Addition reactions of organic carbanion equivalents via hydrazones in water

Article abstract of DOI:10.1016/j.tet.2020.131889

The addition of organometallic reagents to unsaturated bonds is one of the most powerful tools for carbon–carbon bond formations. Alkylation through organometallic reagents requires stoichiometric quantity of metal and tedious anhydrous operation in most cases. Here, we report “umpolung” nucleophilic additions of hydrazones to Michael acceptors, carbonyls and imines in water. Under the catalysis of ruthenium(II), the addition reactions could be carried out in pure water to provide various alkylation products in moderate to good yields.

Full text of DOI:10.1016/j.tet.2020.131889

Journal Pre-proof
Addition reactions of organic carbanion equivalents via hydrazones in water
Yi-Zhan Wang, Qi Liu, Liang Cheng, Song-Chen Yu, Li Liu, Chao-Jun Li
PII:
S0040-4020(20)31153-4
https://doi.org/10.1016/j.tet.2020.131889
TET 131889
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 4 November 2020
Revised Date: 9 December 2020
Accepted Date: 16 December 2020
Please cite this article as: Wang Y-Z, Liu Q, Cheng L, Yu S-C, Liu L, Li C-J, Addition reactions of organic
carbanion equivalents via hydrazones in water, Tetrahedron, https://doi.org/10.1016/j.tet.2020.131889.
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An aqueous umpolung addition with
hydrazones
Yi-Zhan Wanga,b, Qi Liua,b, Liang Chenga,b,*, Song-Chen Yua,b, Li Liua,b,* and Chao-Jun Lic,*
aBeijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Recognition
and Function, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100190, China.
bUniversity of Chinese Academy of Sciences, Beijing 100049, China
cDepartment of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801
Sherbrooke Street West, Montreal, Quebec H3A 0B8, Canada.
R2
NH2
X
cat. [Ru]
N
XH
R1
N2
+
+
H2O
R2 R3
R1
R3
55 Examples
Yield up to 83%
X = O, NR, C-EWG
Graphical Abstract
To create your abstract, type over the instructions in the template box below.
Fonts or abstract dimensions should not be changed or altered.

1
Tetrahedron
journal homepage: www.elsevier.com
An aqueous umpolung addition with hydrazones
Yi-Zhan Wanga,b, Qi Liua,b, Liang Chenga,b,*, Song-Chen Yua,b, Li Liua,b,* and Chao-Jun Lic,*
aBeijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, CAS Research/Education Center
for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
bUniversity of Chinese Academy of Sciences, Beijing 100049, China
cDepartment of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, Quebec H3A 0B8,
Canada.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The addition of organometallic reagents to unsaturated bonds is one of the most powerful tools
for carbon–carbon bond formations. Alkylation through organometallic reagents requires
stoichiometric quantity of metal and tedious anhydrous operation in most cases. Here, we report
“umpolung” nucleophilic additions of hydrazones to Michael acceptors, carbonyls and imines in
water. Under the catalysis of ruthenium(II), the addition reactions could be carried out in pure
water to provide various alkylation products in moderate to good yields.
Available online
Keywords:
Hydrazone
Aqueous
2020 Elsevier Ltd. All rights reserved.
addition
chalcones
Ruthenium catalysis
1. Introduction
advantages such as moisture/air-stable hydrazones as reactants,
good functional group compatibility, no waste metal salts or
The nucleophilic addition reaction plays an important role in
carbon-carbon bond formations.[1] Grignard reagents and other
organometallic reagents serving as nucleophiles have been
widely applied in the addition reaction for constructing various
molecules.[2-3] Different from enolized or enaminized carbon
nucleophiles, organometallic reagents are characterized by polar
umpolung transformations of positively charged carbon atoms
into negatively charged carbons[3]. Polar transformation can
construct a backbone that is difficult to achieve with non-polar
transformation methods[4]. Although enormous progress has been
made for classical organometallic reactions, there are still
obvious shortcomings in view of chemical sustainability. First,
the pre-preparation of metal organic reagents as nucleophiles
requires the production of equivalent amounts of waste metals. A
large amount of scrap metal is both costly to the mining industry
and very unfriendly to the environment. In addition, pre-selective
preparation of organometallic reagents often requires some
halogenated hydrocarbons as feedstock. After the nucleophile is
introduced into the reaction, equivalent halogen is discarded as
waste. Furthermore, due to the sensitivity of organometallic
reagents towards proton, it is often necessary to use a strictly dry
organic solvent and tedious anhydrous operation.
halides and only nitrogen and water as the theoretical
byproducts.[8] On the basis of the environmental concern of
organic solvents, aqueous organic reactions have made great
progress.[9] However, there is no report on transition metal
catalyzed reactions of carbonyl compounds masked as “soft”
alkyl carbanions via hydrazone in aqueous media.[10]
Recently, the metal-catalyzed umpolung chemistry through
hydrazone intermediates using aldehydes and ketones as
carbanion equivalents has attracted much attention in organic
synthesis.[5-7] Comparing with organometallic reactions for
carbon-carbon bond formations, this strategy exhibited unique
Scheme 1. Carbon nucleophiles used in conjugate additions.

2
Tetrahedron
Herein, we report a ruthenium(II)-catalyzed “umpolung”
(dmpe) or 1,2-bis(diphenylphosphanyl)propane (dppp) as the
ligand (Table 1, entries 1-2). When the reaction was carried out
in water in the presence of TBAC as a phase transfer catalyst,
only very low yield of 3a was obtained (entry 3). After screening
different ligands, triphenylphosphine was found to provide the
highest yield (53%) (entries 4-7). Increasing the reaction
temperature from 70 oC to 100oC, the yield was improved slightly
and the reaction did not require the addition of a phase transfer
catalyst (entries 8-9). Furthermore, by removing the additive CsF,
the reaction gave 3a in the optimum yield (71%) (entry 10).
When K3PO4 was changed to other inorganic or organic bases,
the reaction provided relatively lower yields of 52-68% (entries
11-13). The reaction in various organic solvents such as 1,4-
dioxane, DMF, DMSO and toluene could generate 3a, but the
yields were not as good as in water (18-62%, entries 14-17). In
addition, solvent- free conditions resulted in only 46% yield
(entry 18).
nucleophilic additions of hydrazones to unsaturated bonds in
water. The Michael-type addition of hydrazones with chalcones
could be carried out in pure water without using a phase transfer
catalyst or surfactant. Moreover, the addition of hydrazones to
carbonyls and imines in water could also provide the related
alkylation products in the presence of catalytic amount of
tetrabutylammonium chloride. There are no waste metal salts or
halides generation, with nitrogen as the sole byproduct.
2. Results and discussion
The reaction of hydrazone derived from benzaldehyde (1a) with
chalcone 2a was chosen as the model reaction. Initially, the
reaction was carried out in organic solvent with the same reaction
conditions as literature.[6a] The reaction provided the addition
product 3a in 36-40% yields in THF under the catalysis of
[Ru(p-cymene)Cl2]2 and 1,2-bis(dimethylphosphino)-ethane
Table 1: Optimization of reaction conditions[a].
entry
1[e]
2[e]
3[c]
4[c]
5[c]
6[c]
7
ligand
dmpe
dppp
dmpe
dppe
dppp
dppf
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
base
additive
PTC
temp. (oC)
50
solvent
THF
yield (%)[b]
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K2CO3
NaOH
Et3N
CsF
-
40
36
9
CsF
-
50
THF
CsF
TBAC
70
H2O
CsF
TBAC
70
H2O
37
30
40
53
56
59
71
64
52
68
58
49
18
62
46
CsF
TBAC
70
H2O
CsF
TBAC
70
H2O
CsF
TBAC
70
H2O
8
CsF
TBAC
100
100
100
100
100
100
100
100
100
100
100
H2O
9
CsF
-
-
-
-
-
-
-
-
-
-
H2O
10
11
12
13
14
15
16
17
18[d]
-
-
-
-
-
-
-
-
-
H2O
H2O
H2O
H2O
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
1,4-Dioxane
DMF
DMSO
Toluene
none
[a]General reaction conditions: 1a (0.25 mmol, 2.5 equiv.), 2a (0.1 mmol, 1.0 equiv.), [Ru(p-cymene)Cl2]2 (1.5 mol %), ligand (6 mol %), base (0.8 equiv.),
additive (1.0 equiv.), PTC (0.2 equiv.), solvent (0.5 mL) under Ar atmosphere. [b]Yields were determined by crude 1H NMR using 1,3,5-trimethoxybenzene as an
internal standard. [c]Ligand (3 mol %). [d][Ru(p-cymene)Cl2]2 (10 mol %), PPh3 (40 mol %). [e][Ru(p-cymene)Cl2]2 (0.75 mol %), ligand (3 mol %), base (0.25
equiv.), additive (1.0 equiv.) , THF (0.15 mL) under Ar atmosphere.
With the optimized reaction conditions in hand, the scope of
Micheal receptor was explored with benzaldehyde-derived
hydrazone (1a) in H2O at 100 oC under the catalysis of Ru/PPh3
with K3PO4 as a base (Scheme 2). A wide range of α,β-
unsaturated ketones were coupled with hydrazone 1a to give the
corresponding 1,4-addition products in moderate to good yields
(Scheme 2). No carbonyl addition product was observed. This
reaction demonstrated good functional groups compatibility,
including aryl halides (3b-e), aryl nitrile (3f) and trifluoromethyls
(3g). Heteroaromatic substituted α,β-unsaturated ketones 3p, 3q
and 3y could be also used in this reaction. Steric hindrance
affected catalytic reactivity, with lower yields being obtained for
the ortho-substituted chalcone derivatives 3b and 3i compared
with the para-substituted Michael acceptors 3d and 3l. Electronic

3
effect also played a role in this transformation. For para-
substituted substrates 2, electron-donating groups such as OMe
and Ph on 2 gave higher yields than 4'-CN, 4'-CF3 and 4'-Br
substituted substrates (Scheme 2, 3l, 3n vs 3d-g). Conjugated
1,5-unsaturated ketone 2r selectively provided 1,4-addition
product 3r.
Scheme 2. Scope of Michael receptors 2.
the corresponding addition products in 48-66% yields (Scheme 3,
4a-l). Surprisingly, 2-substituted benzaldehyde derived
hydrazones have good reactivities (Scheme 3, 4o-p). In general,
compared to meta and ortho position, the para-substituted
aromatic hydrazones gave relatively low yields (4g vs 4c and 4e;
4h vs 4d and 4f). It may attribute to the competing dimerization
of the hydrazones which is faster in the case of the less sterically
hindered para-substituted substrates.6d
Having established the scope of various α,β-unsaturated
ketones, we turned our attention to nucleophilic partners. A
number of substituted benzaldehyde derived hydrazones were
used as the substrates. The electronic effect of substituents on 1
did not affect the reaction significantly. Both electron-donating
and electron-withdrawing group substituted hydrazones provided

4
Tetrahedron
Scheme 3. Scope of hydrazone and conjugate addition products.

5
Next, the addition reactions of hydrazones with imines and
carbonyl compounds in water were investigated (Scheme 4).
Different from the addition to Michael acceptors, the reaction of
hydrazone with benzaldehyde-derived imine 5 and acetophenone
6 required the participation of a phase transfer catalyst in order
to get satisfying yields. With the reaction conditions optimized
earlier, the reactions of hydrazone 1a with imine 5 and ketone
6a in water provided the corresponding products 7a and 8a in 33%
and 46% yields, respectively (see the Supporting Information for
more details). Decreasing the reaction temperature from 100°C
to 70°C increased the yield to 43% for 7a and 59% for 8a (see
the Supporting Information for more details). After the addition
of TBAC (0.2 equiv.), both 7a and 8a were obtained in 71%
yield. Compared with imine, ketone showed lower reactivity in
the addition reaction with hydrazone in water, which needed a
longer reaction time. 2- ， 3- or 4-Substituted acetophenones
could gave the corresponding products in moderate yields
(Scheme 4, 8b-e).
Fig. 1. Proposed mechanism.
3. Conclusion
In summary, we have developed a ruthenium(II)-catalyzed
“umpolung” nucleophilic additions of hydrazones to unsaturated
bonds in water. Carbon-carbon bonds can be constructed in an
environmentally friendly manner by the addition of hydrazones
to chalcones, carbonyls and imines in pure water. The related
alkylation products were obtained in moderate to good yields.
There are no stoichiometric waste metal salts (except the base
additive which can be further optimized in future) or halide
generation, with dinitrogen as the sole stoichiometric byproduct.
Further transformation of the addition product of hydrazone with
chalcone provided a naphthalene derivative via an intramolecular
Friedel-Crafts reaction.
Scheme 4. Scope of imine and carbonyl compounds.
[a] 1.5 h. [b] 3 h. [c] 9.5 h. [d]18 h.
4. Experimental section
Further transformation of the addition product was
demonstrated in Scheme 5. The alkylation product 4i of
hydrazone with chalcone provided a naphthalene derivative 9a in
68% yield together with a small amount of aromatized product
9b via an intramolecular Friedel-Crafts reaction under the
promotion of AlCl3.
4.1. General exprimental information
1
The H NMR and 13C NMR spectra were recorded on Bruker
Avance 300 (1H, 300 MHz), Bruker Avance 400 (1H, 400 MHz;
13C, 101 MHz) and Bruker Avance III HD 500MHz (1H, 500
MHz; 13C, 126 MHz). All chemical shifts (d) were given in ppm.
Data were reported as follows: chemical shift, integration,
multiplicity (s = single, d = doublet, t = triplet, q = quartet, m =
multiplet) and coupling constants (Hz). Flash column
chromatography was performed using H silica gel. For thin-layer
chromatography (TLC), silica gel plates (HSGF 254) were used
and compounds were visualized by irradiation with UV light. IR
spectra were recorded on Nicolet 6700 instrument. High-
resolution mass spectra (HRMS) were recorded by a Thermo
Fisher Scientific Exactive Orbitrap mass spectrometer.
Scheme 5. Intramolecular Friedel-Crafts reaction of the
addition product 4i.
As shown in Fig. 1, a plausible mechanism is proposed.[6a] The
ruthenium complex A generated from [Ru(p-cymene)Cl2]2 with
PPh3 is coordinated by the Michael acceptor 2 to form complex
B. Then, after deprotonation in the presence of a base,
4.2. General procedure for the synthesis of compounds 3 and 4
A Schlenk tube (10 mL) equipped with a magnetic stir bar
was charged with [Ru(p-cymene)Cl2]2 (0.9 mg, 0.0015 mmol,
1.5 mol%), PPh3 (1.6 mg, 0.006 mmol, 6 mol%), K3PO4 (17 mg,
0.08 mmol, 0.8 equiv.), α,β-unsaturated ketone (0.1 mmol, 1.0
equiv.). The reaction system was then protected with an argon
atmosphere. After that, THF (50 ꢀL) was added to the reaction
system. After stirring for 10 minutes at room temperature,
hydrazone (0.25 mmol, 2.5 equiv.) was added to the system.
hydrazones 1 ligates to complex B and generates
the
nucleophilic addition product 3 via a six-membered-ring
transition state (complex C), by the release of N2 under the base
deprotonation.

6
Tetrahedron
THF was removed in vacuo and filled with argon. Then,
1H), 7.05 (dd, J = 7.3, 5.3 Hz, 4H), 3.64 (p, J = 7.2 Hz, 1H),
3.34-3.23 (m, 2H), 3.03-2.86 (m, 2H); 13C NMR (126 MHz,
CDCl3) δ 198.6, 142.7, 139.5, 137.1, 133.2, 132.1, 129.4, 129.2,
128.7, 128.6, 128.4, 128.1, 126.4, 44.1, 43.1, 42.5; HRMS (ESI,
m/z), calcd for C22H18OBr- [M-H]-, 377.0547; found, 377.0541.
distilled water (0.5 mL) was added to the reaction vessel and
heated to 100 oC. The reaction system was stirred at 100 oC for 6
h and then diluted with 3 mL water. After cooling to room
temperature, 2 mL HCl solution (3 M) was added to the reaction
system, and the mixture was extracted with ethyl acetate (3x5
mL). The combined organic layers was washed with water (5 mL)
and then dried over Na2SO4. The organic layers were
concentrated and the resulting residue was purified by
preparative TLC on silica gel to afford the product.
4.2.6. 4-(4-oxo-1,4-diphenylbutan-2-yl)benzonitrile
(3f)
Yellow solid (19.1 mg, yield 59%); mp. 168-169 C; Rf =
0.15 (petroleum ether / acetone = 10/1); H NMR (500 MHz,
o
1
CDCl3) δ 7.89-7.81 (m, 2H), 7.55-7.50 (m, 2H), 7.43 (t, J = 7.7
Hz, 2H), 7.38-7.25 (m, 3H), 7.22 (t, J = 7.2 Hz, 2H), 7.20-7.13
(m, 1H), 7.05 (t, J = 11.6 Hz, 2H), 3.74 (t, J = 6.4 Hz, 1H), 3.41-
3.29 (m, 2H), 3.08-2.87 (m, 2H); 13C NMR (126 MHz, CDCl3) δ
198.1, 149.9, 138.9, 136.9, 133.4, 132.3, 129.3, 128.8, 128.7,
128.5, 128.1, 126.6, 119.1, 110.4, 43.7, 43.2, 42.8; HRMS (ESI,
m/z), calcd for C23H18NO- [M-H]-, 324.1394; found, 324.1387.
4.2.1. 1,3,4-triphenylbutan-1-one (3a)
White solid (21.3 mg, yield 71%); Rf = 0.25 (petroleum ether
/ acetone = 40/1); mp. 114-115 oC; 1H NMR (300MHz, CDCl3) δ
7.88-7.80 (m, 2H), 7.56-7.48 (m, 1H), 7.44-7.36 (m, 2H), 7.24-
7.13 (m, 8H), 7.07 (dd, J = 9.9, 3.3 Hz, 2H), 3.74-3.59 (m, 1H),
3.39-3.21 (m, 2H), 3.06-2.88 (m, 2H); 13C NMR (126MHz,
CDCl3) δ 199.0, 144.3, 140.0, 137.3, 133.1, 129.4, 128.7, 128.5,
128.3, 128.1, 127.8, 126.5, 126.2, 44.3, 43.2, 43.1; HRMS
(APCI, m/z), calcd for C22H21O+ [M+H]+, 301.1587; found,
301.1588.
4.2.7. 3-(4-(trifluoromethyl)phenyl)-1,4-
diphenylbutan-1-one (3g)
White solid (19.5 mg, yield 53%); mp. 153-154 oC; Rf = 0.25
(petroleum ether / acetone = 40/1); FT-IR (cm-1) 2924, 2358,
1679, 1326, 1129, 690; 1H NMR (300 MHz, CDCl3) δ 7.89-7.80
(m, 2H), 7.58-7.49 (m, 2H), 7.49-7.37 (m, 4H), 7.29 (d, J = 8.0
Hz, 2H), 7.20 (dd, J = 7.3, 4.5 Hz, 2H), 7.11-7.01 (m, 2H), 3.82-
3.68 (m, 1H), 3.34 (dd, J = 6.9, 3.5 Hz, 2H), 2.98 (dd, J = 12.6,
7.5 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 198.4, 148.4, 139.3,
137.1, 133.3, 129.3, 128.8, 128.5, 128.2, 128.1, 126.5, 125.5,
125.4, 43.9, 42.94, 42.90, 1.2; HRMS (APCI, m/z), calcd for
C23H20F3O+ [M+H]+, 369.1461; found, 369.1464.
4.2.2. 3-(2-chlorophenyl)-1,4-diphenylbutan-1-one
(3b)
o
Yellow solid (16.4 mg, yield 49%); mp. 104-105 C; Rf =
0.31 (petroleum ether / acetone = 20/1); FT-IR (cm-1) 3359,
1
2921, 2360, 1685, 1448, 753, 697; H NMR (300 MHz, CDCl3)
δ 7.85 (d, J = 7.5 Hz, 2H), 7.52 (s, 1H), 7.42 (d, J = 7.8 Hz, 2H),
7.32 (dd, J = 7.7, 1.3 Hz, 1H), 7.24-7.05 (m, 8H), 4.29 (s, 1H),
3.34 (dd, J = 15.0, 7.0 Hz, 2H), 3.00 (dd, J = 21.6, 7.4 Hz, 2H);
13C NMR (126 MHz, CDCl3) δ 198.6, 141.3, 139.5, 137.1, 134.2,
133.1, 130.0, 129.4, 128.7, 128.4, 128.2, 128.1, 127.6, 126.9,
126.4, 42.6, 41.3, 39.1; HRMS (ESI, m/z), calcd for C22H18OCl-
[M-H]-, 333.1052; found, 333.1045.
4.2.8. 1,4-diphenyl-3-o-tolylbutan-1-one (3h)
Light yellow oil (13.8 mg, yield 44%); Rf = 0.36 (petroleum
ether / acetone = 20/1); FT-IR (cm-1) 2921, 2360, 1684, 1492,
1
1450, 751, 698; H NMR (300 MHz, CDCl3) δ 7.85 (d, J = 7.7
4.2.3. 3-(3-chlorophenyl)-1,4-diphenylbutan-1-one
(3c)
Hz, 2H), 7.51 (d, J = 6.9 Hz, 1H), 7.40 (t, J = 7.7 Hz, 2H), 7.25
(d, J = 4.2 Hz, 1H), 7.17 (t, J = 7.9 Hz, 4H), 7.05 (d, J = 5.2 Hz,
4H), 4.02-3.86 (m, 1H), 3.33 (dd, J = 16.1, 7.0 Hz, 2H), 3.01-
2.81 (m, 2H), 2.16 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 199.1,
142.6, 140.0, 137.3, 136.4, 133.0, 130.4, 129.4, 128.6, 128.3,
128.1, 126.23, 126.19, 126.15, 125.9, 44.2, 43.2, 37.9, 19.7;
HRMS (ESI, m/z), calcd for C23H21O- [M-H]-, 313.1598; found,
313.1598.
o
Colorless solid (16.7 mg, yield 50%); mp. 108-109 C; Rf =
0.39 (petroleum ether / acetone = 10/1); FT-IR (cm-1) 2922,
1
2361, 1685, 1079, 695, 613; H NMR (300MHz, CDCl3) δ 7.90-
7.80 (m, 2H), 7.52 (d, J = 7.4 Hz, 1H), 7.42 (t, J = 7.5 Hz, 2H),
7.27-7.21 (m, 2H), 7.19 (d, J = 4.9 Hz, 3H), 7.14 (dd, J = 7.8,
5.4 Hz, 4H), 7.10-6.99 (m, 4H), 3.66 (s, 1H), 3.29 (dd, J = 6.9,
3.1 Hz, 2H), 2.96 (dd, J = 9.4, 7.6 Hz, 2H); 13C NMR (101 MHz,
CDCl3) δ 198.5, 146.4, 139.5, 137.1, 134.3, 133.2, 129.7, 129.4,
128.7, 128.4, 128.1, 127.8, 126.8, 126.4, 126.3, 44.0, 43.0, 42.8;
HRMS (ESI, m/z), calcd for C22H18OCl- [M-H]-, 333.1052;
found, 333.1055.
4.2.9. 3-(2-methoxyphenyl)-1,4-diphenylbutan-1-
one (3i)
o
Light yellow solid (19.8 mg, yield 60%); mp. 119-120 C; Rf
= 0.47 (petroleum ether / acetone = 20/1); FT-IR (cm-1) 2919,
1
2359, 1683, 1492, 1241, 1110, 749, 614; H NMR (300 MHz,
4.2.4. 3-(4-chlorophenyl)-1,4-diphenylbutan-1-one
CDCl3) δ 7.84 (d, J = 7.5 Hz, 2H), 7.50 (s, 1H), 7.39 (t, J = 7.6
Hz, 2H), 7.18 (d, J = 7.3 Hz, 2H), 7.12 (dd, J = 10.7, 4.6 Hz,
5H), 6.88-6.77 (m, 2H), 4.02 (s, 1H), 3.74 (s, 3H), 3.32 (dd, J =
18.1, 7.0 Hz, 2H), 3.10-2.91 (m, 2H); 13C NMR (101 MHz,
CDCl3) δ 199.5, 157.4, 140.6, 137.4, 132.8, 132.1, 129.4, 128.5,
128.4, 128.17, 128.15, 127.5, 126.0, 120.6, 110.9, 55.4, 42.8,
(3d)
White solid (21.1 mg, yield 63%); mp. 169-171 oC; Rf = 0.39
1
(petroleum ether / acetone = 10/1); H NMR (500 MHz, CDCl3)
δ 7.89-7.80 (m, 2H), 7.53 (dd, J = 13.2, 5.9 Hz, 1H), 7.41 (dd, J
= 14.6, 7.0 Hz, 2H), 7.23-7.14 (m, 5H), 7.13-7.07 (m, 2H), 7.04
(dd, J = 9.9, 4.3 Hz, 2H), 3.65 (p, J = 7.2 Hz, 1H), 3.35-3.23 (m,
2H), 3.03-2.86 (m, 2H); 13C NMR (126 MHz, CDCl3) δ 198.6,
142.7, 139.5, 137.1, 133.2, 132.1, 129.4, 129.2, 128.7, 128.6,
128.4, 128.1, 126.4, 44.1, 43.1, 42.5; HRMS (ESI, m/z), calcd
for C22H18OCl- [M-H]-, 333.1052; found, 333.1049.
-
41.0, 37.7; HRMS (ESI, m/z), calcd for C23H21O2 [M-H]-,
329.1547; found, 329.1548.
4.2.10. 1,4-diphenyl-3-m-tolylbutan-1-one (3j)
Light yellow oil (13.7 mg, yield 44%); Rf = 0.47 (petroleum
ether / acetone = 10/1); FT-IR (cm-1) 2921, 2361, 1684, 1449,
1
4.2.5. 3-(4-bromophenyl)-1,4-diphenylbutan-1-one
(3e)
1076, 700, 612; H NMR (300 MHz, CDCl3) δ 7.90-7.78 (m,
2H), 7.51 (s, 1H), 7.41 (d, J = 7.7 Hz, 2H), 7.18 (dd, J = 13.5,
7.1 Hz, 3H), 7.11-7.05 (m, 3H), 6.97 (d, J = 9.9 Hz, 3H), 3.63 (s,
1H), 3.40-3.17 (m, 2H), 2.96 (d, J = 7.4 Hz, 2H), 2.29 (s, 3H);
13C NMR (101 MHz, CDCl3) δ 199.1, 144.3, 140.1, 138.0, 137.4,
133.0, 130.8, 130.7, 129.4, 128.6, 128.3, 128.2, 127.3, 126.2,
White solid (22.3 mg, yield 59%); mp. 174-175 oC; Rf = 0.40
(petroleum ether / acetone = 10/1); FT-IR (cm-1) 3027, 2922,
2361, 1685, 1584, 699; 1H NMR (500 MHz, CDCl3) δ 7.86-7.81
(m, 2H), 7.53 (dd, J = 13.1, 5.7 Hz, 1H), 7.41 (t, J = 7.7 Hz,
2H), 7.34 (t, J = 6.4 Hz, 2H), 7.24-7.18 (m, 2H), 7.18-7.13 (m,

7
124.7, 44.2, 43.1, 43.0, 21.6; HRMS (ESI, m/z), calcd for
HRMS (ESI, m/z), calcd for C26H23O+ [M+H]+, 351.1743;
found, 351.1741.
C23H21O- [M-H]-, 313.1598; found, 313.1600.
4.2.11. 3-(3-methoxyphenyl)-1,4-diphenylbutan-1-
4.2.16. 1,4-diphenyl-3-(thiophen-2-yl)butan-1-one
one (3k)
(3p)
Light yellow oil (17.8 mg, yield 54%); Rf = 0.31 (petroleum
Yellow oil (20.8 mg, yield 68%); Rf = 0.41 (petroleum ether /
acetone = 10/1); FT-IR (cm-1) 2922, 2360, 1684, 1448, 1216,
746, 695; 1H NMR (500 MHz, CDCl3) δ 7.93-7.82 (m, 2H), 7.53
(dd, J = 10.5, 4.3 Hz, 1H), 7.42 (t, J = 7.7 Hz, 2H), 7.25-7.21
(m, 2H), 7.17 (dq, J = 9.5, 4.8 Hz, 1H), 7.12 (d, J = 7.2 Hz, 2H),
7.09 (dd, J = 5.1, 0.9 Hz, 1H), 6.84 (dt, J = 7.1, 3.5 Hz, 1H),
6.73 (t, J = 6.0 Hz, 1H), 4.03 (p, J = 7.2 Hz, 1H), 3.32 (ddd, J =
23.2, 16.9, 6.8 Hz, 2H), 3.09-2.97 (m, 2H); 13C NMR (126 MHz,
CDCl3) δ 198.5, 148.1, 139.5, 137.2, 133.2, 129.4, 128.7, 128.4,
128.2, 126.7, 126.4, 124.3, 123.2, 45.2, 43.9, 38.4; HRMS (ESI,
m/z), calcd for C20H17OS- [M-H]-, 305.1006; found, 305.0999.
ether / acetone = 10/1); FT-IR (cm-1) 2922, 1684, 1599, 1451,
1
1260, 699; H NMR (300 MHz, CDCl3) δ 7.89-7.80 (m, 2H),
7.52 (s, 1H), 7.42 (d, J = 7.7 Hz, 2H), 7.22-7.13 (m, 4H), 7.11-
7.05 (m, 2H), 6.78 (d, J = 7.7 Hz, 1H), 6.70 (d, J = 6.5 Hz, 2H),
3.73 (s, 2H), 3.65 (s, 1H), 3.29 (dd, J = 10.2, 7.0 Hz, 2H), 3.03-
2.91 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 199.0, 159.6,
146.0, 139.9, 137.3, 133.1, 130.8, 129.4, 128.7, 128.3, 128.1,
126.2, 120.1, 113.8, 111.7, 55.3, 44.2, 43.2, 43.0; HRMS (ESI,
-
m/z), calcd for C23H21O2 [M-H]-, 329.1547; found, 329.1551.
4.2.12. 3-(4-methoxyphenyl)-1,4-diphenylbutan-1-
one (3l)
4.2.17. 3-(benzofuran-2-yl)-1,4-diphenylbutan-1-
o
one (3q)
Colorless solid (24.1 mg, yield 73%); mp. 146-147 C; Rf =
0.47 (petroleum ether / ethyl acetate = 5/1); 1H NMR (300 MHz,
CDCl3) δ 7.83 (d, J = 7.3 Hz, 2H), 7.51 (t, J = 7.3 Hz, 1H), 7.39
(t, J = 7.5 Hz, 2H), 7.23-7.14 (m, 3H), 7.07 (dd, J = 7.4, 5.4 Hz,
4H), 6.77 (d, J = 8.6 Hz, 2H), 3.74 (s, 3H), 3.61 (p, J = 7.2 Hz,
1H), 3.35-3.17 (m, 2H), 3.03-2.85 (m, 2H); 13C NMR (101 MHz,
CDCl3) δ 199.2, 158.2, 140.1, 137.3, 136.3, 133.0, 129.4, 128.7,
128.6, 128.3, 128.1, 126.2, 113.9, 55.3, 44.5, 43.3, 42.4; HRMS
Yellow solid (15.9 mg, yield 47%); mp. 106-108 C; Rf =
o
0.34 (petroleum ether / acetone = 20/1); FT-IR (cm-1) 3358,
1
2922, 2360, 1685, 1453, 1253, 747, 697; H NMR (300 MHz,
CDCl3) δ 7.89 (s, 2H), 7.52 (d, J = 7.4 Hz, 1H), 7.42 (dd, J =
5.1, 3.6 Hz, 4H), 7.19 (dd, J = 8.8, 4.5 Hz, 4H), 7.13 (d, J = 1.6
Hz, 3H), 6.32 (s, 1H), 3.95 (s, 1H), 3.38 (dd, J = 37.3, 6.8 Hz,
2H), 3.13 (dd, J = 18.3, 7.2 Hz, 2H); 13C NMR (126 MHz,
CDCl3) δ 198.2, 159.9, 154.7, 139.2, 137.0, 133.3, 129.3, 128.7,
128.5, 128.2, 126.5, 123.5, 122.6, 120.7, 111.0, 103.1, 41.5,
(ESI, m/z), calcd for C23H21O2 [M-H]-, 329.1547; found,
329.1540.
-
-
39.9, 36.9; HRMS (ESI, m/z), calcd for C24H19O2 [M-H]-,
4.2.13. 3-(3,4-dimethoxyphenyl)-1,4-diphenylbutan-
1-one (3m)
339.1391; found, 339.1382.
o
4.2.18. 3-benzyl-1,5-diphenylpent-4-en-1-one (3r)
Yellow solid (19.4 mg, yield 54%); mp. 86-88 C; Rf = 0.25
(petroleum ether / acetone = 5/1); FT-IR (cm-1) 3360, 2923,
1683, 1516, 1450, 1261, 1028, 698; 1H NMR (300 MHz, CDCl3)
δ 7.91-7.78 (m, 2H), 7.51 (d, J = 7.3 Hz, 1H), 7.41 (t, J = 7.5
Hz, 2H), 7.18 (dd, J = 12.6, 7.1 Hz, 3H), 7.10-7.04 (m, 2H), 6.73
(d, J = 2.6 Hz, 2H), 6.61 (s, 1H), 3.82 (s, 3H), 3.77 (s, 3H), 3.61
(s, 1H), 3.29 (t, J = 7.3 Hz, 2H), 2.95 (dd, J = 12.5, 7.4 Hz, 2H);
13C NMR (101 MHz, CDCl3) δ 199.2, 148.7, 147.6, 140.0, 137.4,
136.8, 133.1, 129.5, 128.7, 128.3, 128.1, 126.2, 119.3, 111.5,
111.2, 55.9, 44.4, 43.3, 42.9; HRMS (ESI, m/z), calcd for
C24H25O3+ [M+H]+, 361.1798; found, 361.1797.
o
White solid (14.8 mg, yield 46%); mp. 169-171 C; Rf = 0.49
1
(petroleum ether / acetone = 10/1); H NMR (300 MHz, CDCl3)
δ 7.87 (d, J = 7.1 Hz, 2H), 7.53 (s, 1H), 7.42 (s, 2H), 7.25 (s,
10H), 6.33 (d, J = 16.0 Hz, 1H), 6.16 (dd, J = 15.9, 7.9 Hz, 1H),
3.27 (dq, J = 14.2, 7.1 Hz, 1H), 3.14-2.99 (m, 2H), 2.84 (t, J =
8.1 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 199.3, 139.7, 137.5,
137.4, 133.1, 132.8, 130.4, 129.6, 128.7, 128.6, 128.5, 128.2,
127.2, 126.34, 126.28, 43.0, 41.5, 40.5; HRMS (ESI, m/z), calcd
for C24H21O- [M-H]-, 325.1598; found, 325.1593.
4.2.19. 1-(4-chlorophenyl)-3,4-diphenylbutan-1-one
4.2.14. 3-(4-phenyl)-1,4-diphenylbutan-1-one (3n)
(3s)
White solid (28.5 mg, yield 76%); mp. 160-162 oC; Rf = 0.28
(petroleum ether / acetone = 10/1); FT-IR (cm-1) 3027, 2922,
2360, 1683, 1488, 1261, 1022, 697; 1H NMR (300 MHz, CDCl3)
δ 7.90-7.80 (m, 2H), 7.54 (t, J = 6.5 Hz, 3H), 7.48 (d, J = 8.3
Hz, 3H), 7.41 (t, J = 7.9 Hz, 5H), 7.32 (d, J = 7.3 Hz, 1H), 7.19
(d, J = 6.4 Hz, 2H), 7.11 (d, J = 6.7 Hz, 3H), 3.79-3.65 (m, 1H),
3.34 (dd, J = 9.0, 7.0 Hz, 2H), 3.01 (d, J = 7.8 Hz, 2H); 13C
NMR (101 MHz, CDCl3) δ 199.0, 143.4, 141.1, 139.9, 139.3,
137.3, 133.1, 129.5, 128.8, 128.7, 128.4, 128.19, 128.15, 127.2,
127.1, 126.3, 44.2, 43.1, 42.8; HRMS (APCI, m/z), calcd for
C28H23O- [M-H]-, 375.1754; found, 375.1747.
Yellow solid (15.4 mg, yield 46%); mp. 158-160 oC; Rf = 0.44
(petroleum ether / acetone = 10/1); FT-IR (cm-1) 3027, 2923,
2360, 1685, 699; 1H NMR (500 MHz, CDCl3) δ 7.75 (d, J = 8.6
Hz, 2H), 7.36 (d, J = 8.6 Hz, 2H), 7.27-7.19 (m, 4H), 7.19-7.12
(m, 4H), 7.06 (t, J = 7.2 Hz, 2H), 3.64 (p, J = 7.3 Hz, 1H), 3.26
(qd, J = 16.7, 6.9 Hz, 2H), 3.02-2.92 (m, 2H); 13C NMR
(126MHz, CDCl3) δ 197.8, 144.0, 139.8, 139.5, 135.6, 129.6,
129.4, 129.0, 128.6, 128.4, 127.7, 126.7, 126.3, 44.2, 43.3, 43.1;
HRMS (ESI, m/z), calcd for C22H18OCl- [M-H]-, 335.1052;
found, 333.1050.
4.2.20. 3,4-diphenyl-1-m-tolylbutan-1-one (3t)
Yellow solid (17.5 mg, yield 56%); mp. 103-105 oC; Rf = 0.34
(petroleum ether / acetone = 20/1); FT-IR (cm-1) 3027, 2360,
1683, 1102, 615; 1H NMR (300 MHz, CDCl3) δ 7.64 (d, J = 5.3
Hz, 2H), 7.37-7.27 (m, 2H), 7.28-7.23 (m, 2H), 7.21 (dd, J = 4.0,
2.3 Hz, 2H), 7.19-7.11 (m, 4H), 7.11-7.04 (m, 2H), 3.74-3.58 (m,
1H), 3.29 (dd, J = 6.9, 3.5 Hz, 2H), 2.98 (t, J = 6.9 Hz, 2H), 2.36
(s, 3H); 13C NMR (126 MHz, CDCl3) δ 199.2, 144.3, 140.0,
138.4, 137.3, 133.8, 129.4, 128.7, 128.51, 128.47, 128.3, 127.8,
126.5, 126.2, 125.3, 44.4, 43.2, 43.1, 21.5; HRMS (ESI, m/z),
calcd for C23H21O- [M-H]-, 313.1598; found, 313.1591.
4.2.15. 3-(naphthalen-2-yl)-1,4-diphenylbutan-1-
one (3o)
Yellow solid (23.1 mg, yield 66%); mp. 200-202 oC; Rf = 0.32
(petroleum ether / acetone = 10/1); FT-IR (cm-1) 3734, 3057,
1
2360, 1683, 744, 698; H NMR (500 MHz, CDCl3) δ 7.90-7.81
(m, 2H), 7.79-7.69 (m, 3H), 7.59 (s, 1H), 7.51 (t, J = 7.4 Hz,
1H), 7.40 (qd, J = 8.9, 3.4 Hz, 5H), 7.19 (t, J = 7.2 Hz, 2H), 7.14
(d, J = 7.1 Hz, 1H), 7.09 (d, J = 7.0 Hz, 2H), 3.85 (p, J = 7.2
Hz, 1H), 3.40 (ddd, J = 23.3, 16.8, 6.9 Hz, 2H), 3.13-3.01 (m,
2H); 13C NMR (126 MHz, CDCl3) δ 198.9, 141.8, 139.9, 137.3,
133.6, 133.1, 132.5, 129.4, 128.7, 128.4, 128.2, 128.1, 127.8,
127.7, 126.30, 126.29, 126.27, 126.0, 125.5, 44.3, 43.2, 43.0;

8
Tetrahedron
4.2.21. 1-(3-methoxyphenyl)-3,4-diphenylbutan-1-
one (3u)
(dd, J = 8.6, 5.6 Hz, 2H), 6.90 (dd, J = 12.0, 5.4 Hz, 2H), 3.73-
3.58 (m, 1H), 3.34 (dd, J = 6.9, 4.8 Hz, 2H), 2.98 (ddd, J = 21.7,
13.4, 7.3 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 198.9, 162.7,
160.3, 143.9, 137.3, 135.6, 133.2, 130.8, 130.7, 128.7, 128.5,
128.1, 127.8, 126.6, 115.1, 44.3, 43.3, 42.2; HRMS (ESI, m/z),
calcd for C22H18FO- [M-H]-, 317.1347; found, 317.1344.
Colorless oil (18.1 mg, yield 55%); Rf = 0.23 (petroleum ether
/ acetone = 20/1); FT-IR (cm-1) 3027, 2360, 1683, 1453, 1256,
699; H NMR (300 MHz, CDCl3) δ 7.42 (d, J = 7.7 Hz, 1H),
1
7.37 (d, J = 2.3 Hz, 1H), 7.32 (d, J = 8.0 Hz, 1H), 7.24-7.20 (m,
3H), 7.19-7.15 (m, 5H), 7.09-7.03 (m, 3H), 3.81 (s, 3H), 3.65 (d,
J = 7.2 Hz, 1H), 3.41-3.18 (m, 2H), 3.07-2.90 (m, 2H); 13C
NMR (126 MHz, CDCl3) δ 198.9, 159.9, 144.2, 140.0, 138.7,
129.6, 129.4, 128.5, 128.3, 127.8, 126.6, 126.2, 120.8, 119.6,
112.3, 55.6, 44.4, 43.2, 43.1; HRMS (ESI, m/z), calcd for
4.2.27. methyl 4-(4-oxo-2,4-diphenylbutyl)benzoate
(4b)
Yellow solid (17.1 mg, yield 48%); mp. 210-211 oC; Rf = 0.20
(petroleum ether / acetone = 10/1); FT-IR (cm-1) 2922, 2358,
1717, 1508, 1104, 615; 1H NMR (300 MHz, CDCl3) δ 7.94-7.78
(m, 4H), 7.52 (dd, J = 4.9, 3.7 Hz, 1H), 7.42 (dd, J = 10.4, 4.6
Hz, 2H), 7.25-7.19 (m, 2H), 7.19-7.05 (m, 5H), 3.87 (s, 3H),
3.74-3.63 (m, 1H), 3.33 (t, J = 6.6 Hz, 2H), 3.03 (ddd, J = 21.9,
13.3, 7.4 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 198.7, 167.3,
145.5, 143.6, 137.2, 133.2, 129.6, 129.4, 128.7, 128.6, 128.2,
128.1, 127.8, 126.7, 52.1, 44.4, 43.0, 42.9; HRMS (ESI, m/z),
calcd for C24H23O3+ [M+H]+, 359.1642; found, 359.1638.
C23H21O2 [M-H]-, 329.1547; found, 329.1539.
-
4.2.22. 3,4-diphenyl-1-p-tolylbutan-1-one (3v)
o
White solid (16.6 mg, yield 53%); mp. 176-178 C; Rf = 0.41
1
(petroleum ether / acetone = 10/1); H NMR (500 MHz, CDCl3)
δ 7.75 (d, J = 8.2 Hz, 2H), 7.26-7.11 (m, 10H), 7.09-7.04 (m,
2H), 3.66 (p, J = 7.2 Hz, 1H), 3.28 (qd, J = 16.6, 7.0 Hz, 2H),
2.97 (ddd, J = 31.4, 13.5, 7.4 Hz, 2H), 2.38 (s, 3H); 13C NMR
(126 MHz, CDCl3) δ 198.7, 144.3, 143.8, 140.0, 134.9, 129.4,
129.3, 128.5, 128.28, 128.27, 127.8, 126.5, 126.2, 44.2, 43.2,
43.1, 21.7; HRMS (ESI, m/z), calcd for C23H23O+ [M+H]+,
315.1743; found, 315.1740.
4.2.28. 1,3-diphenyl-4-o-tolylbutan-1-one (4c)
o
White solid (21.6 mg, yield 69%); mp. 164-166 C; Rf = 0.40
(petroleum ether / acetone = 20/1); FT-IR (cm-1) 3357, 2923,
1
2360, 1682, 1451, 1261, 750, 698; H NMR (300 MHz, CDCl3)
4.2.23. 1-(4-methoxyphenyl)-3,4-diphenylbutan-1-
δ 7.83 (s, 2H), 7.51 (d, J = 7.4 Hz, 1H), 7.40 (s, 2H), 7.21 (s,
2H), 7.18 (s, 3H), 7.13-6.91 (m, 4H), 3.70-3.55 (m, 1H), 3.35 (t,
J = 6.5 Hz, 2H), 2.96 (ddd, J = 34.1, 13.6, 7.5 Hz, 2H), 2.25 (s,
3H); 13C NMR (101 MHz, CDCl3) δ 199.0, 144.5, 138.2, 137.3,
136.6, 133.0, 130.4, 130.3, 128.6, 128.5, 128.1, 127.7, 126.6,
126.4, 125.7, 44.3, 42.0, 40.7, 19.6; HRMS (ESI, m/z), calcd for
C23H23O+ [M+H]+, 315.1743; found, 315.1737.
one (3w)
Orange solid (27.4 mg, yield 83%); mp. 158-159 oC; Rf = 0.53
1
(petroleum ether / ethyl acetate = 5/1); H NMR (300 MHz,
CDCl3) δ 7.83 (d, J = 8.9 Hz, 2H), 7.24-7.10 (m, 8H), 7.10-7.02
(m, 2H), 6.87 (d, J = 8.9 Hz, 2H), 3.84 (s, 3H), 3.72-3.58 (m,
1H), 3.35-3.16 (m, 2H), 3.06-2.88 (m, 2H); 13C NMR (101 MHz,
CDCl3) δ 197.6, 163.5, 144.4, 140.0, 130.43, 130.41, 129.4,
128.5, 128.3, 127.8, 126.5, 126.2, 113.8, 55.6, 43.9, 43.3, 43.1;
4.2.29. 4-(2-methoxyphenyl)-1,3-diphenylbutan-1-
one (4d)
HRMS (ESI, m/z), calcd for C23H21O2 [M-H]-, 329.1547; found,
-
o
White solid (19.5 mg, yield 59%); mp. 145-147 C; Rf = 0.27
(petroleum ether / acetone = 20/1); H NMR (300 MHz, CDCl3)
329.1540.
1
4.2.24. 1-(naphthalen-1-yl)-3,4-diphenylbutan-1-
one (3x)
δ 7.81 (d, J = 7.3 Hz, 2H), 7.50 (t, J = 7.3 Hz, 1H), 7.39 (s, 2H),
7.22 (d, J = 6.6 Hz, 4H), 7.18-7.08 (m, 2H), 7.00-6.91 (m, 1H),
6.84-6.71 (m, 2H), 3.72 (d, J = 14.0 Hz, 4H), 3.29 (dd, J = 10.6,
7.1 Hz, 2H), 3.06-2.91 (m, 2H); 13C NMR (101 MHz, CDCl3) δ
199.2, 157.8, 144.9, 137.4, 132.8, 131.2, 128.5, 128.3, 128.3,
128.1, 127.7, 127.6, 126.3, 120.3, 110.4, 55.3, 44.1, 41.6, 37.5;
Yellow oil (24.8 mg, yield 71%); Rf = 0.25 (petroleum ether /
1
acetone = 20/1); H NMR (300 MHz, CDCl3) δ 8.21-8.11 (m,
1H), 7.92 (d, J = 8.2 Hz, 1H), 7.87-7.76 (m, 1H), 7.60 (dd, J =
7.2, 1.0 Hz, 1H), 7.53-7.32 (m, 3H), 7.29-7.11 (m, 8H), 7.11-
7.03 (m, 2H), 3.70 (p, J = 7.3 Hz, 1H), 3.47-3.28 (m, 2H), 3.01
(d, J = 7.5 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 203.7, 144.0,
139.9, 136.8, 134.0, 132.4, 130.1, 129.4, 128.5, 128.4, 127.9,
127.8, 127.0, 126.6, 126.5, 126.3, 125.8, 124.4, 48.0, 43.8, 43.2;
HRMS (APCI, m/z), calcd for C26H23O+ [M+H]+, 351.1743;
found, 351.1746.
+
HRMS (ESI, m/z), calcd for C23H23O2 [M+H]+, 331.1693;
found, 331.1690.
4.2.30. 1,3-diphenyl-4-m-tolylbutan-1-one (4e)
Colorless oil (20.7 mg, yield 66%); Rf = 0.39 (petroleum ether
/ acetone = 20/1); FT-IR (cm-1) 3359, 2921, 1684, 1449, 748,
1
697; H NMR (300 MHz, CDCl3) δ 7.83 (d, J = 7.5 Hz, 2H),
4.2.25. 3,4-diphenyl-1-(thiophen-2-yl)butan-1-one
7.50 (d, J = 7.4 Hz, 1H), 7.40 (t, J = 7.6 Hz, 2H), 7.28-7.14 (m,
5H), 7.10 (t, J = 7.6 Hz, 1H), 7.01-6.81 (m, 3H), 3.65 (d, J = 7.2
Hz, 1H), 3.29 (t, J = 6.4 Hz, 2H), 2.94 (d, J = 7.4 Hz, 2H), 2.26
(s, 3H); 13C NMR (101 MHz, CDCl3) δ 199.1, 144.4, 139.9,
137.9, 137.4, 133.0, 130.2, 128.6, 128.5, 128.2, 128.1, 127.8,
127.0, 126.5, 126.4, 44.2, 43.1, 43.1, 21.5; HRMS (APCI, m/z),
calcd for C23H23O+ [M+H]+, 315.1743; found, 315.1746.
(3y)
Yellow solid (20.2 mg, yield 66%); mp. 142-144 oC; Rf = 0.25
(petroleum ether / acetone = 20/1); FT-IR (cm-1) 3026, 2359,
1655, 1451, 1068, 613; H NMR (300 MHz, CDCl3) δ 7.57 (dd,
1
J = 7.0, 2.1 Hz, 2H), 7.27-7.11 (m, 8H), 7.10-7.02 (m, 3H), 3.64
(dd, J = 14.5, 7.2 Hz, 1H), 3.32-3.14 (m, 2H), 3.07-2.89 (m, 2H);
13C NMR (126 MHz, CDCl3) δ 191.9, 144.7, 143.9, 139.8, 133.6,
131.9, 129.4, 128.5, 128.3, 128.1, 127.8, 126.6, 126.3, 45.1,
43.5, 42.9; HRMS (APCI, m/z), calcd for C20H19OS+ [M+H]+,
307.1151; found, 307.1151.
4.2.31. 4-(3-methoxyphenyl)-1,3-diphenylbutan-1-
one (4f)
Yellow solid (20.4 mg, yield 62%); mp. 137-139 oC; Rf = 0.24
1
(petroleum ether / acetone = 20/1); H NMR (300 MHz, CDCl3)
4.2.26. 4-(4-fluorophenyl)-1,3-diphenylbutan-1-one
δ 7.91-7.78 (m, 2H), 7.56-7.46 (m, 1H), 7.45-7.34 (m, 3H), 7.30-
7.08 (m, 6H), 6.75-6.63 (m, 2H), 6.58 (d, J = 1.8 Hz, 1H), 3.75-
3.58 (m, 4H), 3.40-3.20 (m, 2H), 3.05-2.87 (m, 2H); 13C NMR
(126 MHz, CDCl3) δ 199.0, 159.6, 144.3, 141.5, 137.3, 133.1,
129.3, 128.7, 128.5, 128.1, 127.8, 126.6, 121.9, 114.9, 111.9,
(4a)
o
Colorless solid (18.7 mg, yield 59%); mp. 122-124 C; Rf =
0.47 (petroleum ether / acetone = 5/1); FT-IR (cm-1) 3358, 2923,
1684, 1508, 1220, 747, 698; 1H NMR (300 MHz, CDCl3) δ 7.94-
7.84 (m, 2H), 7.56 (dd, J = 10.4, 4.2 Hz, 1H), 7.45 (t, J = 7.5
Hz, 2H), 7.27 (dd, J = 9.2, 4.9 Hz, 2H), 7.22-7.13 (m, 3H), 7.01
+
55.2, 44.2, 43.2, 43.0; HRMS (APCI, m/z), calcd for C23H23O2
[M+H]+, 331.1693; found, 331.1695.

9
1
4.2.32. 1,3-diphenyl-4-p-tolylbutan-1-one (4g)
1170, 779; H NMR (300 MHz, CDCl3) δ 8.30-8.19 (m, 1H),
o
7.83 (d, J = 8.8 Hz, 3H), 7.65 (s, 1H), 7.53 (s, 3H), 7.24-7.09 (m,
5H), 7.06-6.99 (m, 1H), 6.86 (d, J = 8.9 Hz, 2H), 3.87 (d, J =
15.7 Hz, 4H), 3.64-3.19 (m, 4H); 13C NMR (101 MHz, CDCl3) δ
197.6, 163.5, 144.6, 136.1, 134.0, 132.3, 130.41, 130.36, 128.8,
128.5, 127.68, 127.65, 127.0, 126.5, 126.1, 125.6, 125.2, 124.3,
113.8, 55.6, 44.4, 42.3, 40.5; HRMS (ESI, m/z), calcd for
C27H25O2+ [M+H]+, 381.1849; found, 381.1846.
Light yellow solid (16.6 mg, yield 53%); mp. 145-146 C; Rf
1
= 0.38 (petroleum ether / acetone = 20/1); H NMR (300 MHz,
CDCl3) δ 7.88-7.77 (m, 2H), 7.51 (s, 1H), 7.41 (d, J = 7.7 Hz,
2H), 7.27-7.14 (m, 5H), 6.99 (q, J = 8.0 Hz, 4H), 3.65 (s, 1H),
3.29 (t, J = 6.8 Hz, 2H), 2.94 (d, J = 7.4 Hz, 2H), 2.27 (s, 3H);
13C NMR (126 MHz, CDCl3) δ 199.1, 144.4, 137.3, 136.8, 135.7,
133.0, 129.3, 129.0, 128.6, 128.5, 128.1, 127.8, 126.5, 44.2,
43.2, 42.7, 21.2; HRMS (ESI, m/z), calcd for C23H21O- [M-H]-,
313.1598; found, 313.1591.
4.2.38. 3-(4-phenyl)-4-(naphthalen-1-yl)-1-
phenylbutan-1-one (4m)
4.2.33. 4-(4-methoxyphenyl)-1,3-diphenylbutan-1-
Yellow oil (25.1 mg, yield 59%); Rf = 0.25 (petroleum ether /
acetone = 10/1); FT-IR (cm-1) 3359, 2922, 1680, 1508, 1099,
one (4h)
1
o
777, 612; H NMR (300 MHz, CDCl3) δ 8.29-8.10 (m, 2H),
White solid (17.4 mg, yield 53%); mp. 135-136 C; Rf = 0.23
(petroleum ether / acetone = 20/1); H NMR (300 MHz, CDCl3)
1
7.96-7.89 (m, 1H), 7.84 (s, 2H), 7.73-7.64 (m, 1H), 7.57 (s, 1H),
7.48 (dd, J = 6.6, 3.0 Hz, 5H), 7.38-7.31 (m, 1H), 7.25 (s, 7H),
7.10-7.02 (m, 1H), 3.96-3.83 (m, 1H), 3.47 (d, J = 1.5 Hz, 4H);
13C NMR (101 MHz, CDCl3) δ 203.7, 144.2, 136.6, 135.9,
134.04, 133.99, 132.4, 132.2, 130.1, 128.9, 128.6, 128.4, 127.82,
127.75, 127.69, 127.2, 127.1, 126.7, 126.5, 126.1, 125.8, 125.6,
125.3, 124.4, 124.2, 48.5, 42.8, 40.6; HRMS (APCI, m/z), calcd
for C32H27O+ [M+H]+, 427.2056; found, 427.2053.
δ 7.84 (d, J = 7.8 Hz, 2H), 7.50 (d, J = 7.4 Hz, 1H), 7.40 (t, J =
7.5 Hz, 2H), 7.29-7.12 (m, 5H), 6.97 (d, J = 8.5 Hz, 2H), 6.74
(d, J = 8.5 Hz, 2H), 3.75 (s, 3H), 3.62 (s, 1H), 3.29 (dd, J = 6.9,
3.8 Hz, 2H), 2.92 (dd, J = 7.2, 2.7 Hz, 2H); 13C NMR (101 MHz,
CDCl3) δ 199.1, 158.1, 144.4, 137.3, 133.0, 132.0, 130.3, 128.6,
128.5, 128.1, 127.8, 126.5, 113.7, 55.3, 44.2, 43.3, 42.2; HRMS
-
(ESI, m/z), calcd for C23H21O2 [M-H]-, 329.1547; found,
329.1551.
4.2.39. 4-(naphthalen-1-yl)-1-phenyl-3-(thiophen-
2-yl)butan-1-one (4n)
4.2.34. 4-(3,4,5-trimethoxyphenyl)-1,3-
diphenylbutan-1-one (4i)
Yellow oil (26.1 mg, yield 73%); Rf = 0.23 (petroleum ether /
1
acetone = 10/1); FT-IR (cm-1) 2924, 1659, 1415, 1235, 727; H
Orange solid (25.3 mg, yield 65%); mp. 138-140 oC; Rf = 0.45
(petroleum ether / acetone = 2/1); FT-IR (cm-1) 2934, 2356,
1683, 1589, 1454, 1239, 1125, 750, 614; H NMR (300 MHz,
NMR (300 MHz, CDCl3) δ 8.27-8.16 (m, 1H), 7.88-7.77 (m,
1H), 7.72-7.61 (m, 1H), 7.58 (d, J = 4.4 Hz, 4H), 7.29-7.18 (m,
4H), 7.17 (s, 2H), 7.04 (s, 2H), 3.92-3.76 (m, 1H), 3.33 (d, J =
6.8 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ 191.9, 144.6, 144.2,
135.9, 134.0, 133.6, 132.2, 131.9, 128.8, 128.5, 128.1, 127.7,
127.1, 126.7, 126.2, 125.6, 125.2, 124.2, 45.5, 42.4, 40.4; HRMS
(ESI, m/z), calcd for C24H21OS+ [M+H]+, 357.1308; found,
357.1304.
1
CDCl3) δ 7.87 (dd, J = 5.2, 3.3 Hz, 2H), 7.58-7.49 (m, 1H), 7.42
(dd, J = 10.3, 4.6 Hz, 2H), 7.26 (dd, J = 9.1, 5.4 Hz, 2H), 7.22-
7.11 (m, 3H), 6.18 (s, 2H), 3.78 (d, J = 3.8 Hz, 3H), 3.72-3.58
(m, 6H), 3.33 (d, J = 6.9 Hz, 2H), 3.01-2.82 (m, 2H); 13C NMR
(126 MHz, CDCl3) δ 199.0, 152.9, 144.2, 137.3, 136.4, 135.4,
133.1, 128.7, 128.5, 128.1, 127.9, 126.6, 106.4, 61.0, 56.0, 44.0,
43.4, 43.0; HRMS (ESI, m/z), calcd for C25H27O4 [M+H]+,
+
4.2.40. 1-(4-methoxyphenyl)-3-phenyl-4-o-
391.1904; found, 391.1903.
tolylbutan-1-one (4o)
4.2.35. 4-(naphthalen-1-yl)-1,3-diphenylbutan-1-
one (4j)
Colorless solid (28.4 mg, yield 81%); mp. 127-129 C; Rf =
0.23 (petroleum ether / acetone = 20/1); H NMR (300 MHz,
CDCl3) δ 8.23 (d, J = 8.4 Hz, 1H), 7.89-7.77 (m, 3H), 7.65 (s,
1H), 7.58-7.43 (m, 3H), 7.39 (d, J = 7.7 Hz, 2H), 7.27-7.19 (m,
3H), 7.16 (d, J = 7.2 Hz, 3H), 7.05 (s, 1H), 3.86 (s, 1H), 3.61-
3.21 (m, 4H); 13C NMR (101 MHz, CDCl3) δ 199.1, 144.5,
137.3, 136.0, 134.0, 133.1, 132.3, 128.8, 128.6, 128.5, 128.1,
127.7, 127.1, 126.6, 126.1, 125.6, 125.2, 124.3, 44.8, 42.1, 40.6;
HRMS (APCI, m/z), calcd for C26H23O+ [M+H]+, 351.1743;
found, 351.1746.
Yellow solid (26.2 mg, yield 76%); mp. 121-123 oC; Rf = 0.39
(petroleum ether / acetone = 5/1); FT-IR (cm-1) 2932, 1675,
1
o
1600, 1259, 1170, 1029, 834, 700; H NMR (300 MHz, CDCl3)
1
δ 7.84 (d, J = 8.9 Hz, 2H), 7.22 (d, J = 7.0 Hz, 2H), 7.16 (d, J =
7.1 Hz, 3H), 7.11-6.92 (m, 4H), 6.88 (d, J = 8.9 Hz, 2H), 3.85 (s,
3H), 3.62 (s, 1H), 3.41-3.20 (m, 2H), 2.95 (dd, J = 25.1, 7.5 Hz,
2H), 2.24 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 197.6, 163.5,
144.6, 138.2, 136.6, 130.40, 130.35, 130.27, 128.5, 127.7, 126.5,
126.3, 125.7, 113.8, 55.6, 43.9, 42.2, 40.6, 19.5; HRMS (ESI,
m/z), calcd for C24H25O2+ [M+H]+, 345.1849; found, 345.1842.
4.2.41. 4-(2-methoxyphenyl)-1-(4-methoxyphenyl)-
3-phenylbutan-1-one (4p)
o
4.2.36. 1,3-diphenyl-4-(thiophen-2-yl)butan-1-one
(4k)
Colorless solid (25.1 mg, yield 70%); mp. 138-139 C; Rf =
0.31 (petroleum ether / acetone = 5/1); FT-IR (cm-1) 2922, 1675,
1
o
1600, 1493, 1245, 1171, 1029, 754, 700; H NMR (300 MHz,
Yellow solidl (14.9 mg, yield 49%); mp. 93-95 C; Rf = 0.33
(petroleum ether / acetone = 20/1); FT-IR (cm-1) 3359, 2921,
1684, 1449, 1215, 696; 1H NMR (300 MHz, CDCl3) δ 7.92-7.81
(m, 2H), 7.52 (s, 2H), 7.42 (d, J = 7.5 Hz, 2H), 7.31-7.16 (m,
5H), 7.07 (dd, J = 5.1, 1.0 Hz, 1H), 6.84 (s, 1H), 6.68 (d, J = 3.3
Hz, 1H), 3.68 (d, J = 7.2 Hz, 1H), 3.34 (dd, J = 6.9, 1.0 Hz, 2H),
3.31-3.12 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 198.7, 143.8,
142.3, 137.2, 133.1, 128.8, 128.7, 128.6, 128.1, 127.8, 126.8,
125.8, 123.8, 44.3, 43.3, 36.8; HRMS (ESI, m/z), calcd for
C20H17OS- [M-H]-, 305.1006 ; found, 305.1008.
CDCl3) δ 7.81 (d, J = 8.9 Hz, 2H), 7.25-7.07 (m, 6H), 6.95 (s,
1H), 6.86 (d, J = 8.9 Hz, 2H), 6.79 (dd, J = 7.4, 2.6 Hz, 2H),
3.84 (s, 3H), 3.70 (m, 4H), 3.24 (dd, J = 12.1, 7.1 Hz, 2H), 2.98
(d, J = 7.3 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 197.8, 163.3,
157.8, 145.0, 131.1, 130.5, 130.4, 128.4, 128.3, 127.7, 127.5,
126.2, 120.3, 113.6, 110.3, 55.5, 55.3, 43.8, 41.8, 37.4; HRMS
+
(ESI, m/z), calcd for C24H25O3 [M+H]+, 361.1798; found,
361.1790.
4.2.42. 1-(4-methoxyphenyl)-3-phenyl-4-m-
tolylbutan-1-one (4q)
4.2.37. 3-(4-methoxyphenyl)-4-(naphthalen-1-yl)-1-
Yellow solid (24.4 mg, yield 71%); mp. 134-136 oC; Rf = 0.36
(petroleum ether / acetone = 5/1); FT-IR (cm-1) 3360, 2921,
1675, 1601, 1259, 1170, 700, 612; 1H NMR (300 MHz, CDCl3) δ
phenylbutan-1-one (4l)
Yellow oil (20.1 mg, yield 53%); Rf = 0.19 (petroleum ether /
acetone = 10/1); FT-IR (cm-1) 3359, 2924, 1673, 1600, 1259,

10
Tetrahedron
7.83 (d, J = 8.9 Hz, 2H), 7.20 (dd, J = 14.2, 7.0 Hz, 6H), 6.88
14.8, 7.3 Hz, 3H), 7.41 (t, J = 7.5 Hz, 2H), 7.28 (s, 1H), 7.11
(dd, J = 12.2, 7.9 Hz, 2H), 6.82 (dd, J = 5.0, 3.5 Hz, 1H), 6.67
(d, J = 3.0 Hz, 1H), 4.31-4.12 (m, 1H), 3.42 (dd, J = 10.2, 6.8
Hz, 4H); 13C NMR (101 MHz, CDCl3) δ 198.6, 148.1, 137.1,
135.6, 134.0, 133.2, 132.2, 128.9, 128.7, 128.2, 127.7, 127.3,
126.7, 126.3, 125.7, 125.3, 124.4, 124.1, 123.2, 45.8, 41.4, 37.6;
HRMS (ESI, m/z), calcd for C24H19OS- [M-H]-, 355.1162; found,
355.1162.
(dd, J = 10.8, 3.9 Hz, 5H), 3.85 (s, 3H), 3.64 (s, 1H), 3.24 (d, J
= 1.2 Hz, 2H), 2.93 (d, J = 7.4 Hz, 2H), 2.26 (s, 3H); 13C NMR
(101 MHz, CDCl3) δ 197.6, 163.4, 144.5, 139.9, 137.8, 130.5,
130.4, 130.2, 128.4, 128.1, 127.8, 126.9, 126.4, 113.7, 55.6,
+
43.8, 43.3, 43.1, 21.5; HRMS (ESI, m/z), calcd for C24H25O2
[M+H]+, 345.1849; found, 345.1840.
4.2.43. 4-(3-methoxyphenyl)-1-(4-methoxyphenyl)-
3-phenylbutan-1-one (4r)
4.3. General procedure for the synthesis of compounds 7
Yellow solid (24.8 mg, yield 69%); mp. 129-131 oC; Rf = 0.28
(petroleum ether / acetone = 5/1); FT-IR (cm-1) 2934, 1674,
1600, 1259, 1169, 1031, 833, 699; H NMR (300 MHz, CDCl3)
A Schlenk tube (10 mL) equipped with a magnetic stir bar
was charged with [Ru(p-cymene)Cl2]2 (1.8 mg, 0.003 mmol, 1.5
mol%), PPh3 (3.1 mg, 0.012 mmol, 6 mol%), K3PO4 (31.8 mg,
0.15 mmol, 0.75 equiv.), TBAC (11.1 mg, 0.04 mmol, 0.2
equiv.) and N-benzylideneaniline (0.2 mmol, 1.0 equiv.). The
reaction system was then protected with an argon atmosphere.
After that, THF (50 ꢀL) was added and the reaction system was
placed at room temperature. After stirring for 10 min, hydrazone
(0.3 mmol, 1.5 equiv.) was added to the system. THF was
removed in vacuo and argon was filled into the reaction system.
Then, distilled water (0.2 mL) was added to the reaction system
and heated to 70 oC. After stirring at 70 oC for 1.5 h, 3 mL water
was added. After cooling to room temperature, 2 mL HCl
solution (3 M) was added to the reaction system. The mixture
was extracted with ethyl acetate (3x5 mL). The combined
organic layers was washed with water (5 mL) and then dried
over Na2SO4. The organic layers were concentrated and the
resulting residue was purified by preparative TLC on silica gel to
afford the product.
1
δ 7.84 (d, J = 8.9 Hz, 2H), 7.20 (d, J = 7.9 Hz, 6H), 6.88 (d, J =
8.9 Hz, 2H), 6.73-6.64 (m, 2H), 6.61-6.54 (m, 1H), 3.85 (s, 3H),
3.70 (m, 4H), 3.25 (s, 2H), 3.04-2.86 (m, 2H); 13C NMR (101
MHz, CDCl3) δ 197.5, 163.5, 159.5, 144.4, 141.6, 130.4, 129.2,
128.5, 127.8, 126.5, 121.8, 114.9, 113.8, 111.9, 55.6, 55.2, 43.9,
43.2, 43.1; HRMS (ESI, m/z), calcd for C24H25O3 [M+H]+,
+
361.1798; found, 361.1791.
4.2.44. 1-(4-methoxyphenyl)-3-phenyl-4-p-
tolylbutan-1-one (4s)
Yellow solid (23.4 mg, yield 68%); mp. 145-147 oC; Rf = 0.35
(petroleum ether / acetone = 5/1); FT-IR (cm-1) 2922, 1675,
1
1600, 1259, 1170, 1028, 700; H NMR (300 MHz, CDCl3) δ
7.83 (d, J = 8.9 Hz, 2H), 7.22 (d, J = 21.7 Hz, 6H), 6.98 (d, J =
9.0 Hz, 3H), 6.89 (s, 2H), 3.85 (s, 3H), 3.63 (s, 1H), 3.23 (s, 2H),
2.93 (d, J = 6.7 Hz, 2H), 2.27 (s, 3H); 13C NMR (101 MHz,
CDCl3) δ 197.6, 163.4, 144.5, 136.9, 135.6, 130.5, 130.4, 129.3,
129.0, 128.4, 127.8, 126.4, 113.7, 55.6, 43.9, 43.3, 42.7, 21.1;
HRMS (ESI, m/z), calcd for C24H25O+ [M+H]+, 345.1849; found,
345.1841.
4.3.1. 1,2-diphenylethyl)benzenamine (7a)
Colorless solid (38.7 mg, yield 71%); mp. 58-60 oC; Rf = 0.54
1
(petroleum ether / dichloromethane = 2/1); H NMR (300 MHz,
4.2.45. 1,4-bis(4-methoxyphenyl)-3-phenylbutan-1-
one (4t)
CDCl3) δ 7.35-7.26 (m, 5H), 7.25-7.19 (m, 3H), 7.12 (d, J = 6.4
Hz, 2H), 7.03 (d, J = 8.4 Hz, 2H), 6.66-6.56 (m, 1H), 6.45 (d, J
= 7.7 Hz, 2H), 4.65-4.50 (m, 1H), 4.24-3.99 (m, 1H), 3.13 (dd, J
= 14.0, 5.7 Hz, 1H), 3.00 (dd, J = 14.0, 8.2 Hz, 1H); 13C NMR
(101 MHz, CDCl3) δ 147.4, 143.6, 137.8, 129.4, 129.2, 128.71,
128.68, 127.2, 126.9, 126.6, 117.6, 113.8, 59.4, 45.3; HRMS
(ESI, m/z), calcd for C20H20N+ [M+H]+, 274.1590; found,
274.1587.
Yellow solid (21.5 mg, yield 60%); mp. 174-176 oC; Rf = 0.28
(petroleum ether / acetone = 5/1); FT-IR (cm-1) 2930, 1674,
1602, 1510, 1250, 1170, 1031, 613; 1H NMR (300 MHz, CDCl3)
δ 7.84 (d, J = 8.9 Hz, 2H), 7.19 (dd, J = 18.6, 7.2 Hz, 4H), 6.96
(d, J = 8.5 Hz, 3H), 6.88 (d, J = 8.8 Hz, 2H), 6.74 (d, J = 8.6
Hz, 2H), 3.86 (s, 3H), 3.75 (s, 3H), 3.67-3.54 (m, 1H), 3.34-3.14
(m, 2H), 3.00-2.81 (m, 2H); 13C NMR (101 MHz, CDCl3) δ
197.7, 163.5, 161.2, 158.0, 144.5, 130.4, 130.3, 128.4, 127.8,
126.4, 114.4, 113.74, 113.66, 55.6, 55.3, 43.8, 43.5, 42.2; HRMS
4.3.2. N-(2-(2-methoxyphenyl)-1-
phenylethyl)benzenamine (7b)
o
(ESI, m/z), calcd for C24H25O3 [M+H]+, 361.1798; found,
361.1791.
+
Colorless solid (28.4 mg, yield 47%); mp. 133-136 C; Rf =
0.45 (petroleum ether / dichloromethane = 1/1); FT-IR (cm-1)
1
3405, 2921, 2361, 1601, 1494, 1242, 749, 697; H NMR (300
4.2.46. 1-(4-methoxyphenyl)-4-(naphthalen-1-yl)-3-
phenylbutan-1-one (4u)
MHz, CDCl3) δ 7.38 (d, J = 7.2 Hz, 2H), 7.30 (t, J = 7.3 Hz,
2H), 7.24 (s, 2H), 7.01 (t, J = 7.8 Hz, 3H), 6.92-6.80 (m, 2H),
6.57 (t, J = 7.3 Hz, 1H), 6.40 (d, J = 7.7 Hz, 2H), 4.71 (s, 1H),
4.54 (dd, J = 8.7, 4.9 Hz, 1H), 3.88 (s, 3H), 3.10 (dd, J = 13.7,
8.8 Hz, 1H), 3.01 (dd, J = 13.8, 4.9 Hz, 1H); 13C NMR (101
MHz, CDCl3) δ 157.7, 147.9, 144.4, 131.2, 129.1, 128.6, 128.1,
127.04, 126.99, 126.5, 120.9, 116.9, 113.4, 110.6, 59.6, 55.5,
40.1; HRMS (ESI, m/z), calcd for C21H22NO+ [M+H]+, 304.1696;
found, 304.1702.
Yellow oil (26.5 mg, yield 70%); Rf = 0.18 (petroleum ether /
acetone = 10/1); FT-IR (cm-1) 2930, 2360, 1682, 1511, 1248, 778;
1H NMR (300 MHz, CDCl3) δ 8.28-8.14 (m, 1H), 7.86-7.77 (m,
3H), 7.66 (s, 1H), 7.50 (dd, J = 11.6, 7.7 Hz, 3H), 7.40 (d, J =
7.7 Hz, 2H), 7.25 (s, 2H), 7.07 (d, J = 8.8 Hz, 2H), 6.76 (d, J =
8.7 Hz, 2H), 3.80 (d, J = 33.2 Hz, 4H), 3.36 (d, J = 6.7 Hz, 4H);
13C NMR (101 MHz, CDCl3) δ 199.3, 158.2, 137.3, 136.6, 136.1,
134.0, 133.0, 132.3, 130.4, 128.8, 128.7, 128.61, 128.55, 128.1,
127.7, 127.0, 126.1, 125.6, 125.3, 124.3, 113.9, 55.3, 45.0, 41.4,
4.3.3. N-(1-phenyl-2-p-tolylethyl)benzenamine (7c)
40.7; HRMS (ESI, m/z), calcd for C27H23O2 [M-H]-, 379.1704;
found, 379.1703.
-
Colorless oil (28.1 mg, yield 49%); Rf = 0.53 (petroleum ether
1
/ dichloromethane = 2/1); H NMR (300 MHz, CDCl3) δ 7.41-
7.16 (m, 5H), 7.13-6.92 (m, 6H), 6.61 (t, J = 7.3 Hz, 1H), 6.44
(d, J = 7.5 Hz, 2H), 4.65-4.44 (m, 1H), 4.10 (s, 1H), 3.09 (dd, J
= 14.0, 5.5 Hz, 1H), 2.94 (dd, J = 14.0, 8.3 Hz, 1H), 2.28 (s, 3H);
13C NMR (126 MHz, CDCl3) δ 147.5, 143.7, 136.4, 134.7, 129.4,
129.2, 129.1, 128.7, 127.7, 126.6, 117.5, 113.8, 59.3, 44.9, 21.2;
HRMS (ESI, m/z), calcd for C21H22N+ [M+H]+, 288.1747; found,
288.1747.
4.2.47. 4-(naphthalen-1-yl)-3-phenyl-1-(thiophen-
2-yl)butan-1-one (4v)
Yellow oil (26.6 mg, yield 75%); Rf = 0.33 (petroleum ether /
acetone = 10/1); FT-IR (cm-1) 2923, 1683, 1213, 1077, 778, 614;
1H NMR (300 MHz, CDCl3) δ 8.23 (d, J = 8.4 Hz, 1H), 7.85 (dd,
J = 7.1, 5.7 Hz, 3H), 7.70 (d, J = 8.2 Hz, 1H), 7.52 (dd, J =

11
4.4. General procedure for the synthesis of compounds 8
(m, 2H), 3.11 (d, J = 13.3 Hz, 1H), 3.00 (d, J = 13.3 Hz, 1H),
2.34 (s, 3H), 1.81 (s, 1H), 1.54 (s, 3H); 13C NMR (126 MHz,
CDCl3) δ 144.8, 137.0, 136.3, 130.8, 128.9, 128.2, 126.7, 125.0,
74.5, 50.6, 29.6, 21.1; HRMS (APCI, m/z), calcd for C16H17+ [M-
O-H]+, 209.1325; found, 209.1328.
A Schlenk tube (10 mL) equipped with a magnetic stir bar
was charged with [Ru(p-cymene)Cl2]2 (1.8 mg, 0.003 mmol, 1.5
mol%), PPh3 (3.1 mg, 0.012 mmol, 6 mol%), K3PO4 (31.8 mg,
0.15 mmol, 0.75 equiv.), TBAC (11.1 mg, 0.04 mmol, 0.2
equiv.) and ketones (0.2 mmol, 1.0 equiv.). The reaction system
was then protected with an argon atmosphere. After that, THF
(50 ꢀL) was added and the reaction system was placed at room
temperature. After stirring for 10 min, hydrazone (0.3 mmol, 1.5
equiv.) was added. THF was removed in vacuo and argon was
filled into the reaction system. Then, distilled water (0.2 mL)
4.5. General procedure for the synthesis of compounds 9
A Schlenk tube (10 mL) equipped with a magnetic stir bar
was charged with 4-(3,4,5-trimethoxyphenyl)-1,3-diphenylbutan-
1-one (4i) (39 mg, 0.1 mmol), AlCl3 (120 mg, 0.9 mmol, 9
equiv.). After that, acetonitrile (2 mL) was added and heated to
60 C. The reaction system was stirred at 60 C for 12 hours.
After cooling to room temperature, the reaction mixture was
diluted with 3 mL of water. 2 mL HCl solution (3 M) was added
and the reaction mixture was extracted with ethyl acetate (3x5
mL). The combined organic layers were washed with water (5
mL) and then dried over Na2SO4. The organic layers were
concentrated and the resulting residue was purified by
preparative TLC on silica gel to afford the product.
o
o
o
was added to the reaction mixture and heated to 70 C. The
reaction progress was followed by TLC and the reaction time
was determined (3-18 hours). The reaction mixture was diluted
with 3 mL of water. After cooling to room temperature, 2 mL
HCl solution (3 M) was added. The reaction mixture was
extracted with ethyl acetate (3x5 mL). The combined organic
layers were washed with water (5 mL) and then dried over
Na2SO4. The organic layers were concentrated and the resulting
residue was purified by preparative TLC on silica gel to afford
the product.
4.5.1. 1,2-dihydro-5,6,7-trimethoxy-2,4-
diphenylnaphthalene (9a)
o
Colorless solid (25.3 mg, 68%); mp. 74-76 C; Rf = 0.22
(petroleum ether / dichloromethane = 1:1); H NMR (400 MHz,
4.4.1. 1,2-diphenylpropan-2-ol (8a)
1
Colorless oil (30.1 mg, yield 71%); Rf = 0.32 (petroleum ether
CDCl3) δ 7.39-7.18 (m, 10H), 6.57 (s, 1H), 6.02 (d, J = 3.5 Hz,
1H), 3.87 (s, 3H), 3.80 (s, 3H), 3.69 (ddd, J = 12.3, 6.1, 3.6 Hz,
1H), 3.28 (s, 3H), 3.03-2.85 (m, 2H); 13C NMR (126 MHz,
CDCl3) δ 152.73, 151.23, 144.61, 143.11, 141.46, 138.50,
133.60, 132.92, 128.64, 127.80, 127.69, 127.12, 126.66, 126.41,
121.25, 107.26, 61.08, 60.81, 56.13, 41.63, 39.20; HRMS
1
/ acetone = 10/1); H NMR (300 MHz, CDCl3) δ 7.40 (dd, J =
5.4, 3.4 Hz, 2H), 7.37-7.29 (m, 2H), 7.29-7.15 (m, 5H), 7.06-
6.91 (m, 2H), 3.13 (d, J = 13.3 Hz, 1H), 3.02 (d, J = 13.3 Hz,
1H), 1.85 (s, 1H), 1.56 (s, 3H); 13C NMR (101 MHz, CDCl3) δ
147.7, 136.9, 130.7, 128.2, 126.78, 126.77, 125.1, 74.6, 50.6,
29.5; HRMS (APCI, m/z), calcd for C15H15O+ [M-H]+, 211.1117;
found, 211.1116.
(APCI, m/z), calcd for C25H25O3 [M+H]+, 373.1798; found,
+
373.1795.
4.4.2. 2-(2-fluorophenyl)-1-phenylpropan-2-ol (8b)
4.5.2. 1,2,3-trimethoxy-6,8-diphenylnaphthalene
Yellow oil (19.3 mg, yield 42%); Rf = 0.46 (petroleum ether /
(9b)
1
acetone = 10/1); H NMR (300 MHz, CDCl3) δ 7.32 (ddd, J =
o
Light yellow solid (4.4 mg, 12%); mp. 67-69 C; Rf = 0.26
(petroleum ether / dichloromethane = 1:1); H NMR (400 MHz,
8.2, 6.4, 1.7 Hz, 1H), 7.28-7.11 (m, 4H), 7.11-6.92 (m, 4H), 3.33
(d, J = 13.4 Hz, 1H), 3.11 (d, J = 13.4 Hz, 1H), 2.11 (t, J = 5.2
Hz, 1H), 1.64 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 160.6,
158.7, 136.7, 134.1, 134.0, 130.6, 128.9, 128.8, 128.3, 127.6,
127.5, 126.9, 124.13, 124.11, 116.1, 115.9, 73.71, 73.68, 48.14,
48.10, 28.38, 28.35; HRMS (APCI, m/z), calcd for C15H14F+ [M-
O-H]+, 213.1074; found, 213.1076.
1
CDCl3) δ 7.92 (d, J = 1.7 Hz, 1H), 7.71 (d, J = 7.3 Hz, 2H),
7.51-7.29 (m, 9H), 7.10 (s, 1H), 4.02 (s, 3H), 3.91 (s, 3H), 3.27
(s, 3H); 13C NMR (126 MHz, CDCl3) δ 153.26, 149.78, 144.53,
142.53, 140.75, 139.00, 137.38, 132.45, 129.12, 128.95, 127.52,
127.42, 127.30, 127.00, 126.23, 124.49, 121.77, 103.63, 61.27,
+
60.73, 55.98; HRMS (APCI, m/z), calcd for C25H23O3 [M+H]+,
371.1642; found, 371.1639.
4.4.3. 2-(4-bromophenyl)-1-phenylpropan-2-ol (8c)
Orange oil (33.1 mg, yield 57%); Rf = 0.34 (petroleum ether /
1
acetone = 10/1); H NMR (300 MHz, CDCl3) δ 7.48-7.38 (m,
2H), 7.30-7.16 (m, 5H), 7.04-6.93 (m, 2H), 3.09 (d, J = 13.3 Hz,
1H), 2.99 (d, J = 13.3 Hz, 1H), 1.84 (s, 1H), 1.54 (s, 3H); 13C
NMR (126 MHz, CDCl3) δ 146.8, 136.4, 131.2, 130.7, 128.3,
127.1, 127.0, 120.7, 74.4, 50.5, 29.6; HRMS (APCI, m/z), calcd
for C15H14BrO- [M-H]-, 289.0234; found, 289.0240.
Acknowledgments
This work was supported by the National Key R&D Program
of China (2016YFA0602900, 2017YFA0208100, and
2020YFA0707901), National Natural Science Foundation of
China (22022704, 91853124, 21977097, 21778057, and
21420102003) and Chinese Academy of Sciences.
4.4.4. 2-(3-methoxyphenyl)-1-phenylpropan-2-ol
(8d)
Orange oil (24.1 mg, yield 50%); Rf = 0.29 (petroleum ether /
1
acetone = 10/1); H NMR (300 MHz, CDCl3) δ 7.26-7.17 (m,
References and notes
4H), 7.06-6.93 (m, 4H), 6.78 (ddd, J = 8.2, 2.4, 0.9 Hz, 1H), 3.78
(s, 3H), 3.12 (d, J = 13.3 Hz, 1H), 3.00 (d, J = 13.3 Hz, 1H),
1.86 (s, 1H), 1.54 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 159.6,
149.6, 136.8, 130.7, 129.2, 128.2, 126.8, 117.6, 112.0, 111.2,
74.5, 55.4, 50.5, 29.6; HRMS (EI, m/z), calcd for C16H18O2+ [M]+,
242.1307; found, 242.1306.
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Supplementary Material
Supplementary material that may be helpful in the review
process should be prepared and provided as a separate electronic
file. That file can then be transformed into PDF format and
submitted along with the manuscript and graphic files to the
appropriate editorial office.
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Declaration of interests
☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: