129.61, 128.97, 128.64, 128.54,
126.30, 124.76, 122.70, 39.25. IR (KBr) 3062, 3028, 1722, 1570,
1451, 1252, 1070, 783, 746, 699 cmÀ1. HRMS (ESI) calcd. for
C15H13Br [MÀH]+, 271.0128; found, 271.0125.
1176, 1090, 1034, 827 cmÀ1
.
5.24, (E)-1-(3-Chlorophenyl)-3-phenylpropene: Light yellow
oil. Yield, 75%. 1H NMR (400 MHz, CDCl3) d 7.18–7.36 (m, 9H),
6.38–6.45 (m, 2H), 3.56 (d, 2H, J = 4.40 Hz). 13C NMR (100 MHz
CDCl3) d 139.70, 139.38, 134.36, 130.91, 129.70, 128.64, 127.01,
126.29, 124.31, 123.76, 39.25. IR (KBr) 3062, 3027, 2925, 1595,
1572, 1196, 1077, 785, 747, 699 cmÀ1. HRMS (ESI) calcd. for
C15H13Cl [MÀH]+, 227.0633; found, 227.0637.
5.16,
(E)-1-(3-Bromophenyl)-3-(4-methylphenyl)propene:
Light yellow oil. Yield, 72%. 1H NMR (400 MHz, CDCl3) d 7.54–
7.55 (m, 2H), 7.36 (dd, 2H, J = 0.96, 7.80 Hz), 7.17–7.30 (m, 4H),
6.43 (d, 1H, J = 15.88 Hz), 6.36–6.40 (m, 1H), 3.56 (d, 2H,
J = 3.44 Hz), 2.38 (s, 3H). 13C NMR (100 MHz, CDCl3) d 139.71,
136.57, 135.82, 131.28, 129.94, 129.38, 128.98, 128.53, 124.73,
122.69, 38.83, 21.02. IR (KBr) 3054, 2922, 2856, 1687, 1344,
5.25,
(E)-1-(3-Chlorophenyl)-3-(4-methylphenyl)propene:
Light yellow oil. Yield, 71%. 1H NMR (400 MHz, CDCl3) d 7.15–
7.35 (m, 8H), 6.36–6.39 (m, 2H), 3.52 (d, 2H, J = 4.88 Hz), 2.36 (s,
3H). 13C NMR (100 MHz, CDCl3) d 139.39, 136.57, 135.80, 134.39,
131.19, 129.47, 128.52, 126.93, 126.03, 124.27, 38.82, 21.00. IR
(KBr) 3023, 2981, 2921, 1698, 1428, 1264, 1077, 785, 749,
691 cmÀ1. HRMS (ESI) calcd. for C16H15Cl[MÀH]+, 241.0790; found,
241.0782.
.
1265, 1020, 741 cmÀ1 HRMS (ESI) calcd. for C16H15Br [M]+,
286.0357; found, 286.0358.
5.17,
(E)-1-(3-Bromophenyl)-3-(4-methoxyphenyl)propene:
Light yellow oil, Yield, 73%. 1H NMR (400 MHz CDCl3) d 7.11–
7.32 (m, 6H), 6.84–6.88 (m, 2H), 6.33–6.41 (m, 2H), 3.80 (s, 3H),
3.48 (d, 2H, J = 4.88 Hz). 13C NMR (100 MHz, CDCl3) d 158.16,

1524
M.L.N. Rao et al. / Journal of Organometallic Chemistry 695 (2010) 1518–1525
5.26,
(E)-1-(3-Chlorophenyl)-3-(4-methoxyphenyl)propene:
1035, 968, 848 cmÀ1. HRMS (ESI) calcd. for C16H22O [MÀH]+,
Light yellow oil. Yield, 70%. 1H NMR (400 MHz, CDCl3) d 7.18–
7.36 (m, 4H), 7.17 (d, 2H, J = 8.28 Hz), 6.88 (d, 2H, J = 8.76 Hz),
6.34–6.43 (m, 2H), 3.83 (s, 3H), 3.50 (d, 2H, J = 4.64 Hz); 13C NMR
229.1598; found, 229.1554.
Acknowledgements
(100 MHz, CDCl3)
d 158.12, 139.40, 134.40, 131.68, 131.34,
129.58, 126.94, 126.02, 124.28, 113.95, 55.27, 38.35. IR (KBr)
2997, 2990, 2839, 1600, 1510, 1312, 1248, 1174, 1095, 1036,
820 cmÀ1. HRMS (ESI) calcd. for C15H13ClO [M]+, 258.0811; found,
258.0814.
We thank the Department of Science and Technology (DST),
New Delhi, for financial support of this work. D.B. and S.G.
acknowledges IIT Kanpur and Council of Scientific and Industrial
Research (CSIR), New Delhi, respectively, for research fellowships.
5.27, (E)-1-(2-Chlorophenyl)-3-phenylpropene: Pale yellow oil.
Yield, 85%. 1H NMR (400 MHz, CDCl3) d 7.53 (dd, 1H, J = 1.68,
7.56 Hz), 7.17–7.37 (m, 8H), 6.90 (d, 1H, J = 15.64 Hz), 6.32–6.40
(m, 1H), 3.63 (d, 2H, J = 7.08 Hz). 13C NMR (100 MHz, CDCl3) d
139.83, 135.57, 132.72, 132.10, 129.60, 128.53, 128.12, 127.34,
126.73, 126.26, 39.55. IR (KBr) 3061, 3027, 1469, 1452, 1051,
965, 748, 698 cmÀ1. HRMS (ESI) calcd. for C15H13Cl [MÀH]+,
227.0633; found, 227.0627.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jorganchem.2010.03.010.
References
5.28,
(E)-1-(2-Chlorophenyl)-3-(4-methylphenyl)propene:
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(2004) 5459–5470.
Light yellow oil. Yield, 80%. 1H NMR (400 MHz, CDCl3) d 7.52 (d,
2H, J = 7.56 Hz), 7.36 (d, 2H, J = 7.56 Hz), 7.14–7.27 (m, 4H), 6.88
(d, 1H, J = 15.60 Hz), 6.30–6.38 (m, 1H), 3.58 (d, 2H, J = 7.08 Hz),
2.36 (s, 3H). 13C NMR (100 MHz, CDCl3) d 136.74, 135.75, 132.71,
132.39, 129.57, 129.21, 128.51, 128.05, 127.09, 126.73, 39.13,
21.00. IR (KBr) 3020, 2925, 2856, 1467, 1436, 1264, 1033, 966,
749 cmÀ1. HRMS (ESI) calcd. for C16H15Cl [M]+, 242.0862; found,
242.0860.
5.29,
(E)-1-(2-Chlorophenyl)-3-(4-methoxyphenyl)propene:
Light yellow oil. Yield, 77%. 1H NMR (400 MHz, CDCl3) d 7.52 (d,
2H, J = 7.56 Hz), 7.35 (d, 2H, J = 7.56 Hz), 7.19 (d, 2H, J = 8.32 Hz),
6.84–6.89 (m, 3H), 6.29–6.36 (m, 1H), 3.79 (s, 3H), 3.56 (d, 2H,
J = 7.08 Hz). 13C NMR (100 MHz, CDCl3) d 158.16, 135.64, 132.71,
132.55, 131.85, 129.57, 128.05, 127.01, 126.73, 113.98, 55.28,
38.65. IR (KBr) 2931, 2905, 2833, 1609, 1511, 1300, 1245, 1176,
[10] C. Welter, A. Dahnz, B. Brunner, S. Streiff, P. Dubon, G. Helmchen, Org. Lett. 7
(2005) 1239–1242.
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Kawamura, Organometallics 17 (1998) 4835–4841.
1034, 966, 752 cmÀ1 HRMS (ESI) calcd. for C16H15ClO [M]+,
.
258.0811; found, 258.0813.
5.30, (E)-1-(3-methoxyphenyl)-3-phenylpropene [59]: Colour-
less oil, Yield, 70%. 1H NMR (400 MHz, CDCl3) d 7.20–7.35 (m,
4H), 6.91–6.98 (m, 4H), 6.78 (dd, 1H, J = 2.44, 8.26 Hz), 6.33–6.47
(m, 2H), 3.81 (s, 3H), 3.57 (d, 2H, J = 6.36 Hz). 13C NMR (100 MHz,
CDCl3) d 159.77, 140.07, 138.92, 130.95, 129.55, 128.66, 126.18,
118.80, 112.83, 111.33, 55.16, 39.28. IR (KBr) 3028, 2937, 2835,
1721, 1598, 1490, 1455, 1263, 1043, 752, 699 cmÀ1. HRMS (ESI)
calcd. for C16H16O [M+H]+, 225.1279; found, 225.1275.
5.31, (E)-1-Cyclohexyl-3-phenylpropene [60]: Colourless oil.
Yield, 68%. 1H NMR (400 MHz, CDCl3) d 7.21–7.34 (m, 5H), 5.46–
5.60 (m, 2H), 3.35 (d, 2H, J = 5.36 Hz), 1.96–2.01 (m, 1H), 1.57–
1.77 (m, 6H), 1.07–1.34 (m, 4H). 13C NMR (100 MHz, CDCl3) d
141.21, 138.10, 128.43, 128.27, 126.10, 125.80, 40.62, 39.08,
33.10, 26.20, 26.08. IR (KBr) 2922, 2850, 1725, 1510, 1440, 1175,
960, 846 cmÀ1. HRMS (ESI) calcd. for C15H20 [M]+, 200.1565; found,
200.1560.
5.32, (E)-1-Cyclohexyl-3-(4-methylphenyl)propene [61]: Col-
ourless oil. Yield, 71%. 1H NMR (400 MHz, CDCl3) d 7.12–7.29 (m,
4H), 5.47–5.58 (m, 2H), 3.33 (d, 2H, J = 5.60 Hz), 2.36 (s, 3H),
1.94–2.01 (m, 1H), 1.66–1.77 (m, 6H), 1.13–1.30 (m, 4H). 13C
NMR (100 MHz, CDCl3) d 138.13, 137.82, 135.22, 128.96, 128.31,
126.38, 40.60, 38.65, 33.10, 26.20, 26.08, 20.97. IR (KBr) 2925,
2852, 1720, 1513, 1449, 1178, 968, 843 cmÀ1. HRMS (ESI) calcd.
for C16H22 [M]+, 214.1721; found, 214.1721.
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