Bi(OTf)3 catalyzed disproportionation reaction of cinnamyl alcohols

Article abstract of DOI:10.1016/j.tet.2017.05.006

Bi(OTf)₃ catalyzed disproportionation reaction of cinnamyl alcohols provides chalcones and benzyl styrenes. The use of various metal triflates is investigated herein for facile and efficient redox transformation. A plausible mechanism has been proposed.

Full text of DOI:10.1016/j.tet.2017.05.006

Accepted Manuscript
Bi(OTf) catalyzed disproportionation reaction of cinnamyl alcohols
3
Chieh-Kai Chan, Yu-Lin Tsai, Meng-Yang Chang
PII:
S0040-4020(17)30471-4
10.1016/j.tet.2017.05.006
TET 28672
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 28 March 2017
Revised Date: 24 April 2017
Accepted Date: 1 May 2017
Please cite this article as: Chan C-K, Tsai Y-L, Chang M-Y, Bi(OTf) catalyzed disproportionation
3
reaction of cinnamyl alcohols, Tetrahedron (2017), doi: 10.1016/j.tet.2017.05.006.
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Bi(OTf)3 Catalyzed Disproportionation Reaction of
Cinnamyl Alcohols
Chieh-Kai Chan, Yu-Lin Tsai and Meng-Yang Chang*
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University Hospital, Kaohsiung Medical University, Kaohsiung 807, Taiwan
O
OH
O
NaBH4
Bi(OTf)
3
+
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
THF, MeOH
CH Cl
2
2
3
4
3
5

ACCEPTED MANUSCRIPT
Tetrahedron
1
TETRAHEDRON
Pergamon
Bi(OTf)3 Catalyzed Disproportionation Reaction of Cinnamyl
Alcohols
Chieh-Kai Chan, Yu-Lin Tsai, and Meng-Yang Chang*
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University Hospital, Kaohsiung Medical University,
Kaohsiung 807, Taiwan
Abstract — Bi(OTf)3 catalyzed disproportionation reaction of cinnamyl alcohols provides chalcones and benzyl styrenes.
The use of various metal triflates is investigated herein for facile and efficient redox transformation. A plausible mechanism
has been proposed.
Ir3+-Sn4+ (Roy work),6a and the other is Fe3+ (Zhou work).6b
Introduction
Inspired by the above two catalytic systems, we explored
the synthetic scope for the disproportionation of cinnamyl
alcohols by the use of various metal triflates, as shown in
Scheme 1. In our ongoing research interests in the synthetic
applications of metal triflates,7 we turned the synthetic aim
to the chemoselective disproportionation from cinnamyl
alcohols to chalcones and benzyl styrenes.
The classical redox disproportionation reaction of two
non-enolizable arylaldehydes involving the key step of
hydrogen transfer was first reported by Cannizzaro.1 In
1906, Tishchenko developed a disproportionation route to
ester products from two aldehyde molecules via an
intramolecular 1,3-hydride shift.2 About 20 years later, Al3+
catalysis of the hydride shift from the α-carbon of alcohols
to carbonyls had been demonstrated by Meerwein,3a
Ponndorf3b and Verley3c (MPV) via a six-membered
transition state. The reversible nature of this MPV
reduction had been realized by Oppenauer.4 However,
different promoter mediated disproportionation reactions
have been regarded, such as metal ions, bases, or Lewis
acids, despite over a century of research.5 It therefore
remained a challenge to develop an alternative catalytic
system for the potential redox disproportionation. Among a
number of disproportionation routes, the novel redox type
of alcohols represents an efficient and versatile conversion
for the formation of hydrocarbons and carbonyls.
Results and discussion
According to the previous synthetic process,8 chalcones
3 were easily prepared in nearly quantitative yields by
NaOH-mediated aldol condensation of acetophenones 1
and arylaldehydes 2 (Ar = Ph, 4-MeOC6H4, 4-FC6H4, 3,4-
CH2O2C6H3, 4-MeC6H4, 2-naphthyl, 3,4,5-(MeO)3C6H2, 4-
ClC6H4, 3-MeOC6H4, 4-PhC6H4, 2-furyl, 2,4-(MeO)2C6H3,
3,4-Cl2C6H3) in refluxing MeOH. With skeleton 3 in hand,
we employed 3a (Ar = Ph) as the model substrate to
examine the disproportionation. First, NaBH4 mediated 1,2-
reduction of 3a provided 4a in an excellent conversion
yield (~100%) in the co-solvent of THF and MeOH (v/v =
o
1/1) at 0 C for 10 min.9 For the purification procedure on
Scheme 1. Disproportionation Reaction of Alcohols
silica gel, some impurity was isolated. Furthermore, 4a was
slowly deteriorated in a CDCl3 solution (monitored by H
1
OH
O
NMR and TLC). To avoid the decomposition problems and
increase the purity of 4a, we decided to use crude 4a as the
starting material to treat with metal triflates, as shown in
Table 1. Next, controlling the reaction conditions (rt, 5 mL
of CH2Cl2, 1 h), Bi(OTf)3 (2 mol %) was chosen as the
optimal catalyst for the disproportionation of 4a among the
various screened commercially available 13 metal triflates,
which included Bi(OTf)3, In(OTf)3, Sn(OTf)2, Ga(OTf)3,
Sc(OTf)3, Fe(OTf)3, AgOTf, Zn(OTf)2, Yb(OTf)3,
Sm(OTf)3, Ni(OTf)2, Ln(OTf)3, and Cu(OTf)2; we found
that only Bi(OTf)3 provided better reactivity within 1 h
(entry 1). For the disproportionation reaction of 4a,
In(OTf)3 Sn(OTf)2, Ga(OTf)3, and Sc(OTf)3 provided the
promoters
+
Ar
Ar
Ar
Ar
Ar
Ar
3+
6b
3+
4+
6a
Fe (Zhou work)
Ir -Sn (Roy work)
M(OTf) (this work)
n
Therefore, in comparison with the reported works on
establishing the disproportionation of allylic alcohols, we
found that only two promoters are documented.6 One is
———
Keywords: Disproportionation; Cannizzaro; Tishchenko; MPV reduction;
Oppenauer; Metal Triflate.
*Corresponding author. Tel.: +886 7 3121101 ext 2220
e-mail: mychang@kmu.edu.tw

ACCEPTED MANUSCRIPT
2
Tetrahedron
transformation from 4a to 5a and 3a within 1 h (entries 2-
5). For an elongated time (1 ꢀ 20 h), the conversion was
also achieved and similar yields of 3a and 5a with a ratio of
1:1 were observed. For entries 1-5, the disproportionation
reaction of 4a provided the redox products 3a and 5a with a
ratio of 1 : 1 and no isolation of diallylic ether 6a was
detected. Although entries 1 and 5 gave comparable results
for the distributed yields of 3a and 5a in initial screening
experiments, Bi(OTf)3 possessed a relatively inexpensive
and low-toxic Lewis acid than Sc(OTf)3.10 When the
reaction was treated with Fe(OTf)3 at rt for 1 h (entry 6),
25% of 3a and 22% of 5a were formed, along with a
dimerized product 6a (15%). For elongated time (20 h), the
yields with similar ratios (1 : 1 : 1) were increased slightly.
However, with the use of AgOTf, Zn(OTf)2, Yb(OTf)3
Sm(OTf)3, Ni(OTf)2, Ln(OTf)3, and Cu(OTf)2, only
diallylic ether 6a was isolated in entries 7-13. The plausible
mechanism for the formation of 6a should be generated by
the dehydrative dimerization of 2 equivalents of 4a. The
phenomenon is similar to Roy6a and Zhou6b reports.
Furthermore, after controlling the Bi(OTf)3 as the catalyst,
the factors of equivalency, concentration and solvent were
studied next. When using 10 mol % of Bi(OTf)3, the
isolated yields was similar to that of 2 mol % (entry 14).
No obvious change occurred after decreasing the reaction
concentration (5 mL ꢀ 20 mL), as shown in entry 15. After
changing the solvents (from CH2Cl2 to MeNO2), the yields
of 3a and 5a were decreased to 35% and 32%, respectively
(entry 16). Compared with room temperature condition
(entry 1), 3a and 5a provided poorer yields (38% and 34%)
by elevating the temperature (rt ꢀ reflux, entry 17). With
the results in hand, we commenced the study with the other
Bi(III) salts, Bi(TFA)3 and Bi(OAc)3, in CH2Cl2 (5 mL) as
the medium at rt for 1 h. However, none of them provided
higher yields than Bi(OTf)3 (entries 18-19). By the
involvement of 2 mol % TfOH (entry 20), only 6a was
isolated in low yield (10%). For the combination of
Bi(OTf)3 and TfOH with the catalytic amounts (2 mol %),
the result (entry 21) was better than entry 20. But, when the
reaction was treated with the combination of catalytic
Bi(OTf)3 (2 mol %) and stoichiometric TfOH (100 mol %),
complex mixture was detected. According to the results, we
envisioned that 2 mol % of Bi(OTf)3/CH2Cl2 (5 mL)/rt/1 h
condition would be an optimal combination for the
disproportionation of 3a.11
Table 1. Reaction Conditionsa-b
O
Ph
Ph
Ph
3a
5a
Ph
Ph
O
OH
M(OTf)
CH Cl
NaBH4
n
O
+
Ph
Ph
Ph
Ph
THF, MeOH
2
2
Ph
Ph
3a
4a (~100%)
Ph
6a
entry catalysts (mol %) 3a (%)c
5a (%)c
6a (%)c
ND
ND
ND
ND
ND
20 (24)d
65
1
Bi(OTf)3 (2)
In(OTf)3 (2)
Sn(OTf)2 (2)
Ga(OTf)3 (2)
Sc(OTf)3 (2)
Fe(OTf)3 (2)
AgOTf (2)
48 (46)d
40 (42)d
34 (35)d
36 (37)d
40 (40)d
26 (30)d
ND
45 (45)d
37 (36)d
36 (38)d
36 (40)d
41 (40)d
25 (31)d
ND
2
3
4
5
Table 2. Synthesis of 3 and 5a-b
6
7
O
8
Zn(OTf)2 (2)
Yb(OTf)3 (2)
Sm(OTf)3 (2)
Ni(OTf)2 (2)
La(OTf)3 (2)
Cu(OTf)2 (2)
Bi(OTf)3 (10)
Bi(OTf)3 (2)e
Bi(OTf)3 (2)f
Bi(OTf)3 (2)g
Bi(TFA)3 (2)
Bi(OAc)3 (2)
TfOH (2)
ND
ND
70
Ar
Ar
Ar
Ar
O
OH
9
ND
ND
72
Bi(OTf)
NaBH4
3
3
+
Ar
Ar
Ar
Ar
10
11
12
13
14
15
16
17
18
19
20
21
22
ND
ND
70
THF, MeOH
CH Cl
2
2
3
4
ND
ND
72
(100% conversion yields)
5
ND
ND
69
entry 3, Ar =
4, %c
3, %d
5, %d
ND
ND
73
1
2
3
4
5
6
7
8
9
3a, Ph
4a, 100 3a, 48 5a, 45
4b, 100 3b, 46 5b, 39
4c, 100 3c, 41 5c, 39
4d, 100 3d, 44 5d, 38
4e, 100 3e, 42 5e, 37
4f, 100 3f, 43 5f, 40
43
44
ND
ND
ND
ND
ND
ND
10h
ND
ND
3b, 4-MeOC6H4
3c, 4-FC6H4
45
42
35
32
3d, 3,4-CH2O2C6H3
3e, 4-MeC6H4
3f, 2-naphthyl
38
34
22
26
10
11
3g, 3,4,5-(MeO)3C6H2 4g, 100 3g, 41 5g, 39
ND
ND
Bi(OTf)3 (2)i
Bi(OTf)3 (2)j
30
28
3h, 4-ClC6H4
4h, 100 3h, 44 5h, 38
4i, 100 3i, 41 5i, 38
4j, 100 3j, 42 5j, 35
3i, 3-MeOC6H4
ND
ND
aThe reactions were run on a 1.0 mmol scale with 3a,
NaBH4 (35 mg, 1.0 mmol), THF/MeOH (3 mL/3 mL), 0 oC,
10 min. bThe reactions were run on a resulting crude 4a,
CH2Cl2 (5 mL), rt, 1 h. cIsolated yields. d20 h. eCH2Cl2 (20
mL). fMeNO2 (5 mL). gReflux. hMajor complex mixture
was isolated. iTfOH (2 mol %). jTfOH (100 mol %).
10 3j, 4-PhC6H4
11 3k, 2,4-(MeO)2C6H3 4k, 100 3k, 21 5k,─e
12 31, 2-furyl
41, 100 31, 12 5l, ─e
aThe reactions were run on a 1.0 mmol scale with 3a-l,
NaBH4 (35 mg, 1.0 mmol), THF/MeOH (3 mL/3 mL), 0 oC,
10 min. bThe reactions were run on a resulting crude 4a-l,

ACCEPTED MANUSCRIPT
Tetrahedron
3
Bi(OTf)3 (13 mg, 2 mol%), CH2Cl2 (5 mL), rt, 1 h.
cConversion yields (by TLC analysis). dIsolated yields.
eComplex mixture.
was maintained as 3/1 (entry 7). For tricyclic 9-anthrancyl
group with the bulky steric hindrance, only 22 % of 3t and
20% of 5t/5t’ (3/1) were observed (entry 8). For the two-
step route of asymmetric oxygenated chalcones (3u-v), the
afforded yields of 3u and 5u/5u’ (3/1) were similar to 3v
and 5v/5v’ (1/1) (entries 9-10). According to the above
experimental results (Tables 1-3), a possible two-step
reaction mechanism is shown in Scheme 2. The initial
reduction of 3 yields 4 by NaBH4. By the Bi(OTf)3
catalyzed complexation of two molecules of 4, A1/A2 and
B1/B2 could be generated via paths a and b. On basis of the
eight-membered conformation (path a), 3 and 5’ are
provided via an intramolecular 1,8-hydride shift (pink
circle) on A1 or A2 and the removal of Bi(O)OTf and
TfOH (2 equiv). In path b, intramolecular 1,6-hydride shift
(green circle) could trigger the transformation from B1 or
B2 to 3 and 5 and release the Bi(O)OTf and TfOH via the
six-membered conformation. Subsequently, Bi(OTf)3 is
regenerated by complexation of Bi(O)OTf and TfOH. From
the experimental results, we envisioned that the present
plausible mechanism provided the reasonable explanation
for no generation of 3’ via the intramolecular hydride shift
of four plausible intermediates A1/A2 and B1/B2. Among
the inseparated mixture of 5 and 5’, the isolated ratio of 5
was better than 5’ due to B1/B2 with a six-membered
conformation being orientated and formed more easily than
A1/A2 with an eight-membered conformation. Following a
successful two-step protocol, we further explored the
conversion of other substrate scopes; the results are shown
in Scheme 3. By the above protocol, enedione 7 was
transformed into 2,5-diphenyltetrahydrofuran 8 in a 71%
yield via the 1,4- and 1,2-reduction followed by Bi(OTf)3-
catalyzed ring-closure. However, when dienone 9 was
treated by a two-step strategy, a complex mixture was
afforded.
With the optimal condition (Table 1, entry 1), we further
explored the substrate scope of the disproportionation
reaction; the results are shown in Table 2 and entries 1-12.
For the two-step route (NaBH4 mediated reduction with
100% conversion yields and Bi(OTf)3 catalyzed reaction),
different diversified and well-tolerated aryl (Ar) groups of
chalcones 3a-j (entries 1-10) performed similar distributed
ratios (3/5
=
1/1) and isolated yields (3/5
=
38%~48%/35%~45%), including electron-donating aryl
groups 4-MeOC6H4, 3,4-CH2O2C6H3, 3,4,5-(MeO)3C6H2,
4-ClC6H4, 3-MeOC6H4), electron-neutral aryl group (Ph,
Tol, 2-naphthyl, biphenyl), and an electron-withdrawing
aryl group (4-FC6H4). In entry 12, however, the optimal
condition was inappropriate for the 2-furyl group due to 31
being provided in a 12% yield. Among the complex
product mixture, only trace amounts of 5k-l were detected.
From the results, we found that 2,4-(MeO)2C6H3 and 2-
furyl group were unstable in converting into a complex
mixture via intramolecular annulation under Bi(OTf)3
catalyzed conditions. With the above results, we focused
next on the two-step route of asymmetric chalcones (Ar ≠
Ar1), as shown in Table 3. By NaBH4 mediated reduction
(100% conversion yields) and Bi(OTf)3 catalyzed reaction
protocol, chalcones 3m-r (Ar or Ar1 = Ph, 4-MeC6H4, 4-
FC6H4, 4-MeOC6H4) obeyed the above-mentioned reaction
behaviour to afford sole 3m-r (38~42%) and two pairs of
inseparated 5m-o and 5m’-o’ (35~40%, entries 1-6).
Interestingly, 3’ was not detected. On the basis of NMR
spectrums, the ratios of 5m-o and 5m’-o’ were determined
as 1/1~4/1. When Ar1 was changed to bicyclic 2-naphthyl
(3s), 41% of 3s was isolated and the ratios of 5s/5s’ (33%)
Table 3. Synthesis of 3 and 5-5’a-b
O
1
1
Ar
Ar
Ar
Ar
O
OH
4
3
NaBH4
Bi(OTf)
5
3
1
1
and
Ar
Ar
Ar
Ar
+
O
THF, MeOH
CH Cl
2
2
1
1
3
Ar
Ar
Ar
Ar
(100% conversion yields)
3' (not detected)
5'
entry 3, Ar =, Ar1 =
4, %c
3, %d
5+5’, %,d ratio
1
2
3
4
5
6
7
8
9
3m, Ph, 4-MeC6H4
4m, 100 3m, 38 5m/5m’, 38, 4:1
3n, Ph, 4-FC6H4
4n, 100 3n, 40
4o, 100 3o, 42
4p, 100 3p, 41
4q, 100 3q, 39
4r, 100 3r, 40
4s, 100 3s, 41
4t, 100 3t, 22
4u, 100 3u, 30
5n/5n’, 40, 1:1
5o/5o’, 40, 3:1
5m/5m’, 38, 5:2
5n/5n’, 36, 1:1
5o/5o’, 35, 3:1
5s/5s’, 33, 3:1
5t/5t’, 20, 3:1
5u/5u’, 32, 3:1
5v/5v’, 33, 1:1
3o, Ph, 4-MeOC6H4
3p, 4-MeC6H4, Ph
3q, 4-FC6H4, Ph
3r, 4-MeOC6H4, Ph,
3s, Ph, 2-naphthyl
3t, Ph, 9-anthracyl
3u, Ph, 3,4-CH2O2C6H3
10 3v, Ph, 3,4,5-(MeO)3C6H2 4v, 100 3v, 33

ACCEPTED MANUSCRIPT
4
Tetrahedron
aThe reactions were run on a 1.0 mmol scale with 3m-v, NaBH4 (35 mg, 1.0 mmol), THF/MeOH
(3 mL/3 mL), 0 oC, 10 min. bThe reactions were run on a resulting crude 4m-v, Bi(OTf)3 (13 mg,
2 mol%), CH2Cl2 (5 mL), rt, 1 h. cConversion yields (by TLC analysis). dIsolated yields.
Scheme 2. Proposed Mechanism
mCPBA and intramolecular annulation of the resulting
epoxide with Bi(OTf)3, 11 was generated in a 91% yield.
The present (3+2) annulation strategy provided a new
synthetic method for the formation of 1,3-diarylindene
skeleton. In order to find further insight for the Bi(OTf)3
mediated disproportionation process, 4a-1 (prepared from
NaBD4 mediated reduction of 3a) was chosen as the
deuterated model substrate (Scheme 5). When the reaction
of in-situ generated 4a-1 was treated with Bi(OTf)3, 3a and
a mixture of di-deuterated 5w and 5x (ratio, 4:5) were
obtained in 41% and 34% yields, respectively. The
expected results of the redox procedure demonstrated that
hydride of benzylic position on I and II triggered the
formation of two structural frameworks 3 and 5 via
intramolecular SN2’- or SN2-type deuterium transfer.
Ar
Ar
1
Ar
TfO
O
TfO
O
H
Bi
O
Bi
O
H
1
1
1
Ar
Ar
Ar
Ar
Ar
1
Ar
H
1
Ar
Ar
Ar
A1
A2
5'
path a
TfO
O
+
Bi
O
OH
NaBH
4
Bi(OTf)
1
1
3
+
Ar
Ar
Ar
Ar
O
H
3
4
3
H O
2
2 TfOH
+
path b
TfO
Ar
Ar
1
1
Ar
Ar
O
H
O
H
Bi
Bi
1
1
TfO
O
Ar
O
Ar
1
Ar
Ar
Ar
Ar
B1
B2
5
Scheme 3. Reactions of 7 and 9
Conclusion
O
1) NaBH4, THF, MeOH
2) Bi(OTf) CH Cl
In summary, we have developed a Bi(OTf)3 catalyzed
disproportionation from cinnamyl alcohols to chalcones
and benzyl styrenes in CH2Cl2 at rt. The use of various
metal triflates was well-investigated for a facile conversion.
A plausible mechanism has been proposed. Further
investigations regarding the synthetic application of metal
triflates are on-going in our laboratory.
Ph
Ph
Ph
Ph
O
O
3,
2
2
7
8 (71%)
O
1) NaBH4, THF, MeOH
2) Bi(OTf) CH Cl
complex mixture
Ph
Ph
3,
2
2
9
Scheme 4. Synthesis of 11
Experimental section
OMe
MeO
OMe
Ph
MeO
General. All reagents and solvents were obtained from
commercial sources and used without further purification.
Reactions were routinely carried out under an atmosphere of
air with magnetic stirring. Products in organic solvents were
dried with anhydrous magnesium sulfate before concentration
in vacuo. Melting points were determined with a SMP3
melting apparatus. 1H and 13C NMR spectra were recorded on
a Varian INOVA-400 spectrometer operating at 400 and at
100 MHz, respectively. High resolution mass spectra (HRMS)
were measured with a mass spectrometer Finnigan/Thermo
Quest MAT 95XL.
O
NaBH4 then
mCPBA
then Bi(OTf)
Ph
Ph
BF3-OEt2
veratrole
3
Ph
Ph
10 (79%)
Ph
3a
11 (91%)
Scheme 5. Control Deuterated Experiments
NaBD4
(99% D)
O
OH
Bi(OTf)
3
3a
5w / 5x
(4 : 5, 34%)
+
Ph
Ph
Ph
Ph
(41%)
D
THF, MeOH
CH Cl
2
2
3a
4a-1
D
Ph
A representative synthetic procedure of skeletons 3 and 5
is as follows: NaBH4 (68 mg, 2.0 mmol) was added to a
solution of chalcones 3 (1.0 mmol) in the co-solvent of
MeOH (3 mL) and THF (3 mL) at rt. The reaction mixture
was stirred at rt for 30 min and the solvent was
concentrated. The residue was diluted with water (10 mL)
and the mixture was extracted with EtOAc (3 x 20 mL).
The combined organic layers were washed with brine,
dried, filtered and evaporated to afford crude product.
Without further purification, Bi(OTf)3 (13 mg, 0.02 mmol)
was added to a solution of resulting crude 4 in CH2Cl2 (5
mL) at rt. The reaction mixture was stirred at rt for 1 h and
the solvent was concentrated. The residue was diluted with
water (10 mL) and the mixture was extracted with EtOAc
(3 x 20 mL). The combined organic layers were washed
D
TfO
O
Ph
O
Ph
Bi
O
D
+
Ph
D
Bi
TfO
O
Ph
Ph
deuterium
transfer
Ph
Ph
II
I
S 2'
N
S 2
N
D
D
O
D
D
Ph
Ph
Ph
3a
Ph
Ph
Ph
5w
5x
To explore the two-step synthetic application, the indene
skeleton was examined (Scheme 4). By the involvement of
veratrole,12 10 with the 1,1,3-triarylpropene skeleton was
isolated in a 79% yield via reduction and Friedel-Crafts
alkylation. Furthermore, by the oxidation of 10 with

ACCEPTED MANUSCRIPT
Tetrahedron
5
with brine, dried, filtered and evaporated to afford crude
product. Purification on silica gel (hexanes/EtOAc =
10/1~6/1) afforded skeletons 3 and 5.
1,3-Dinaphthalen-2-ylpropenone (3f).13d Yield = 43% (132
mg); Colorless solid; mp = 197-198 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C23H17O 309.1280, found 309.1283; H NMR (400 MHz,
1,3-Diphenylpropenone (3a).13a Yield = 48% (100 mg);
Colorless solid; mp = 38-40 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI, M++1) calcd for
CDCl3): δ 8.59 (s, 1H), 8.15 (dd, J = 1.6, 8.8 Hz, 1H),
8.07-7.79 (m, 10 H), 7.65-7.52 (m, 4H); 13C NMR (100
MHz, CDCl3): δ 190.27, 144.87, 135.66, 135.51, 134.41,
133.41, 132.61, 132.47, 130.67, 129.93, 129.54, 128.75,
128.66, 128.59, 128.38, 127.84, 127.81, 127.38, 126.79
(2x), 124.54, 123.74, 122.23.
1
C15H13O 209.0961, found 209.0966; H NMR (400 MHz,
CDCl3): δ 8.05-8.02 (m, 2H), 7.83 (d, J = 15.6 Hz, 1H),
7.67-7.61 (m, 2H), 7.60-7.49 (m, 4H), 7.44-7.40 (m, 3H);
13C NMR (100 MHz, CDCl3): δ 190.44, 144.75, 138.11,
134.79, 132.72, 130.47, 128.88 (2x), 128.55 (2x), 128.43
(2x), 128.38 (2x), 121.99.
1,3-Bis-(3,4,5-trimethoxyphenyl)propenone (3g). Yield =
41% (159 mg); Colorless solid; mp = 130-132 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1,3-Bis-(4-methoxyphenyl)propenone (3b). Yield = 46%
1
M++1) calcd for C21H25O7 389.1600, found 389.1602; H
o
(123 mg); Colorless solid; mp = 80-82 C (recrystallized
NMR (400 MHz, CDCl3): δ 7.69 (dd, J = 1.6, 15.6 Hz, 1H),
7.32 (dd, J = 0.8, 15.6 Hz, 1H), 7.24 (d, J = 1.2 Hz, 2H),
6.84 (d, J = 1.6 Hz, 2H), 3.93 (s, 3H), 3.92 (s, 3H), 3.91 (s,
3H), 3.90 (br s, 6H), 3.88 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 189.35, 153.43 (2x), 153.09 (2x), 144.88, 142.52,
140.49, 133.52, 130.30, 121.25, 106.24 (2x), 105.75 (2x),
60.91, 60.88, 56.41 (2x), 56.21 (2x).
1,3-Bis-(4-chlorophenyl)propenone (3h).13b Yield = 44%
(121 mg); Colorless solid; mp = 156-158 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
C15H11Cl2O 277.0187, found 277.0186; 1H NMR (400
MHz, CDCl3): δ 7.94 (d, J = 8.4 Hz, 2H), 7.74 (d, J = 15.6
Hz, 1H), 7.55 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 8.4 Hz, 2H),
7.43 (d, J = 15.6 Hz, 1H), 7.37 (d, J = 8.4 Hz, 2H); 13C
NMR (100 MHz, CDCl3): δ 188.70, 143.68, 139.30,
136.57, 136.24, 133.13, 129.82 (2x), 129.57 (2x), 129.21
(2x), 128.91 (2x), 121.79.
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C17H17O3 269.1178, found 269.1174; H NMR (400 MHz,
CDCl3): δ 8.02 (d, J = 8.8 Hz, 2H), 7.76 (d, J = 15.2 Hz,
1H), 7.57 (d, J = 8.8 Hz, 2H), 7.41 (d, J = 15.2 Hz, 1H),
6.95 (d, J = 8.8 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.85 (s,
3H), 3.82 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 188.59,
163.16, 161.40, 143.66, 131.22, 130.57 (2x), 129.99 (2x),
127.68, 119.41, 114.27 (2x), 113.67 (2x), 55.34, 55.26.
1,3-Bis-(4-fluorophenyl)propenone (3c).13b Yield = 41%
(100 mg); Colorless solid; mp = 105-107 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
C15H11F2O 245.0778, found 245.0778; 1H NMR (400 MHz,
CDCl3): δ 8.06-8.02 (m, 2H), 7.77 (d, J = 15.6 Hz, 1H),
7.64-7.60 (m, 2H), 7.42 (d, J = 15.6 Hz, 1H), 7.19-7.08 (m,
4H); 13C NMR (100 MHz, CDCl3): δ 188.51, 165.59 (d, J
= 252.5 Hz), 164.07 (d, J = 250.9 Hz), 143.64, 134.41 (d, J
= 3.0 Hz), 131.02 (d, J = 9.1 Hz, 2x), 130.75 (d, J = 3.1
Hz), 130.33 (d, J = 8.4 Hz, 2x), 121.25, 116.11 (d, J = 22.0
Hz, 2x), 115.72 (d, J = 22.0 Hz, 2x).
1,3-Bis-(3-methoxyphenyl)propenone (3i). Yield = 41%
(110 mg); Colorless oil; HRMS (ESI, M++1) calcd for
1
C17H17O3 269.1178, found 269.1180; H NMR (400 MHz,
1,3-Bis-benzo[1,3]dioxol-5-ylpropenone (3d). Yield = 44%
(130 mg); Colorless solid; mp = 174-176 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
CDCl3): δ 7.76 (d, J = 16.0 Hz, 1H), 7.60-7.58 (m, 1H),
7.54-7.53 (m, 1H), 7.48 (d, J = 16.0 Hz, 1H), 7.39 (t, J =
8.0 Hz, 1H), 7.32 (t, J = 8.0 Hz, 1H), 7.22 (d, J = 8.0 Hz,
1H), 7.15-7.10 (m, 2H), 6.96-6.93 (m, 1H), 3.86 (s, 3H),
3.83 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 190.05,
159.85, 159.80, 144.62, 139.45, 136.15, 129.83, 129.46,
122.28, 121.00, 120.94, 119.15, 116.21, 113.36, 112.82,
55.34, 55.21.
1
C17H13O5 297.0763, found 297.0766; H NMR (400 MHz,
CDCl3): δ 7.71 (d, J = 15.6 Hz, 1H), 7.62 (dd, J = 1.6, 8.0
Hz, 1H), 7.51 (d, J = 1.6 Hz, 1H), 7.31 (d, J = 15.6 Hz,
1H), 7.14 (d, J = 1.6 Hz, 1H), 7.10 (dd, J = 1.6, 8.0 Hz,
1H), 6.88 (d, J = 8.0 Hz, 1H), 6.83 (d, J = 8.0 Hz, 1H),
6.05 (s, 2H), 6.01 (s, 2H); 13C NMR (100 MHz, CDCl3): δ
188.07, 151.55, 149.76, 148.36, 148.23, 144.03, 133.13,
129.43, 125.01, 124.46, 119.71, 108.61, 108.37, 107.85,
106.59, 101.80, 101.58.
1,3-Bis-biphenyl-4-ylpropenone (3j).13e Yield = 42% (151
mg); Colorless solid; mp = 199-201 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C27H21O 361.1593, found 361.1590; H NMR (400 MHz,
1,3-Di-p-tolylpropenone (3e).13c Yield = 42% (99 mg);
Colorless solid; mp = 127-129 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI, M++1) calcd for
CDCl3): δ 8.14 (d, J = 8.0 Hz, 2H), 7.91 (d, J = 15.6 Hz,
1H), 7.75 (d, J = 8.0 Hz, 4H), 7.69-7.61 (m, 7H), 7.52-7.38
(m, 6H); 13C NMR (100 MHz, CDCl3): δ 189.83, 145.50,
144.26, 143.28, 140.11, 139.92, 136.95, 133.88, 129.10
(2x), 128.97 (2x), 128.93 (2x), 128.90 (2x), 128.18, 127.88,
127.58 (2x), 127.27 (4x), 127.03 (2x), 121.82.
1
C17H17O 237.1280, found 237.1285; H NMR (400 MHz,
CDCl3): δ 7.95 (d, J = 8.4 Hz, 2H), 7.80 (d, J = 15.2 Hz,
1H), 7.53 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 15.2 Hz, 1H),
7.29 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 2.42 (s,
3H), 2.37 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 189.80,
144.25, 143.31, 140.74, 135.60, 132.09, 129.52 (2x),
129.13 (2x), 128.45 (2x), 128.28 (2x), 120.85, 21.48, 21.35.
1,3-Bis-(2,4-dimethoxyphenyl)propenone (3k). Yield
=
21% (69 mg); Colorless solid; mp = 126-128 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C19H21O5 329.1389, found 329.1385; H
1

ACCEPTED MANUSCRIPT
6
Tetrahedron
NMR (400 MHz, CDCl3): δ 7.93 (d, J = 15.6 Hz, 1H), 7.70
(d, J = 8.4 Hz, 1H), 7.52 (d, J = 8.8 Hz, 1H), 7.45 (d, J =
16.0 Hz, 1H), 6.55-6.43 (m, 4H), 3.87 (s, 3H), 3.85 (s, 3H),
3.84 (s, 3H), 3.82 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
191.17, 163.63, 162.55, 160.05, 160.01, 137.80, 132.50,
130.11, 125.33, 122.71, 117.46, 105.28, 104.95, 98.60,
98.27, 55.59, 55.39, 55.37, 55.34.
1,3-Difuran-2-ylpropenone (3l).13f Yield = 12% (23 mg);
Colorless oil; HRMS (ESI, M++1) calcd for C11H9O3
189.0552, found 189.0553; 1H NMR (400 MHz, CDCl3): δ
7.61 (d, J = 1.6 Hz, 1H), 7.59 (d, J = 16.0 Hz, 1H), 7.49 (d,
J = 1.6 Hz, 1H), 7.30-7.27 (m, 2H), 6.68 (d, J = 3.2 Hz,
1H), 6.55-6.53 (m, 1H), 6.47-6.46 (m, 1H); 13C NMR (100
MHz, CDCl3): δ 177.58, 153.58, 151.43, 146.44, 144.93,
129.71, 118.74, 117.29, 116.23, 112.58, 112.36.
1-(4-Fluorophenyl)-3-phenylpropenone (3q).13g Yield =
39% (88 mg); Colorless solid; mp
75-77 oC
=
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C15H12FO 227.0872, found 227.0871; H
NMR (400 MHz, CDCl3): δ 8.07-8.02 (m, 2H), 7.80 (d, J =
15.6 Hz, 1H), 7.64-7.60 (m, 2H), 7.49 (d, J = 15.6 Hz, 1H),
7.42-7.37 (m, 3H), 7.18-7.12 (m, 2H); 13C NMR (100 MHz,
CDCl3): δ 188.58, 165.46 (d, J = 252.4 Hz), 144.86, 134.64,
134.40 (d, J = 3.0 Hz), 130.97 (d, J = 9.1 Hz, 2x), 130.51,
128.85 (2x), 128.35 (2x), 121.43, 115.58 (d, J = 21.9 Hz,
2x).
1-(4-Methoxyphenyl)-3-phenylpropenone (3r).13g Yield =
40% (95 mg); Colorless solid; mp = 105-107 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C16H15O2 239.1072, found 239.1074; H
NMR (400 MHz, CDCl3): δ 8.04 (d, J = 9.2 Hz, 2H), 7.80
(d, J = 16.0 Hz, 1H), 7.65-7.61 (m, 2H), 7.54 (d, J = 16.0
Hz, 1H), 7.43-7.38 (m, 3H), 6.97 (d, J = 8.8 Hz, 2H), 3.86
(s, 3H); 13C NMR (100 MHz, CDCl3): δ 188.53, 163.33,
143.79, 134.98, 130.98, 130.70 (2x), 130.21, 128.81 (2x),
128.24 (2x), 121.78, 113.74 (2x), 55.35.
1-Phenyl-3-p-tolylpropenone (3m).13g Yield = 38% (84
o
mg); Colorless solid; mp = 88-90 C (recrystallized from
hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C16H15O 223.1123, found 223.1123; H NMR (400 MHz,
CDCl3): δ 8.03-8.01 (m, 2H), 7.80 (d, J = 15.2 Hz, 1H),
7.60-7.48 (m, 6H), 7.23 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H);
13C NMR (100 MHz, CDCl3): δ 190.63, 144.91, 141.06,
138.35, 132.62, 132.14, 129.68 (2x), 128.55 (2x), 128.43
(4x), 121.10, 21.49.
3-Naphthalen-2-yl-1-phenylpropenone (3s).13h Yield
=
41% (106 mg); Colorless solid; mp = 155-157 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C19H15O 259.1123, found 259.1130; H
1
3-(4-Fluorophenyl)-1-phenylpropenone (3n).13b Yield =
NMR (400 MHz, CDCl3): δ 8.09-8.06 (m, 2H), 7.98 (d, J =
15.6 Hz, 2H), 7.88-7.82 (m, 2H), 7.80 (s, 1H), 7.96 (s, 1H),
7.64 (d, J = 15.6 Hz, 1H), 7.61-7.58 (m, 1H), 7.54-7.50 (m,
4H); 13C NMR (100 MHz, CDCl3): δ 190.37, 144.80 (2x),
138.20, 134.29, 133.26, 132.68, 132.28, 130.54, 128.63,
128.55 (2x), 128.44 (2x), 127.71, 127.27, 126.67, 123.59,
122.10.
40% (90 mg); Colorless solid; mp
=
79-81 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C15H12FO 227.0872, found 227.0874; H
NMR (400 MHz, CDCl3): δ 8.01 (d, J = 8.4 Hz, 2H), 7.77
(d, J = 15.6 Hz, 1H), 7.66-7.60 (m, 2H), 7.59-7.57 (m, 1H),
7.51 (d, J = 8.0 Hz, 2H), 7.46 (d, J = 15.6 Hz, 1H), 7.13-
7.08 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 190.24,
164.02 (d, J = 250.9 Hz), 143.44, 138.10, 132.79, 131.12
(d, J = 3.1 Hz), 130.30 (d, J = 9.1 Hz, 2x), 128.61 (2x),
128.43 (2x), 121.76 (d, J = 2.3 Hz), 116.08 (d, J = 22.0 Hz,
2x).
3-Anthracen-9-yl-1-phenylpropenone (3t). Yield = 22%
o
(68 mg); Colorless solid; mp = 132-134 C (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C23H17O 309.1280, found 309.1286; H NMR (400 MHz,
CDCl3): δ 8.30 (s, 1H), 8.11-8.09 (m, 2H), 7.94-7.88 (m,
3H), 7.61-7.58 (m, 2H), 7.47-7.39 (m, 5H), 7.27-7.23 (m,
1H), 7.09-7.05 (m, 2H); 13C NMR (100 MHz, CDCl3): δ
192.56, 139.24 (2x), 137.51, 132.33 (2x), 131.01 (2x),
130.75 (2x), 128.70 (2x), 128.04 (2x), 127.75 (2x), 127.18,
125.80 (2x), 125.41 (2x), 125.04 (2x).
3-(4-Methoxyphenyl)-1-phenylpropenone (3o).13g Yield =
42% (100 mg); Colorless oil; HRMS (ESI, M++1) calcd for
1
C16H15O2 239.1072, found 239.1076; H NMR (400 MHz,
CDCl3): δ 7.99 (d, J = 8.4 Hz, 2H), 7.76 (d, J = 15.6 Hz,
1H), 7.54 (d, J = 8.4 Hz, 2H), 7.45 (d, J = 7.6 Hz, 2H),
7.39 (d, J = 15.6 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H), 3.76 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 190.07, 161.42,
144.34, 138.20, 132.29, 129.98 (2x), 128.29 (2x), 128.14
(2x), 127.27, 119.38, 114.15 (2x), 55.06.
3-Phenyl-1-p-tolylpropenone (3p).13g Yield = 41% (91 mg);
Colorless oil; HRMS (ESI, M++1) calcd for C16H15O
223.1123, found 223.1122; 1H NMR (400 MHz, CDCl3): δ
7.95 (d, J = 8.0 Hz, 2H), 7.82 (d, J = 15.6 Hz, 1H), 7.63-
7.61 (m, 2H), 7.54 (d, J = 15.6 Hz, 1H), 7.40-7.38 (m, 3H),
7.28 (d, J = 8.0 Hz, 2H), 2.40 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 189.63, 144.09, 143.38, 135.40, 134.76, 130.18,
129.11 (2x), 128.70 (2x), 128.44 (2x), 128.19 (2x), 121.82,
21.41.
3-Benzo[1,3]dioxol-5-yl-1-phenylpropenone (3u).13g Yield
= 30% (76 mg); Colorless solid; mp = 106-108 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C16H13O3 253.0865, found 253.0866; H
NMR (400 MHz, CDCl3): δ 8.02-7.99 (m, 2H), 7.73 (d, J =
15.6 Hz, 1H), 7.59-7.55 (m, 1H), 7.52-7.47 (m, 2H), 7.36
(d, J = 15.6 Hz, 1H), 7.16 (d, J = 1.2 Hz, 1H), 7.12 (dd, J =
1.6, 8.0 Hz, 1H), 6.84 (d, J = 8.0 Hz, 1H), 6.02 (s, 2H); 13
C
NMR (100 MHz, CDCl3): δ 190.36, 149.89, 148.39,
144.63, 138.38, 132.59, 129.34, 128.54 (2x), 128.37 (2x),
125.17, 120.10, 108.63, 106.63, 101.59.
1-Phenyl-3-(3,4,5-trimethoxyphenyl)propenone (3v). Yield
= 33% (98 mg); Colorless solid; mp = 141-142 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,

ACCEPTED MANUSCRIPT
Tetrahedron
7
1
M++1) calcd for C18H19O4 299.1283, found 299.1284; H
(E)-2-(3-(2-Naphthyl)allyl)naphthalene (5f). Yield = 40%
NMR (400 MHz, CDCl3): δ 7.99-7.97 (m, 2H), 7.68 (d, J =
15.6 Hz, 1H), 7.56-7.51 (m, 1H), 7.48-7.43 (m, 2H), 7.39
(d, J = 15.6 Hz, 1H), 6.82 (s, 2H), 3.87 (s, 6H), 3.86 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 190.24, 153.25,
144.78 (2x), 140.21, 138.05, 132.53, 130.15, 128.41 (2x),
128.27 (2x), 121.19, 105.48 (2x), 60.76, 55.99 (2x).
(118 mg); Colorless solid; mp = 134-136 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C23H19 295.1487, found 295.1488; H NMR (400 MHz,
CDCl3): δ 7.86-7.78 (m, 6H), 7.74 (br s, 2H), 7.63 (dd, J =
1.6, 8.8 Hz, 1H), 7.52-7.42 (m, 5H), 6.69 (d, J = 15.6 Hz,
1H), 6.59 (dt, J = 6.4, 15.6 Hz, 1H), 3.79 (d, J = 6.4 Hz,
2H); 13C NMR (100 MHz, CDCl3): δ 137.60, 134.91,
133.68, 133.64, 132.78, 132.19, 131.39, 129.55, 128.09,
128.07, 127.86, 127.64, 127.61, 127.50, 127.47, 126.79,
126.16, 125.99, 125.77, 125.60, 125.34, 123.57, 39.56.
Cinnamylbenzene (5a).14a Yield = 45% (87 mg); Colorless
oil; HRMS (ESI, M++1) calcd for C15H15 195.1174, found
1
195.1180; H NMR (400 MHz, CDCl3): δ 7.40-7.20 (m,
10H), 6.49 (d, J = 16.0 Hz, 1H), 6.38 (dt, J = 3.2, 16.0 Hz,
1H), 3.58 (d, J = 6.8 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 140.14, 137.45, 131.04, 129.20, 128.65 (2x),
128.47 (4x), 127.08, 126.16, 126.10 (2x), 39.33.
(E)-1,2,3-Trimethoxy-5-(3-(3,4,5-
trimethoxyphenyl)allyl)benzene (5g).14c Yield = 39% (146
mg); Colorless oil; HRMS (ESI, M++1) calcd for C21H27O6
375.1808, found 375.1809; 1H NMR (400 MHz, CDCl3): δ
6.59 (br s, 2H), 6.46 (br s, 2H), 6.40-6.35 (m, 1H), 6.28-
6.21 (m, 1H), 3.86 (br s, 6H), 3.85 (br s, 6H), 3.83 (br s,
6H), 3.48 (d, J = 6.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 153.29 (2x), 153.25 (2x), 135.76, 133.09, 130.96
(2x), 128.50 (2x), 105.67 (2x), 103.27 (2x), 60.85, 60.81,
56.09 (2x), 56.06 (2x), 39.61.
(E)-1-Methoxy-4-(3-(4-methoxyphenyl)allyl)benzene
(5b).14a Yield = 39% (99 mg); Colorless oil; HRMS (ESI,
1
M++1) calcd for C17H19O2 255.1385, found 255.1386; H
NMR (400 MHz, CDCl3): δ 7.31 (d, J = 8.8 Hz, 2H), 7.17
(d, J = 8.4 Hz, 2H), 6.89-6.83 (m, 4H), 6.40 (d, J = 15.6 Hz,
1H), 6.22 (dt, J = 6.8, 15.6 Hz, 1H), 3.81 (br s, 6H), 3.49
(d, J = 6.8 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 158.79,
158.00, 132.45, 130.35, 130.08, 129.53 (2x), 127.48,
127.17 (2x), 113.89 (2x), 113.85 (2x), 55.24 (2x), 38.39.
(E)-1-Chloro-4-(3-(4-chlorophenyl)allyl)benzene (5h).14c
Yield = 38% (100 mg); Colorless oil; HRMS (ESI, M++1)
1
calcd for C15H13Cl2 263.0394, found 263.0392; H NMR
(E)-1-Fluoro-4-(3-(4-fluorophenyl)allyl)benzene
(5c).14c
(400 MHz, CDCl3): δ 7.30 (d, J = 8.4 Hz, 2H), 7.28 (br s,
4H), 7.17 (d, J = 8.4 Hz, 2H), 6.42-6.37 (m, 1H), 6.30 (dt,
J = 6.8, 15.6 Hz, 1H), 3.52 (d, J = 6.4 Hz, 2H); 13C NMR
(100 MHz, CDCl3): δ 138.24, 135.71, 132.80, 132.03,
130.21, 129.97 (2x), 129.29, 128.64 (2x), 128.59 (2x),
127.30 (2x), 38.52.
Yield = 39% (90 mg); Colorless oil; HRMS (ESI, M++1)
1
calcd for C15H13F2 231.0985, found 231.0986; H NMR
(400 MHz, CDCl3): δ 7.36-7.31 (m, 2H), 7.23-7.19 (m,
2H), 7.06-6.98 (m, 4H), 6.42 (d, J = 15.6 Hz, 1H), 6.26 (dt,
J = 6.8, 15.6 Hz, 1H), 3.53 (d, J = 6.8 Hz, 2H); 13C NMR
(100 MHz, CDCl3): δ 162.08 (d, J = 244.1 Hz), 161.51 (d,
J = 243.3 Hz), 135.61 (d, J = 3.0 Hz), 133.48 (d, J = 3.8
Hz), 130.00, 129.99 (d, J = 8.4 Hz, 2x), 128.76, 128.74,
127.76 (d, J = 7.5 Hz), 115.36 (d, J = 21.2 Hz, 2x), 115.23
(d, J = 21.2 Hz, 2x), 38.37.
(E)-1-Methoxy-3-(3-(3-methoxyphenyl)allyl)benzene
(5i).14d Yield = 38% (97 mg); Colorless oil; HRMS (ESI,
1
M++1) calcd for C17H19O2 255.1385, found 255.1380; H
NMR (400 MHz, CDCl3): δ 7.25 (d, J = 8.0 Hz, 1H), 7.21
(d, J = 8.0 Hz, 1H), 6.98-6.77 (m, 6H), 6.47-6.32 (m, 2H),
3.81 (s, 6H), 3.53 (d, J = 6.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 159.77, 141.71, 138.92, 131.04, 129.43 (2x),
129.34, 121.05, 118.83, 114.39, 112.86 (2x), 111.54,
111.36, 55.17, 55.15, 39.31.
(E)-1,2-Methylenedioxy-4-(3-(3,4-
methylenedioxyphenyl)allyl)benzene (5d). Yield = 38%
(107 mg); Colorless oil; HRMS (ESI, M++1) calcd for
1
C17H15O4 283.0970, found 283.0972; H NMR (400 MHz,
CDCl3): δ 6.90 (d, J = 1.6 Hz, 1H), 6.80-6.66 (m, 5H), 6.34
(d, J = 16.0 Hz, 1H), 6.14 (dt, J = 7.2, 16.0 Hz, 1H), 5.93
(s, 2H), 5.92 (s, 2H), 3.43 (d, J = 6.8 Hz, 2H); 13C NMR
(100 MHz, CDCl3): δ 147.95, 147.68, 146.82, 145.89,
138.82, 134.07, 131.96, 130.51, 127.62, 121.33, 120.53,
109.13, 108.21, 105.54, 100.94, 100.81, 38.89.
(E)-1-Phenyl-4-(3-(4-biphenyl)allyl)benzene (5j).14c Yield
= 35% (121 mg); Colorless solid; mp = 141-143 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C27H23 347.1800, found 347.1802; H
NMR (400 MHz, CDCl3): δ 7.64-7.57 (m, 8H), 7.49-7.45
(m, 6H), 7.38-7.35 (m, 4H), 6.62-6.43 (m, 2H), 3.65 (d, J =
6.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 141.00,
140.77, 139.90, 139.22, 136.50, 131.84, 130.76, 129.21,
129.09 (2x), 128.74 (2x), 128.72 (2x), 127.24 (2x), 127.19
(2x), 127.08, 127.02 (2x), 126.88 (2x), 126.74, 126.55 (2x),
39.02.
(E)-4-Methyl-1-(3-(4-methylphenyl)allyl)benzene (5e).14c
Yield = 37% (82 mg); Colorless oil; HRMS (ESI, M++1)
1
calcd for C17H19 223.1487, found 223.1489; H NMR (400
MHz, CDCl3): δ 7.47 (d, J = 8.0 Hz, 2H), 7.37-7.33 (m,
4H), 7.31 (d, J = 8.0 Hz, 2H), 6.64 (d, J = 16.0 Hz, 1H),
6.51 (dt, J = 6.8, 16.0 Hz, 1H), 3.71 (d, J = 6.4 Hz, 2H),
2.55 (s, 3H), 2.53 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
137.16, 136.60, 135.45, 134.73, 130.67, 129.11 (2x),
129.09 (2x), 128.49 (2x), 128.37, 125.97 (2x), 38.86, 21.06,
20.94.
(E)-4-Cinnamyl-1-methylbenzene (5m) and (E)-3-(4-
methylphenyl)allyl)benzene (5m’).14e Two isomers, ratio =
4:1; Yield = 38% (79 mg); Colorless oil; HRMS (ESI,
1
M++1) calcd for C16H17 209.1330, found 209.1330; H
NMR (400 MHz, CDCl3): δ 7.62-7.35 (m, 9H), 6.73-6.53
(m, 2H), 3.80-3.76 (m, 2H), 2.59 (s, 3H).

ACCEPTED MANUSCRIPT
8
Tetrahedron
(E)-4-Cinnamyl-1-fluorobenzene (5n) and (E)-3-(4-
fluorophenyl)allyl)benzene (5n’).14f Two isomers, ratio =
1:1; Yield = 40% (85 mg); Colorless oil; HRMS (ESI,
entry 7) was added to a solution of resulting crude 4a in
CH2Cl2 (5 mL) at rt. The reaction mixture was stirred at rt
for 1 h and the solvent was concentrated. The residue was
diluted with water (10 mL) and the mixture was extracted
with EtOAc (3 x 20 mL). The combined organic layers
were washed with brine, dried, filtered and evaporated to
afford crude product. Purification on silica gel
(hexanes/EtOAc = 10/1~6/1) afforded 6a. Two isomers,
ratio = 1:1; Yield = 65% (131 mg); Colorless oil; HRMS
(ESI, M++1) calcd for C30H27O 403.2062, found 403.2066;
1H NMR (400 MHz, CDCl3): δ 7.56-7.28 (m, 20H), 6.71
(dd, J = 3.2, 15.6 Hz, 2H), 6.51-6.40 (m, 2H), 5.21 (t, J =
8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 141.23,
141.15, 136.60 (2x), 131.53, 131.33, 130.46, 130.29,
128.51 (4x), 128.48 (2x), 127.70 (2x), 127.68 (2x), 127.65
(2x), 127.05 (4x), 126.60 (2x), 126.58 (2x), 79.21, 79.09.
1
M++1) calcd for C15H14F 213.1079, found 213.1082; H
NMR (400 MHz, CDCl3): δ 7.45-7.23 (m, 7H), 7.10-7.02
(m, 2H), 6.54-6.31 (m, 3H), 3.62-3.57 (m, 2H).
(E)-4-Cinnamyl-1-methoxybenzene (5o) and (E)-3-(4-
methoxyphenyl)allyl)benzene (5o’).14e Two isomers, ratio =
3:1; Yield = 40% (90 mg); Colorless oil; HRMS (ESI,
1
M++1) calcd for C16H17O 225.1280, found 225.1275; H
NMR (400 MHz, CDCl3): δ 7.39-7.17 (m, 7H), 6.90-6.84
(m, 2H), 6.48-6.21 (m, 2H), 3.82 (s, 3H), 3.58-3.51 (m,
2H).
(E)-2-Cinnamylnaphthalene
(5s)
and
(E)-2-(3-
phenyl)allyl)naphthalene (5s’).14e Two isomers, ratio = 1:1;
Yield = 33% (81 mg); Colorless oil; HRMS (ESI, M++1)
calcd for C19H17 245.1330, found 245.1332; H NMR (400
2,5-Diphenyltetrahydrofuran (8).16 NaBH4 (68 mg, 2.0
mmol) was added to a solution of enedione 7 (236 mg, 1.0
mmol) in the co-solvent of MeOH (3 mL) and THF (3 mL)
at rt. The reaction mixture was stirred at rt for 30 min and
the solvent was concentrated. The residue was diluted with
water (10 mL) and the mixture was extracted with EtOAc
(3 x 20 mL). The combined organic layers were washed
with brine, dried, filtered and evaporated to afford crude
product. Without further purification, Bi(OTf)3 (13 mg,
0.02 mmol) was added to a solution of resulting crude diol
in CH2Cl2 (5 mL) at rt. The reaction mixture was stirred at
rt for 1 h and the solvent was concentrated. The residue
was diluted with water (10 mL) and the mixture was
extracted with EtOAc (3 x 20 mL). The combined organic
layers were washed with brine, dried, filtered and
evaporated to afford crude product. Purification on silica
gel (hexanes/EtOAc = 10/1~6/1) afforded 8. Yield = 71%
(159 mg); Colorless oil; HRMS (ESI, M++1) calcd for
1
MHz, CDCl3): δ 7.87-7.61 (m, 4H), 7.52-7.23 (m, 8H),
6.68-6.44 (m, 2H), 3.76-3.64 (m, 2H).
(E)-9-Cinnamylanthracene
(5t)
and
(E)-9-(3-
phenyl)allyl)anthracene (5t’). Two isomers, ratio = 1:1;
Yield = 20% (59 mg); Colorless oil; HRMS (ESI, M++1)
1
calcd for C23H19 295.1487, found 295.1488; H NMR (400
MHz, CDCl3): δ 8.31 (s, 1H), 7.94-7.90 (m, 4H), 7.58-7.52
(m, 1H), 7.45-7.28 (m, 7H), 7.15 (d, J = 16.0 Hz, 1H),
7.07-7.04 (m, 2H), 6.57-6.51 (m, 1H), 4.42 (d, J = 8.0 Hz,
1H).
(E)-4-Cinnamyl-1,2-methylenedioxybenzene (5u) and (E)-
3-(3,4-methylenedioxyphenyl)allyl)benzene (5u’).14g Two
isomers, ratio = 3:1; Yield = 32% (76 mg); Colorless oil;
HRMS (ESI, M++1) calcd for C16H15O2 239.1072, found
1
239.1077; H NMR (400 MHz, CDCl3): δ 7.39-7.20 (m,
5H), 6.79-6.70 (m, 3H), 6.47-6.29 (m, 2H), 5.94 (s, 2H),
3.48 (d, J = 6.4 Hz, 2H).
1
C16H17O 225.1280, found 225.1283; H NMR (400 MHz,
CDCl3): δ 7.53 (d, J = 7.6 Hz, 2H), 7.49 (d, J = 7.2 Hz,
2H), 7.45-7.41 (m, 4H), 7.37-7.32 (m, 2H), 5.34 (t, J = 6.0
Hz, 1H), 5.12 (t, J = 5.2 Hz, 1H), 2.58-2.43 (m, 2H), 2.12-
2.00 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 143.59,
142.87, 128.28 (2x), 128.26 (2x), 127.21, 127.10, 125.91
(2x), 125.50 (2x), 81.24, 81.14, 35.49, 34.29.
(E)-5-Cinnamyl-1,2,3trimethoxybenzene (5v) and (E)-3-
(3,4,5-trimethyloxyphenyl)allyl)benzene (5v’).14h Two
isomers, ratio = 1:1; Yield = 33% (94 mg); Colorless oil;
HRMS (ESI, M++1) calcd for C18H21O3 285.1490, found
1
285.1493; H NMR (400 MHz, CDCl3): δ 7.40 (d, J = 8.0
Hz, 2H), 7.34-7.31 (m, 2H), 7.25-7.21 (m, 1H), 6.50 (d, J =
15.6 Hz, 1H), 6.49 (br s, 2H), 6.41-6.34 (m, 1H), 3.87 (br s,
9H), 3.52 (d, J = 6.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 153.13 (2x), 137.25, 136.32, 135.76, 131.01,
128.83, 128.39 (2x), 127.05 (2x), 126.01 (2x), 105.46,
60.69, 55.93 (2x), 39.56.
3-(3,4-Dimethoxyphenyl)-1,3-Diphenylprop-1-ene (10).17
NaBH4 (68 mg, 2.0 mmol) was added to a solution of 3a
(208 mg, 1.0 mmol) in the co-solvent of MeOH (3 mL) and
THF (3 mL) at rt. The reaction mixture was stirred at rt for
30 min and the solvent was concentrated. The residue was
diluted with water (10 mL) and the mixture was extracted
with EtOAc (3 x 20 mL). The combined organic layers
were washed with brine, dried, filtered and evaporated to
afford crude product. Without further purification, BF3-
OEt2 (285 mg, 2.0 mmol) was added to a solution of
resulting crude 4a and veratrole (280 mg, 2.0 mmol) in
CH2Cl2 (5 mL) at rt. The reaction mixture was stirred at rt
for 20 h and the solvent was concentrated. The residue was
diluted with water (10 mL) and the mixture was extracted
with EtOAc (3 x 20 mL). The combined organic layers
were washed with brine, dried, filtered and evaporated to
((1E,1'E)-oxybis(prop-1-ene-3,1,3-triyl))tetrabenzene
(6a).15 NaBH4 (68 mg, 2.0 mmol) was added to a solution
of 3a (208 mg, 1.0 mmol) in the co-solvent of MeOH (3
mL) and THF (3 mL) at rt. The reaction mixture was
stirred at rt for 30 min and the solvent was concentrated.
The residue was diluted with water (10 mL) and the
mixture was extracted with EtOAc (3 x 20 mL). The
combined organic layers were washed with brine, dried,
filtered and evaporated to afford crude product. Without
further purification, AgOTf (5 mg, 0.02 mmol; for Table 1,

ACCEPTED MANUSCRIPT
Tetrahedron
9
afford crude product. Purification on silica gel
HRMS (FAB, M+) calcd for C15H12D2 196.1219, found
196.1228; H NMR (400 MHz, CDCl3): δ 7.45-7.27 (m,
10H), 6.54 (d, J = 16.0 Hz, 5/9H for 5x), 6.46-6.40 (m, 1H,
for 5w+5x), 3.58 (br s, 4/9H, for 5w).
1
(hexanes/EtOAc = 10/1~6/1) afforded 10. Yield = 79%
o
(261 mg); Colorless solid; mp = 80-81 C (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C23H23O2 331.1698, found 331.1697; H NMR (400 MHz,
CDCl3): δ 7.48 (d, J = 7.2 Hz, 2H), 7.45-7.28 (m, 8H), 6.91
(s, 1H), 6.90 (d, J = 9.2 Hz, 2H), 6.80 (dd, J = 7.2, 16.0 Hz,
1H), 6.48 (d, J = 16.0 Hz, 1H), 4.97 (d, J = 7.2 Hz, 1H),
3.93 (s, 3H), 3.90 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
148.70, 147.42, 143.39, 137.00, 135.79, 132.49, 131.01,
128.34 (2x), 128.27 (2x), 128.21 (2x), 127.47, 126.19,
126.04 (2x), 120.40, 111.82, 110.92, 55.56, 55.53, 55.45.
Acknowledgments
The authors would like to thank the Ministry of Science
and Technology of the Republic of China for its financial
support (MOST 105-2113-M-037-001).
References and notes
5,6-Dimethoxy-1,3-diphenyl-1H-indene (11). mCPBA
(70%, 172 mg, 0.7 mmol) was added to a solution of 10
(165 mg, 0.5 mmol) in the CH2Cl2 (3 mL). The reaction
mixture was stirred at rt for 4 h and the solvent was
concentrated. The residue was diluted with water (10 mL)
and the mixture was extracted with EtOAc (3 x 20 mL).
The combined organic layers were washed with brine,
dried, filtered and evaporated to afford crude product.
Without further purification, Bi(OTf)3 (13 mg, 0.02 mmol)
was added to a solution of resulting crude diol in CH2Cl2
(5 mL) at rt. The reaction mixture was stirred at rt for 1 h
and the solvent was concentrated. The residue was diluted
with water (10 mL) and the mixture was extracted with
EtOAc (3 x 20 mL). The combined organic layers were
washed with brine, dried, filtered and evaporated to afford
crude product. Purification on silica gel (hexanes/EtOAc =
10/1~6/1) afforded 11. Yield = 91% (149 mg); Colorless
(1) Cannizzaro, S. Ann 1853, 88, 129-130.
(2) (a) Tischtschenko, W. J. Russ. Phys. Chem. Soc. 1906, 38, 355-418.
(b) Tischtschenko, W. Chem. Zentralbl. 1906, 771, 1309-1311. (c)
Claisen, L. Ber. Dtsch. Chem. Ges. 1887, 20, 646-650.
(3) (a) Meerwein, H.; Schmidt, R. Justus Liebigs Ann Chem. 1925, 39,
221-238. (b) Ponndorf, W. Angew. Chem. 1926, 39, 138-146. (c)
Verley, M. Bull. Soc. Chim. Fr. 1925, 37, 871-874.
(4) Oppenauer, R. V. Recl. Trav. Chim. Pays-Bas 1937, 56, 137-144.
(5) Recent examples on the disproportionation reactions, see: (a) Wang,
X.; Du, C.; Shi, H.; Pang, Y.; Jin, S.; Hou, Y.; Wang, Y.; Peng, X.;
Xiao, J.; Liu, Y.; Liu, Y.; Cheng, M. Tetrahedron 2015, 71, 6744-
6748. (b) Nakamura, T.; Tateishi, K.; Tsukagoshi, S.; Hashimoto, S.;
Watanabe, S.; Soloshonok, V. A.; Acena, J. L.; Kitagawa, O.
Tetrahedron 2012, 68, 4013-4017. (c) Stueckler, C.; Reiter, T. C.;
Baudendistel, N.; Faber, K. Tetrahedron 2010, 66, 663-667. (d)
Justicia, J.; Jiménez, T.; Morcillo, S. P.; Cuerva, J. M.; Oltra, J. E.
Tetrahedron 2009, 65, 10837-10841. (e) L’Hermite, N.; Giraud, A.;
Provot, O.; Peyrat, J.-F.; Alami, M.; Brion, J.-D. Tetrahedron 2006,
62, 11994-12002. (f) Fry, A. J. Tetrahedron 2016, 62, 6558-6565. (g)
Gerdin, M.; Moberg, C. Org. Lett. 2006, 8, 2929-2932. (h)
Matsukawa, S.; Hinakubo, Y. Org. Lett. 2003, 5, 1221-1223. (i)
Harischandra, D. N.; Lowery, G.; Zhang, R.; Newcomb, M. Org.
Lett. 2009, 11, 2089-2091. (j) Curran, S. P.; Connon, S. J. Org. Lett.
2012, 14, 1074-1077. (k) Mojtahedi, M. M.; Roholah, E. A.; Abaee,
M. S. Org. Lett. 2007, 9, 2791-2793. (l) Korth, H.-G.; Mulder, P. J.
Org. Chem. 2015, 80, 8206-8216. (m) Zhang, L.; Wang, S.; Zhou, S.;
Yang, G.; Sheng, E. J. Org. Chem. 2006, 71, 3149-3153. (n)
Yusubov, M. S.; Chi, K.-W.; Park, J. Y.; Karimov, R.; Zhdankin, V.
V. Tetrahedron Lett. 2006, 47, 6305-6308. (o) Hatano, B.;
Kadokawa, J.-i.; Tagaya, H. Tetrahedron Lett. 2002, 43, 5859-5861.
(p) Sominsky, L.; Rozental, E.; Gottlieb, H.; Gedanken, A.; Hoz, S. J.
Org. Chem. 2004, 69, 1492-1496.
o
solid; mp = 141-142 C (recrystallized from hexanes and
EtOAc); HRMS (ESI, M++1) calcd for C23H21O2 329.1542,
1
found 329.1544; H NMR (400 MHz, CDCl3): δ 7.47-7.44
(m, 2H), 7.27-7.12 (m, 9H), 6.98 (s, 1H), 6.75 (s, 1H), 4.90
(s, 1H), 3.92 (s, 3H), 3.79 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 149.00, 148.66, 147.77, 142.09, 140.30, 135.83,
135.20, 128.87 (2x), 128.40 (2x), 127.82 (2x), 127.68,
126.87, 126.63, 126.23 (2x), 107.91, 104.58, 56.27, 56.18,
56.12.
(6) Examples on the disproportionation reactions of allylic alcohols, for
Ir3+-Sn3+, see: (a) Chatterjee, P. N.; Roy, S. Tetrahedron 2012, 68,
3776-3785. For Fe3+, see: (b) Wang, J.; Huang, W.; Zhangm Z.;
Xiang, X.; Liu, R.; Zhou, X. J. Org. Chem. 2009, 74, 3299-3304.
(7) For Bi(OTf)3, see: (a) Chang, M.-Y.; Cheng, Y.-C.; Lu, Y.-J. Org.
Lett. 2015, 17, 3142-3145. (b) Chang, M.-Y.; Cheng, Y.-C.; Lu, Y.-
J. Org. Lett. 2015, 17, 1264-1267. (c) Chan, C.-K.; Chen, Y.-C.;
Chen, Y.-L.; Chang, M.-Y. Tetrahedron 2015, 71, 9187-9195. For
In(OTf)3, see: (d) Chang, M.-Y.; Lu, Y.-J.; Cheng, Y.-C.
Tetrahedron 2015, 71, 6840-6845. For Sc(OTf)3, see: (e) Chang, M.-
Y.; Chen, Y.-C.; Chan, C.-K.; Huang, G. G. Tetrahedron 2015, 71,
2095-2104. For Fe(OTf)3, see: (f) Chang, M.-Y.; Chen, Y.-H.;
Cheng, Y.-C. Tetrahedron 2016, 72, 518-524. For Tm(OTf)3, see: (g)
Chang, M.-Y.; Cheng, Y.-C. Synlett 2016, 27, 1931-1935. For
Sn(OTf)2, see: (h) Chan, C.-K.; Chen, Y.-H.; Chang, M.-Y.
Tetrahedron 2016, 72, 5121-5131. For Ga(OTf)3, see: (i) Wang, H.-
S.; Chan, C.-K.; Chang, M.-Y. Tetrahedron 2016, 72, 5132-5141.
For Cu(OTf)2, see: (j) Chan, C.-K.; Wang, H.-S.; Hsu, R.-T.; Chang,
M.-Y. Synthesis 2017, 49, 2045-2056.
Synthesis of deuterated 5w and 5x: NaBD4 (68 mg, 2.0
mmol) was added to a solution of 3a (208 mg, 1.0 mmol)
in the co-solvent of MeOH (3 mL) and THF (3 mL) at rt.
The reaction mixture was stirred at rt for 30 min and the
solvent was concentrated. The residue was diluted with
water (10 mL) and the mixture was extracted with EtOAc
(3 x 20 mL). The combined organic layers were washed
with brine, dried, filtered and evaporated to afford crude
product. Without further purification, Bi(OTf)3 (13 mg,
0.02 mmol) was added to a solution of resulting crude 4a-1
in CH2Cl2 (5 mL) at rt. The reaction mixture was stirred at
rt for 1 h and the solvent was concentrated. The residue
was diluted with water (10 mL) and the mixture was
extracted with EtOAc (3 x 20 mL). The combined organic
layers were washed with brine, dried, filtered and
evaporated to afford crude product. Purification on silica
gel (hexanes/EtOAc = 10/1~6/1) afforded 3a and a mixture
of 5w and 5x. For 3a, Yield = 41% (85 mg); For a mixture
of 5w and 5x (7:10), Yield = 34% (67 mg); Colorless oil;
(8) (a) Chang, M.-Y.; Tai, H.-Y.; Chen, Y.-L.; Hsu, R.-T. Tetrahedron
2012, 68, 7941-7948. (b) Chang, M.-Y.; Chan, C.-K.; Wu, M.-H.
Tetrahedron 2013, 69, 7916-7924 and referneces cited therein.
(9) Chang, M.-Y.; Tsai, C.-Y.; Wu, M.-H. Tetrahedron 2013, 69, 6364-
6370 and references cited therein.

ACCEPTED MANUSCRIPT
10
Tetrahedron
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250-253.
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Supplementary Material
Experimental procedure and scanned photocopies of NMR
(CDCl3) spectral data were supported.
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