Oxidative acylation of α,α-diarylallylic alcohols: Synthesis of 1,2,4-triarylbutane-1,4-diones

Article abstract of DOI:10.1002/aoc.4407

A metal-free mediated oxidative acylation of α,α-diarylallylic alcohols with simple aromatic aldehydes for the synthesis of 1,2,4-triphenylbutane-1,4-diones is presented. In the presence of TBPB (tert-butyl peroxybenzoate), desired products were obtained in good to excellent yields for 28 examples. This protocol features high regioselectivity, wide functional group tolerance and atom economy.

Full text of DOI:10.1002/aoc.4407

Received: 9 March 2018
DOI: 10.1002/aoc.4407
Revised: 4 April 2018
Accepted: 6 April 2018
F U L L P A P E R
Oxidative acylation of α,α‐diarylallylic alcohols: Synthesis of
1,2,4‐triarylbutane‐1,4‐diones
Yong Li1 | Yuting Leng1,2 | Shiwei Wang3 | Yuhui Gao1 | Huiyan Lv1 | Junbiao Chang1,2
Yusheng Wu1,4 | Yangjie Wu1
|
1 College of Chemistry and Molecular
A metal‐free mediated oxidative acylation of α,α‐diarylallylic alcohols with
simple aromatic aldehydes for the synthesis of 1,2,4‐triphenylbutane‐1,4‐diones
is presented. In the presence of TBPB (tert‐butyl peroxybenzoate), desired prod-
ucts were obtained in good to excellent yields for 28 examples. This protocol
features high regioselectivity, wide functional group tolerance and atom
economy.
Engineering, Key Laboratory of Chemical
Biology and Organic Chemistry of Henan
Province, Zhengzhou University,
Zhengzhou 450001, People's Republic of
China
2 School of Pharmaceutical Sciences,
Collaborative Innovation Center of New
Drug Research and Safety Evaluation,
Zhengzhou University, Zhengzhou
450001, People's Republic of China
3 School of Mechanics and Engineering
Science, Zhengzhou University,
Zhengzhou, Henan 450001, People's
Republic of China
KEYWORDS
α,α‐diarylallylic alcohols, 1,4‐dione synthesis, oxidative acylation
4 Tetranov Biopharm LLC, Zhengzhou
450052, People's Republic of China
Correspondence
Yuting Leng, College of Chemistry and
Molecular Engineering, Collaborative
Innovation Center of New Drug Research
and Safety Evaluation, Zhengzhou
University, Zhengzhou 450001, China.
Email: yutingleng@zzu.edu.cn
Yangjie Wu, College of Chemistry and
Molecular Engineering, Zhengzhou
University, Zhengzhou 450001, China.
Email: wyj@zzu.edu.cn
Funding information
Natural Science Foundation of Henan
Province, Grant/Award Number:
182300410211; National Natural Science
Foundation of China, Grant/Award
Number: 2117220051603192
1 | INTRODUCTION
for the synthesis of 1,4‐diols, as well as five‐membered
hetereocycles, such as furans, pyrroles, thiophenes and
1,4‐Dicarbonyl compounds have attracted considerable
attention due to their wide application in organic synthe-
sis especially for natural products and bioactive com-
pounds.[1] They are a type of versatile building blocks
selenophenes.[2] Enormous efforts have been devoted to
developing efficient methods for building such a structure
of 1,4‐dicarbonyl compounds, although each protocol has
its limitations.[3]
Appl Organometal Chem. 2018;e4407.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
1 of 11
https://doi.org/10.1002/aoc.4407

2 of 11
LI ET AL.
The traditional synthesis methods were based on a
and various aryl coupling partners and prepared ketones
and aldehydes with high enantiomeric excess.[10] In this
context, many other groups have reported the conversion
of substituted allylic alcohols to aldehydes or ketones and
multicomponent coupling approaches, including more
recent examples from Lei and co‐workers,[11] Jiang and
co‐workers,[12] Kommu and co‐workers,[13] Alacid and
Nájera,[14] Skrydstrup and co‐workers[15] and Pan
et al.[16] Despite the great successes achieved in this field,
some problems exist with these procedures, such as (1)
the product will be contaminated with residual metal
reagents or organic catalysts used in the reaction, (2)
the side reactions of two substrates are difficult to avoid
and (3) the use of a toxic reagent, thereby limiting appli-
cations, especially in the pharmaceutical industry.
Stetter reaction catalyzed by cyanide or thiazolium salts;
however, these can lead to undesired side products.[4]
Transition metal‐mediated strategies have been devel-
oped, including isomerization of alkynediols,[5]
difunctionalization of alkenes[6] as well as the reductive
coupling of acid chlorides with unsaturated ketones or
with cyclopropanols.[7] However, in these cases, the
drawbacks include unstable starting materials, reactive
intermediates and requirement for special reagents, lead-
ing to the weak endurance of substrates. Other
approaches include the oxidative homocoupling of ketone
enolates and preparation of symmetric 1,4‐diketones.[8,9]
Sigman and co‐workers researched a series of Pd‐cata-
lyzed redox‐relay reactions between alkenyl alcohols
TABLE 1 Optimization of reaction conditionsa
Entry
Oxidant (equiv.)
Solvent
Temp. (°C)
Yield (%)
1
DTBP (4)b
TBHP (4)c
TBHP (4)d
TBPB (4)e
K2S2O8 (4)
H2O2 (4)
O2
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
DCE
110
110
110
110
110
110
110
110
110
110
110
110
110
110
80
33
83
2
3
25
4
94
5
50
6
45
7
32
8
TBPB (4)
TBPB (4)
TBPB (4)
TBPB (4)
TBPB (4)
TBPB (3)
TBPB (2)
TBPB (4)
TBPB (4)
TBPB (4)
50
9
Xylene
59
10
11
12
13
14
15
16
17f
p‐Xylene
Chlorobenzene
DMF
28
46
73
Toluene
Toluene
Toluene
Toluene
Toluene
76
59
Trace
88
140
110
78
aReaction conditions: 1a (0.2 mmol), 2a (0.3 mmol) and oxidant in solvent (1 ml), under air, 24 h; isolated yields based on 1a.
bDTBP: di‐tert‐butyl peroxide.
cTBHP: tert‐butyl hydroperoxide (70% in decane).
dTBHP: tert‐butyl hydroperoxide (70% in aqueous solution).
eTBPB: tert‐butyl peroxybenzoate.
fUnder nitrogen atmosphere.

LI ET AL.
3 of 11
Therefore, the development of simple, efficient and envi-
ronmentally benign methods for synthesizing various 1,4‐
dicarbonyl compounds is appealing.
Herein, based on the fact that allyl alcohol is easily
isomerized in the reaction, which results in substituent
migration rearrangement,[17,18] we report our recent
efforts in developing a metal‐free mediated oxidative acyl-
ation of α,α‐diarylallylic alcohols for the synthesis of
1,2,4‐triarylbutane‐1,4‐diones.
the reaction using TBHP in water as an oxidant gave a
lower yield (25%, entry 3). Surprisingly, an excellent yield
of 94% was afforded when TBPB was oxidant and the
reaction temperature was 110 °C for 24 h (entry 4). Other
oxidants, such as K2S2O8, H2O2 and O2, were not found to
be very effective in the reaction (entries 5–7). Among the
solvents examined (toluene, DCE, xylene, chlorobenzene,
DMF), toluene was found to be superior (entries 4, 8–12).
Decreasing the loading of TBPB resulted in a significant
decrease in the yield (entry 14), while almost no product
was obtained at 80 °C (entry 15) when decreasing the
reaction temperature. Increasing the reaction tempera-
ture, a lower yield of 88% of product 3a was obtained
(entry 16). When the reaction was carried out under
nitrogen atmosphere, the desired product 3a was
obtained with a yield of 78% (entry 17), which indicated
that a certain amount of oxygen in air could facilitate
the reaction. Finally, the optimized reaction conditions
were identified as follows: TBPB as the oxidant and tolu-
ene as the solvent, at 110 °C in an oil bath under air
atmosphere for 24 h.
2 | RESULTS AND DISCUSSION
Initially, the reaction of α,α‐diphenylallylic alcohol (1a)
with benzaldehyde (2a) was chosen as a model reaction
to screen various reaction parameters. The results are
summarized in Table 1. Only 33% yield of the desired
product 3a was obtained when di‐tert‐butyl peroxide
was used as oxidant and toluene as solvent (Table 1, entry
1). The molecular structure of product 3a was confirmed
from its NMR spectrum. To our delight, an 83% yield of
3a was obtained in the presence of tert‐butyl
peroxybenzoate (TBPB) in decane (entry 2). However,
With the optimized reaction conditions in hand
(Table 1, entry 4), the scope of α,α‐diarylallylic alcohols
TABLE 2 Substrate scope of α,α‐diarylallylic alcoholsa
aReaction conditions: 1a–1 k (0.2 mmol), 2a (0.3 mmol), TBPB (4 equiv.), in solvent (1 ml), under air, at 120 °C for 24 h; isolated yields based on 1a–1 k.
bRatio of 3fa to its isomer was determined by 1H NMR analysis of the isolated product.

4 of 11
LI ET AL.
TABLE 3 Substrate scope of aromatic aldehydesa
aReaction conditions: 1a (0.2 mmol), 2b–2u (0.3 mmol), TBPB (4 equiv.), in toluene (1 ml), at 120 °C, under air for 24 h; isolated yields based on 1a.
SCHEME 1 Experiment for reaction
mechanism
including symmetric and asymmetric ones was examined
in the acylation with benzaldehyde (Table 2). The reac-
tion could proceed well with a series of substituted
diarylallylic alcohols, affording the corresponding prod-
ucts 3aa–3 ka in moderate to good yields. For the sym-
metric α,α‐diarylallylic alcohols with electron‐donating
and electron‐withdrawing group in aromatic rings, such
as methyl, chloro, fluoro and trifluoromethyl, the reac-
tion proceeded smoothly and provided the desired prod-
ucts in yields of 35–94% (3aa–3ea). When the aromatic
rings in asymmetric α,α‐diarylallylic alcohols were
substituted by groups such as methyl, methoxy and
chloro, the products were isolated in yields of 38–97%
(3fa–3 ka). Moreover, the transformation was obviously
SCHEME 2 Plausible reaction mechanism

LI ET AL.
5 of 11
affected by electronic effect and steric hindrance. The
major products were obtained by a priority migration of
the aromatic ring which had lower electron cloud density
(3ga and 3 ha). With asymmetric α,α‐diarylallylic alco-
hols bearing an electron‐withdrawing group on the ortho
position of the aromatic ring, only steric hindrance
control product was afforded in a yield of 38% (3 ka) by
a priority migration of the aromatic ring which had weak
space resistance.
at high temperature. Benzaldehyde (2a) was converted
into an acyl radical I with the aid of tert‐butoxyl
radical. Then, the radical intermediate II was formed
by the addition of allylic alcohol 1a with acyl radical.
Subsequently, an intramolecular radical addition of the
carbon radical with benzene ring in intermediate II
occurred to generate the spiro[2,5] octadienyl radical
III, followed by the migration of the electron‐deficient
aryl group preferentially releasing IV. It is notable that
ortho‐substituted benzene rings are reluctant to migrate
owing to a sterically congested radical III which is
difficult to form, and this is consistent with the
experimental results. Finally, the desired product 3aa
was generated by further oxidation or charge
migration eliminating the hydrogen radical. The benzo-
ate radical received a hydrogen radical to give a
benzoic acid.
Encouraged by the results obtained with α,α‐
diarylallylic alcohols, this reaction system was applied
to expand the substrates to various aromatic aldehydes
(Table 3). It was found that various aromatic aldehydes
could be employed as suitable substrates under these
reaction conditions, giving the corresponding products
3ab–3ao, 3aq–3ar and 3at in moderate to excellent
yields for most cases. The results are summarized in
Table 3. The reaction efficiency was not significantly
affected by electronic variation of substrates. For
instance, aromatic aldehydes with electron‐donating
and weakly electron‐withdrawing substituents, such as
Me, MeO, F, Cl, Br, CF3, Ph and PhO at the para posi-
tion or meta position, gave the desired products in good
to excellent yields. The steric effect played an important
role in the reaction; for example, benzaldehydes bearing
an ortho‐methyl or other groups such as Me, MeO, F
and CF3 led to an evident decrease of reaction yields
(3ad, 3ag, 3aj, 3 am, 3ap). While this reaction was
not applied to aliphatic aldehydes. When caproaldehyde
and cyclohexanecarboxaldehyde were used as the sub-
strates, the corresponding products were not obtained.
It is worth noting that all the halogen (F, Cl, Br) atoms
substituted on the aromatic ring provided the products
in good yields of 70–85% (3ak–3ao). These results
showed that halogen groups especially Cl and Br com-
monly used in organic synthesis were compatible with
the present conditions, which made this reaction partic-
ularly attractive for increasing the molecular complexity
by various chemical transformations.
3 | CONCLUSIONS
In summary, we have developed a novel acylation of α,α‐
diarylallylic alcohols via an addition with aryl aldehyde
and an aryl rearrangement involving new C (Ar)─ C
(sp3) and C (sp3)─ C (CO) bond formation. A variety of
1,2,4‐triphenylbutane‐1,4‐diones were obtained in moder-
ate to excellent yields. In addition, chemoselective migra-
tion of the two different aryl groups was observed in the
reaction. Currently, experiments towards enlarging the
scope of the system to the synthesis of other 1,4‐dione
compounds and further mechanistic studies are under-
way in our laboratory.
4 | EXPERIMENTAL
1H NMR spectra were recorded with a Bruker DPX‐400
(400 MHz) spectrometer with deuterated chloroform as
solutions. The chemical shifts are reported in ppm rela-
tive to tetramethylsilane. 13C NMR spectra were
recorded at 100 MHz with a Bruker DPX‐400. The
chemical shifts are reported relative to residual CHCl3
(77.00 ppm). The multiplicity of signals is designated
by the following abbreviations: s (singlet), d (doublet),
t (triplet), q (quartet), m (multiplet). Coupling constants
J are reported in hertz (Hz). HRMS was conducted
using an Agilent LC‐MSD‐Trap‐XCT spectrometer with
micromass MS software using electrospray ionization
(ESI). Dichloromethane, ethyl acetate and hexane (ana-
lytical grade) were used for column chromatography
without purification. The other chemicals were obtained
from commercial sources and used as received unless
otherwise noted.
To gain further insight into the possible radical mech-
anism, a control experiment with substrates 1a and 2a in
the presence of 2 equiv. of (2,2,6,6‐tetramethylpiperidin‐
1‐yl) oxyl (TEMPO) was carried out (Scheme 1). As
expected, the formation of the desired product 3aa was
suppressed, and only the TEMPO–benzoyl adduct 4 was
observed (determined using high‐resolution MS (HRMS)
analysis). This result indicated that TBPB‐mediated reac-
tion of 1a with benzaldehyde might be a radical‐initiated
route to the target product.
A reaction mechanism was proposed, as outlined in
Scheme 2, based on the results obtained and previous
19]
literature.[18g,
First, tert‐butoxyl radical and benzo-
ate radical were generated by the homolysis of TBPB

6 of 11
LI ET AL.
7.54 (t, J = 7.3 Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H), 7.24 (d,
J = 7.5 Hz, 2H), 7.18 (d, J = 7.9 Hz, 2H), 7.10 (d,
J = 7.6 Hz, 2H), 5.27 (dd, J = 9.8, 3.5 Hz, 1H), 4.18 (dd,
J = 18.0, 10.0 Hz, 1H), 3.26 (dd, J = 18.0, 3.7 Hz, 1H),
2.34 (s, 3H), 2.28 (s, 3H). 13C NMR (100 MHz, CDCl3, δ,
ppm): 198.6, 198.2, 143.6, 137.0, 136.6, 135.9, 133.9,
128.9, 129.2, 129.1, 128.8, 128.5, 128.2, 128.1, 126.8, 48.2,
43.8, 21.7, 21.1. HRMS (ESI+): calcd for C24H22O2
[M + H]+: 343.1693, found 343.1695.
4.1 | General Procedure for Preparation of
α,α‐Diarylallylic Alcohols[20]
A 50 ml dry round‐bottom flask was equipped with a mag-
netic stir bar and charged with diarylmethyl ketone (42 mg,
5 mmol) and tetrahydrofuran (50 ml), which was stirred for
10 min at 0 °C under nitrogen atmosphere. Then, to the
reaction system was added ethylmagnesium bromide
(6 mmol, 1.2 equiv.). After 20 min, the system was heated
to room temperature. Subsequently, the resulting solution
was washed with saturated ammonium chloride solution
and was extracted with ethyl acetate. Combined organic
layers were treated with saturated NaCl aqueous solution,
and then the organic layers were dried over Na2SO4 and
filtered. After evaporation of the solvent under vacuum,
the residue was purified by column chromatography on
silica gel (100–200 mesh) using hexane–EtOAc as eluent
to afford the corresponding desired product.
4.2.3 | 1,2‐Bis (4‐fluorophenyl)‐4‐
phenylbutane‐1,4‐dione (3ca)
1
Yellow liquid (yield: 35%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.04 (dd, J = 8.4, 5.6 Hz, 2H), 7.9 (d, J = 7.4 Hz,
2H), 7.58–7.55 (m, 1H), 7.47–7.43 (m, 2H), 7.33–7.30 (m,
2H), 7.10–7.06 (m, 2H), 7.03–6.98 (m, 2H), 5.26 (dd,
J = 9.9, 5.6 Hz, 1H), 4.17 (dd, J = 18.0, 10.1 Hz, 1H),
3.30 (dd, J = 18.0, 3.7 Hz, 1H). 13C NMR (100 MHz,
CDCl3, δ, ppm): 197.9, 197.3, 165.7 (d, J = 254.4 Hz),
162.1 (d, J = 146.7 Hz), 136.3, 134.1 (d, J = 3.4 Hz),
133.5, 132.7 (d, J = 2.7 Hz), 131.6 (d, J = 9.3 Hz), 129.8
(d, J = 8.0 Hz), 128.7, 128.2, 116.2 (d, J = 21.5 Hz),115.7
(d, J = 22.0 Hz), 115.0 (d, J = 21.4 Hz), 47.8, 43.9. 19F
NMR (163 MHz, CDCl3, δ, ppm): 15.3. HRMS (ESI+):
calcd for C22H16F2O2 [M + H]+: 351.1191, found
351.1195.
4.2 | General Procedure for Reaction of
α,α‐Diarylallylic Alcohols with
Arylaldehyde
A 25 ml Schlenk flask was equipped with a magnetic stir
bar and charged with α,α‐diarylallylic alcohol (0.2 mmol),
arylaldehyde 2a (0.3 mmol, 1.5 equiv.), TBPB (0.8 mmol,
4 equiv.) and toluene (1.0 ml). The resulting mixture was
heated at 110 °C for 24 h, and cooled to room tempera-
ture. The resulting solution was directly filtered through
a pad of silica gel using a sintered glass funnel which then
was washed using EtOAc. The resulting solution was con-
centrated under reduced pressure. The residue was puri-
fied by chromatography on silica gel (EtOAc–petroleum
ether 1/10–1/15, v/v) to give the desired product.
4.2.4 | 1,2‐Bis (4‐chlorophenyl)‐4‐
phenylbutane‐1,4‐dione (3da)
1
Yellow liquid (yield: 88%). H NMR (400 MHz, CDCl3, δ,
ppm): 7.95 (t, J = 7.6 Hz, 4H), 7.63 (t, J = 7.3 Hz, 1H),
7.45 (t, J = 7.6 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.28 (s,
4H), 5.24 (dd, J = 10.0, 3.7 Hz, 1H), 4.16 (dd, J = 18.1,
10.0 Hz, 1H), 3.30 (dd, J = 18.0, 3.6 Hz, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 197.7, 197.5, 139.6, 136.7,
136.2, 134.6, 133.6, 133.5, 130.3, 129.6, 129.5, 128.9,
128.7, 128.2, 47.9, 43.7. HRMS (ESI+): calcd for
C22H16Cl2O2 [M + H]+: 383.0600, found 383.0605.
4.2.1 | 1,2,4‐Triphenylbutane‐1,4‐dione
(3aa)
1
Yellow liquid (yield: 94%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.34 (d, J = 7.4 Hz, 2H), 7.97 (d, J = 7.4 Hz, 2H),
7.54 (t, J = 7.4 Hz, 1H), 7.49–7.35 (m, 7H), 7.30 (t,
J = 7.4, 2H), 7.23–7.20 (m, 1H), 5.33 (dd, J = 10.0,
3.4 Hz, 1H), 4.21 (dd, J = 18.0, 10.1 Hz, 1H), 4.21 (dd,
J = 18.0, 3.5 Hz, 1H). 13C NMR (100 MHz, CDCl3, δ,
ppm): 198.9, 198.1, 138.7, 136.5, 133.3, 132.9, 129.2, 128.9,
128.6, 128.5, 128.3, 128.2, 127.4, 48.7, 43.9. HRMS (ESI+):
calcd for C22H18O2 [M + H]+: 315.1380, found 315.1383.
4.2.5 | 4‐Phenyl‐1,2‐bis (4‐
(trifluoromethyl)phenyl)butane‐1,4‐dione
(3ea)
1
Yellow liquid (yield: 75%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.30 (s, 1H), 8.21 (d, J = 7.8 Hz, 1H), 7.98 (d,
J = 7.5 Hz, 2H), 7.79 (d, J = 7.7 Hz, 1H), 7.65 (s, 1H),
7.60–7.52 (m, 4H),7.46 (t, J = 7.6 Hz, 3H), 5.39 (dd,
J = 10.3, 3.3 Hz, 1H), 4.26 (dd, J = 18.0, 10.3 Hz, 1H),
3.39 (dd, J = 18.0, 3.4 Hz, 1H). 13C NMR (100 MHz,
CDCl3, δ, ppm): 197.5, 197.2, 138.8, 136.7, 135.9, 133.7,
131.9, 131.7, 129.9, 129.7 (dd, J = 7.4, 3.9 Hz), 129.4,
4.2.2 | 4‐Phenyl‐1,2‐di‐p‐tolylbutane‐1,4‐
dione (3ba)
1
Yellow liquid (yield: 70%). H NMR (400 MHz, CDCl3, δ,
ppm): 7.97 (d, J = 7.4 Hz, 2H), 7.93 (d, J = 8.1 Hz, 2H),

LI ET AL.
7 of 11
128.7, 128.2, 125.7 (dd, J = 7.5, 3.7 Hz), 124.9 (dd, J = 8.1,
4.3 Hz), 124.7 (dd, J = 7.0, 3.4 Hz), 48.4, 44.0. HRMS (ESI
+): calcd for C24H16F6O2 [M + H]+: 451.1127, found
451.1127.
7.39 (m, 4H), 7.29 (dd, J = 12.3, 8.5 Hz, 4H), 5.31 (dd,
J = 9.8, 3.8 Hz, 1H), 4.17 (dd, J = 18.0, 9.8 Hz, 1H),
3.27 (dd, J = 18.1, 3.9 Hz, 1H). 13C NMR (100 MHz,
CDCl3, δ, ppm): 198.7, 197.8, 137.1, 136.3, 136.2, 133.4,
133., 129.63, 129.4, 128.9, 128.7(d, J = 1.2 Hz), 128.2,
47.9, 43.7. HRMS (ESI+): calcd for C22H17ClO2 [M + H]
+: 349.0990, found 349.0995.
4.2.6 | 2,4‐Diphenyl‐1‐(p‐tolyl)butane‐1,4‐
dione (3fa) and 1,4‐diphenyl‐2‐(p‐tolyl)
butane‐1,4‐dione (3fa′)
Yellow liquid (yield: 76%, 3fa:3fa′= 17:13). 1H NMR
(400 MHz, CDCl3, δ, ppm): 8.04–7.93 (m, 4H), 7.56–7.52
(m, 1H), 7.50–7.35 (m, 4H), 7.31–7.18 (m, 4H), 7.12–7.10
(m, 1H), 5.33–5.27 (m, 1H), 4.23–4.16 (m, 1H), 3.31–3.25
(m, 1H). 13C NMR (100 MHz, CDCl3, δ, ppm): 199.0,
198.4, 198.2, 198.1, 143.7, 138.9, 137.1, 136.5, 136.4,
135.5, 133.8, 133.2, 132.8, 129.9, 129.2, 129.1, 129.1,
128.9, 128.5, 128.5, 128.2, 128.2, 128.1, 127.3, 48.5, 48.3,
43.9, 43.82, 21.6, 21.0. HRMS (ESI+): calcd for C23H20O2
[M + H]+: 329.1536, found 329.1539.
4.2.10 | 2,4‐Diphenyl‐1‐(o‐tolyl)butane‐1,4‐
dione (3ja)
1
Yellow liquid (yield: 76%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.01 (d, J = 7.5 Hz, 2H), 7.93 (d, J = 7.6 Hz, 1H),
7.56 (t, J = 7.1 Hz, 1H), 7.46 (t, J = 7.5 Hz, 2H), 7.30–
7.28 (m, 5H), 7.25–7.21 (m, 2H), 7.14 (d, J = 7.4 Hz,
1H), 5.14 (dd, J = 10.5, 3.0 Hz, 1H), 4.27 (dd, J = 18.0,
10.5 Hz, 1H), 3.28 (dd, J = 18.1, 3.1 Hz, 1H), 2.28 (s,
3H). 13C NMR (100 MHz, CDCl3, δ, ppm): 202.7, 198.3,
138.3, 138.3, 137.8, 136.5, 133.3, 131.5, 130.9, 129.1,
128.6, 128.5, 128.4, 128.2, 127.4, 125.5, 51.7, 43.3, 20.7.
HRMS (ESI+): calcd for C23H20O2 [M + H]+: 329.1536,
found 329.1543.
4.2.7 | 2‐(4‐Methoxyphenyl)‐1,4‐
diphenylbutane‐1,4‐dione (3ga)
1
Yellow liquid (yield: 97%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.25 (d, J = 8.8 Hz, 2H), 7.98 (d, J = 7.4 Hz, 2H),
7.55 (t, J = 7.3 Hz, 1H), 7.44 (t, J = 7.7 Hz, 2H), 7.36 (t,
J = 7.2 Hz, 2H), 7.30 (t, J = 7.3 Hz, 2H), 7.22 (t,
J = 7.1 Hz, 1H), 6.87 (d, J = 8.8 Hz, 2H), 5.29 (dd,
J = 9.8, 3.6 Hz, 1H), 4.20 (dd, J = 18.0, 10.0 Hz, 1H),
3.82 (s, 3H), 3.27 (dd, J = 18.0, 3.7 Hz, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 198.2, 197.3, 163.3, 139.2,
136.5, 133.2, 131.3, 129.4, 129.2, 128.6, 128.2, 127.3,
113.7, 55.4, 48.4, 43.8. HRMS (ESI+): calcd for C23H20O3
[M + H]+: 345.1485, found 345.1490.
4.2.11 | 1‐(2‐Chlorophenyl)‐2,4‐
diphenylbutane‐1,4‐dione (3ka)
1
Yellow liquid (yield: 76%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.01 (d, J = 7.4 Hz, 2H), 7.79 (d, J = 6.2 Hz, 1H),
7.57 (t, J = 7.3 Hz, 1H), 7.48–7.44 (m, 2H), 7.31–7.28
(m, 7H), 7.24–7.22 (m, 1H), 5.16 (dd, J = 9.6, 3.8 Hz,
1H), 4.22 (dd, J = 18.0, 9.7 Hz, 1H), 3.28 (dd, J = 18.1,
3.9 Hz, 1H), 2.28 (s, 3H). 13C NMR (100 MHz, CDCl3, δ,
ppm): 200.5, 198.0, 138.5, 136.7, 136.5, 133.4, 131.6,
131.6, 130.6, 129.4, 129.0, 128.8, 128.7, 128.2, 127.7,
126.5, 52.6, 42.6. HRMS (ESI+): calcd for C22H17ClO2
[M + H]+: 349.0990, found 349.0992.
4.2.8 | 2‐(4‐(Trifluoromethyl)phenyl)‐1,4‐
diphenylbutane‐1,4‐dione (3ha)
1
Yellow liquid (yield: 61%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.03–7.96 (m, 4H), 7.57–7.40 (m, 10H), 5.43–5.40
(m, 1H), 4.24–4.17 (m, 1H), 3.36–3.30 (m, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 198.4, 197.5, 142.7, 136.3,
136.2, 133.5, 133.3, 129.7 (q, J = 33.0 Hz), 128.9, 128.7,
4.2.12 | 4‐(3,4‐Dimethylphenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3ab)
1
128.7, 128.2, 126.2 (q,
J
=
3.6 Hz), 124.0 (q,
Yellow liquid (yield: 85%). H NMR (400 MHz, CDCl3, δ,
J = 272.0 Hz), 48.4, 43.7. HRMS (ESI+): calcd for
ppm): 8.03 (d, J = 7.4 Hz, 2H), 7.75–7.70 (m, 2H), 7.49–
7.45 (m, 1H), 7.40–7.35 (m, 4H), 7.32–7.28 (m, 2H),
7.24–7.17 (m, 2H), 5.32 (dd, J = 10.0, 3.5 Hz, 1H), 4.18
(dd, J = 17.9, 10.0 Hz, 1H), 3.29 (dd, J = 17.9, 3.6 Hz,
1H), 2.28 (d, J = 4.5 Hz, 6H). 13C NMR (100 MHz, CDCl3,
δ, ppm): 199.1, 197.9, 142.8, 138.8, 136.9, 136.6, 134.4,
132.9, 129.8, 129.4, 129.1, 128.9, 128.5, 128.3, 127.3,
125.9, 48.7, 43.9, 20., 19.8. HRMS (ESI+): calcd for
C24H22O2 [M + H]+: 343.1693, found 343.1698.
C23H17F3O2 [M + H]+: 383.1214, found 383.1258.
4.2.9 | 2‐(4‐Chlorophenyl)‐1,4‐
diphenylbutane‐1,4‐dione (3ia)
1
Yellow liquid (yield: 79%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.01 (d, J = 7.4 Hz, 2H), 7.97 (d, J = 7.4 Hz, 2H),
7.56 (t, J = 7.3 Hz, 1H), 7.51 (t, J = 7.4 Hz, 1H), 7.46–

8 of 11
LI ET AL.
127.4, 120.9, 120.0, 112.1, 55.4, 48.6, 44.1. HRMS (ESI+):
calcd for C23H20O3 [M + H]+: 345.1485, found 345.1486.
4.2.13 | 1,2‐Diphenyl‐4‐(m‐tolyl)butane‐
1,4‐dione (3ac)
1
Yellow liquid (yield: 73%). H NMR (400 MHz, CDCl3, δ,
4.2.17 | 4‐(2‐Methoxyphenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3ag)
ppm): 8.03 (d, J = 7.5 Hz, 2H), 7.77 (d, J = 7.7 Hz, 2H),
7.48–7.45 (m, 1H), 7.40–7.28 (m, 8H), 7.23–7.19 (m, 1H),
5.32 (dd, J = 10.0, 3.5 Hz, 1H), 4.20 (dd, J = 18.0,
10.1 Hz, 1H), 3.29 (dd, J = 18.0, 3.6 Hz, 1H), 2.37 (s,
3H). 13C NMR (100 MHz, CDCl3, δ, ppm): 199.0, 198.3,
138.8, 138.4, 136.5, 134.0, 132.9, 129.2, 128.9, 128.8,
128.5, 128.5, 128.3, 127.4, 125.4, 48.8, 43.9, 21.4. HRMS
(ESI+): calcd for C23H20O2 [M + H]+: 329.1536, found
329.1538.
1
Yellow liquid (yield: 39%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.03 (d, J = 7.3 Hz, 2H), 7.35 (dd, J = 7.7, 1.3 Hz,
1H), 7.50–7.28 (m, 8H), 7.23–7.20 (m, 1H), 7.00–6.94 (m,
2H), 5.31 (dd, J = 10.2, 3.7 Hz, 1H), 4.16 (dd, J = 18.6,
10.2 Hz, 1H), 3.87 (s, 3H), 3.25 (dd, J = 18.7, 3.7 Hz, 1H).
13C NMR (100 MHz, CDCl3, δ, ppm): 199.7, 199.3, 159.0,
138.9, 136.7, 133.8, 132.7, 130.6, 129.1, 128.9, 128.5, 128.4,
127.4, 127.1, 120.6, 111.6, 55.5, 49.1, 48.9. HRMS (ESI+):
calcd for C23H20O2 [M + H]+: 345.1485, found 345.1489.
4.2.14 | 1,2‐Diphenyl‐4‐(o‐tolyl)butane‐1,4‐
dione (3ad)
1
4.2.18 | 1,2‐Diphenyl‐4‐(4‐
(trifluoromethyl)phenyl)butane‐1,4‐dione
(3ah)
Yellow liquid (yield: 61%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.02 (d, J = 7.4 Hz, 2H), 7.75 (d, J = 7.6 Hz, 1H),
7.46 (t, J = 7.3 Hz, 1H), 7.40–7.36 (m, 2H), 7.34–7.27
(m, 5H), 7.25–7.18 (m, 3H), 5.32 (dd, J = 10.1, 3.7 Hz,
1H), 4.17 (dd, J = 17.9, 10.1 Hz, 1H), 3.25 (dd, J = 17.9,
3.8 Hz, 1H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl3, δ,
ppm): 202.0, 198.9, 138.7, 138.3, 137.4, 136.5, 132.9,
131.9, 131.5, 129.2, 128.9, 128.8, 128.5, 128.3, 127.4,
125.7, 49.2, 46.5, 21.3. HRMS (ESI+): calcd for C23H20O2
[M + H]+: 329.1536, found 329.1539.
1
Yellow liquid (yield: 62%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.08 (d, J = 8.1 Hz, 2H), 8.02 (d, J = 7.5 Hz, 2H),
7.71 (d, J = 8.1 Hz, 2H), 7.49 (t, J = 7.3 Hz, 1H), 7.41–7.30
(m, 6H), 7.25–7.22 (m, 1H), 5.33 (dd, J = 10.0, 3.5 Hz,
1H), 4.21 (dd, J = 18.1, 10.1 Hz, 1H), 3.28 (dd, J = 18.0,
3.5 Hz, 1H). 13C NMR (100 MHz, CDCl3, δ, ppm): 198.7,
197.3, 139.1, 138.4, 136.3, 135.0, 134.5 (dd, J = 65.5,
32.7 Hz), 133.0, 129.3, 128.9, 128.6, 128.5, 128.2, 127.5,
125.7 (dd, J = 7.0, 3.3 Hz), 48.9, 44.0. HRMS (ESI+): calcd
for C23H17F3O2 [M + H]+: 328.1253, found 328.1258.
4.2.15 | 4‐(4‐Methoxyphenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3ae)
1
Yellow liquid (yield: 93%). H NMR (400 MHz, CDCl3, δ,
4.2.19 | 1,2‐Diphenyl‐4‐(3‐
(trifluoromethyl)phenyl)butane‐1,4‐dione
(3ai)
ppm): 8.03 (d, J = 7.5 Hz, 2H), 7.95 (d, J = 8.8 Hz, 2H),
7.49–7.45 (m, 1H), 7.40–7.35 (m, 4H), 7.32–7.28 (m, 2H),
7.23–7.20 (m, 1H), 6.90 (d, J = 8.7 Hz, 2H), 5.32 (dd,
J = 10.1, 3.6 Hz, 1H), 4.17 (dd, J = 17.9, 10.1 Hz, 1H),
3.84 (s, 3H), 3.26 (dd, J = 17.8, 3.6 Hz, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 199.1, 196.6, 163.6, 138.8,
136.6, 132.9, 130.5, 129.6, 129.2, 128.9, 128.5, 128.3,
127.3, 113.7, 55.5, 48.7, 43.6. HRMS (ESI+): calcd for
C23H20O3 [M + H]+: 345.1485, found 345.1490.
1
Yellow liquid (yield: 64%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.23 (s, 1H), 8.16 (d, J = 7.7 Hz, 1H), 8.02 (d,
J = 7.5 Hz, 2H), 7.81 (d, J = 7.6 Hz, 1H), 7.60–7.56 (m,
1H), 7.51–7.47 (m, 1H), 7.42–7.30 (m, 6H), 7.25–7.22 (m,
1H), 5.34 (dd, J = 10.1, 3.4 Hz, 1H), 4.22 (dd, J = 18.0,
10.2 Hz, 1H), 3.29 (dd, J = 18.0, 3.5 Hz, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 198.7, 196.9, 138.4, 136.9,
136.3, 133.1, 131.3, 131.5 (dd, J = 65.9, 33.0 Hz), 129.7 (dd,
J = 7.2, 3.6 Hz), 129.3, 128.9, 128.6, 128.2, 127.6, 125.6
(dd, J = 7.7, 3.7 Hz), 122.3, 48.8, 43.9. HRMS (ESI+): calcd
for C23H17F3O2 [M + H]+: 383.1253, found 383.1257.
4.2.16 | 4‐(3‐Methoxyphenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3af)
1
Yellow liquid (yield: 68%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.03 (d, J = 7.3 Hz, 2H), 7.57 (d, J = 7.5 Hz, 1H),
7.47 (d, J = 7.7 Hz, 2H), 7.41–7.34 (m, 5H), 7.32–7.28
(m, 2H), 7.24–7.20 (m, 1H), 7.11–7.08 (m, 1H), 5.31 (dd,
J = 10.0, 3.4 Hz, 1H), 4.19 (dd, J = 18.0, 10.1 Hz, 1H),
3.81 (s, 3H), 3.25 (dd, J = 18.1, 3.6 Hz, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 198.9, 197.9, 159.8, 138.6,
137.8, 136.5, 132.9, 129.6, 129.2, 128.9, 128.5, 128.3,
4.2.20 | 1,2‐Diphenyl‐4‐(2‐
(trifluoromethyl)phenyl)butane‐1,4‐dione
(3aj)
1
Yellow liquid (yield: 40%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.01 (d, J = 7.5 Hz, 2H), 7.72–7.69 (m, 2H), 7.65–

LI ET AL.
9 of 11
7.62 (m, 1H), 7.57–7.53 (m, 1H), 7.50–7.47 (m, 1H), 7.41–
7.37 (m, 2H), 7.31–7.28 (m, 4H), 7.23–7.20 (m, 1H), 5.35
(dd, J = 10.1, 3.6 Hz, 1H), 4.10 (dd, J = 18.4, 10.2 Hz,
1H), 3.12 (dd, J = 18.4, 3.5 Hz, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 202.4, 198.7, 138.2, 136.2,
133.1, 131.9, 130.2, 129.3, 129.0, 128.5, 128.2, 127.6,
127.5, 126.6 (dd, J = 10.0, 5.0 Hz), 49.1, 47.7. HRMS
(ESI+): calcd for C23H17F3O2 [M + H]+: 383.1253, found
383.1256.
(d, J = 1.8 Hz), 48.5 (d, J = 8.2 Hz). HRMS (ESI+): calcd
for C22H17FO2 [M + H]+: 333.1285, found 333.1291.
4.2.24 | 4‐(4‐Chlorophenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3an)
1
Yellow liquid (yield: 78%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.02 (d, J = 7.4 Hz, 2H), 7.91 (d, J = 8.4 Hz, 2H),
7.49 (t, J = 7.3 Hz, 1H), 7.42–7.38 (m, 4H), 7.36–7.29
(m, 4H), 7.24–7.21 (m, 1H), 5.31 (dd, J = 10.1, 3.4 Hz,
1H), 4.17 (dd, J = 18.0, 10.1 Hz, 1H), 3.25 (dd, J = 17.8,
3.5 Hz, 1H). 13C NMR (100 MHz, CDCl3, δ, ppm): 198.8,
196.9, 139.7, 138.5, 136.3, 134.8, 133.0, 129.6, 129.3,
128.9, 128.9, 128.5, 128.2, 127.5, 48.8, 43.8. HRMS (ESI
+): calcd for C22H17ClO2 [M + H]+: 349.0990, found
349.0995.
4.2.21 | 4‐(4‐Fluorophenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3ak)
1
Yellow liquid (yield: 85%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.03–7.98 (m, 4H), 7.47 (t, J = 7.29 Hz, 1H), 7.40–
7.36 (m, 3H), 7.34–7.28 (m, 3H), 7.24–7.20 (m, 1H), 7.10
(t, J = 8.5 Hz, 2H), 5.31 (dd, J = 10.1, 3.5 Hz, 1H), 4.18
(dd, J = 17.9, 10.2 Hz, 1H), 3.25 (dd, J = 17.9, 3.5 Hz,
1H). 13C NMR (100 MHz, CDCl3, δ, ppm): 198.9, 196.5,
165.9 (d, J = 255 Hz), 138.6, 136.4, 132.9, 130.8 (d,
J = 9.4 Hz), 129.3, 128.9, 128.5, 128.2, 128.2, 127.4,
126.9, 115.7 (d, J = 21.9 Hz), 48.8, 43.8. HRMS (ESI+):
calcd for C22H17FO2 [M + H]+: 333.1285, found 333.1290.
4.2.25 | 4‐(3‐Bromophenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3ao)
1
Yellow liquid (yield: 73%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.10 (s, 1H), 8.02 (d, J = 7.3 Hz, 2H), 7.90 (d,
J = 7.7 Hz, 1H), 7.68 (d, J = 7.9 Hz, 1H), 7.51–7.47 (m,
1H), 7.42–7.40 (m, 2H), 7.35–7.29 (m, 5H), 7.25–7.21 (m,
1H), 5.31 (dd, J = 10.0, 3.6 Hz, 1H), 4.16 (dd, J = 18.0,
10.1 Hz, 1H), 3.25 (dd, J = 18.0, 3.6 Hz, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 198.7, 196.8, 138.4, 138.2,
136.3, 136.1, 133.0, 131.3, 130.2, 129.3, 128.9, 128.6,
128.2, 127.5, 126.7, 122.9, 48.8, 43.9. HRMS (ESI+): calcd
for C22H17BrO2 [M + H]+: 393.0485, found 393.0489.
4.2.22 | 4‐(3‐Fluorophenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3al)
1
Yellow liquid (yield: 84%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.02 (d, J = 7.5 Hz, 2H), 7.76 (d, J = 7.5 Hz, 1H),
7.65 (d, J = 9.1 Hz, 1H), 7.50–7.46 (m, 1H), 7.42–7.29
(m, 7H), 7.24–7.21 (m, 2H), 5.31 (dd, J = 10.1, 3.4 Hz,
1H), 4.18 (dd, J = 18.0, 10.1 Hz, 1H), 3.25 (dd, J = 18.0,
3.5 Hz, 1H). 13C NMR (100 MHz, CDCl3, δ, ppm):
198.75, 196.91, 162.85 (d, J = 247.7 Hz), 138.57 (d,
J = 6.2 Hz), 138.5, 136.4, 133.0, 130.3 (d, J = 7.6 Hz),
129.3, 128.9, 128.6, 128.2, 127.5, 123.9 (d, J = 3.0 Hz),
120.29 (d, J = 21.5 Hz), 114.9 (d, J = 22.4 Hz), 48.8,
43.9. HRMS (ESI+): calcd for C22H17FO2 [M + H]+:
333.1285, found 333.1288.
4.2.26 | 4‐([1,1′‐Biphenyl]‐4‐yl)‐1,2‐
diphenylbutane‐1,4‐dione (3aq)
1
Yellow liquid (yield: 63%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.05 (d, J = 6.8 Hz, 4H), 7.66 (d, J = 8.2 Hz, 2H),
7.62 (d, J = 7.4 Hz, 2H), 7.51–7.37 (m, 8H), 7.33–7.30
(m, 2H), 7.25–7.21 (m, 1H), 5.55 (dd, J = 10.0, 3.4 Hz,
1H), 4.25 (dd, J = 17.9, 3.5 Hz, 1H), 3.33 (dd, J = 18.0,
3.6 Hz, 1H). 13C NMR (100 MHz, CDCl3, δ, ppm): 198.9,
197.7, 145.9, 139.9, 138.7, 136.5, 135.2, 132.9, 129.2,
128.9, 128.8, 128.5, 128.3, 127.4, 127.3, 128.3, 48.8, 43.9.
HRMS (ESI+): calcd for C28H22O2 [M + H]+: 391.1693,
found 391.1699.
4.2.23 | 4‐(2‐Fluorophenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3am)
1
Yellow liquid (yield: 70%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.03 (d, J = 7.4 Hz, 2H), 7.88–7.84 (m, 1H), 7.54–
7.46 (m, 2H), 7.42–7.38 (m, 2H), 7.36–7.28 (m, 4H),
7.24–7.18 (m, 2H), 7.15–7.10 (m, 1H), 5.53–5.29 (m, 1H),
4.23–4.15 (m, 1H), 3.37–3.31 (m, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 198.9, 196.3 (d, J = 4.1 Hz),
162.3 (d, J = 4.1 Hz), 138.5, 136.5, 134.8 (d, J = 9.0 Hz),
132.9, 130.8 (d, J = 2.3 Hz), 129.2, 128.9, 128.5, 128.3,
127.3, 124.4 (d, J = 3.4 Hz), 116.7 (d, J = 23.7 Hz), 48.8
4.2.27 | 4‐(3‐Phenoxyphenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3ar)
1
Yellow liquid (yield: 82%). H NMR (400 MHz, CDCl3, δ,
ppm): 8.01 (d, J = 7.4 Hz, 2H), 7.69 (d, J = 7.7 Hz, 1H),
7.59 (s, 1H), 7.46–7.43 (m, 1H), 7.39–7.28 (m, 9H), 7.21–
7.17 (m, 2H), 7.11–7.07 (m, 1H), 7.98 (d, J = 7.7 Hz,
2H), 5.29 (dd, J = 10.1, 3.4 Hz, 1H), 4.16 (dd, J = 18.1,

10 of 11
LI ET AL.
10.2 Hz, 1H), 3.27 (dd, J = 18.1, 3.4 Hz, 1H). 13C NMR
(100 MHz, CDCl3, δ, ppm): 198.9, 197.5, 157.8, 156.6,
138.5, 138.2, 136.5, 132.9, 130.0, 129.3, 128.9, 128.57,
128.3, 127.5, 123.9, 123.6, 123.1, 119.2, 117.9, 48.8, 44.1.
HRMS (ESI+): calcd for C28H22O3 [M + H]+: 407.1642,
found 407.1645.
Porretta, D. Deidda, R. Pompei, A. Tafi, F. Manetti, Bioorg.
Med. Chem. 2004, 12, 1453.
[3] For representative examples of synthetic methods to 1,4‐
diketones, see a) P. Setzer, A. Beauseigneur, M. S. M. Pearson‐
Long, P. Bertus, Angew. Chem. Int. Ed. 2010, 49, 8691. b) Y.
Nishiyama, A. Kobayashi, Tetrahedron Lett. 2006, 47, 5565. c)
M. Sauthier, Y. Castanet, A. Mortreux, Chem. Commun. 2004,
1520. d) S. L. Huang, L. Kötzner, C. K. De, B. List, J. Am. Chem.
Soc. 2015, 137, 3446.
4.2.28 | 4‐(4‐Ethoxyphenyl)‐1,2‐
diphenylbutane‐1,4‐dione (3ac)
[4] H. Stetter, Angew. Chem. Int. Ed. Engl. 1976, 15, 639.
[5] X. Y. Lu, J. G. Ji, D. W. Ma, W. Shen, J. Org. Chem. 1991, 56,
1
Yellow liquid (yield: 55%). H NMR (400 MHz, CDCl3,
5774.
δ, ppm): 8.03 (d,
J = 7.3 Hz, 2H), 7.94 (d,
[6] a) H.‐L. Huang, H. Yan, C. Yang, W. Xia, Chem. Commun.
2015, 51, 4910. b) H.‐L. Huang, H. Yan, G.‐L. Gao, C. Yang,
W. Xia, Asian J. Org. Chem. 2015, 4, 674. c) L.‐W. Zheng, H.‐
L. Huang, C. Yang, W.‐J. Xia, Org. Lett. 2015, 17, 1034.
J = 8.8 Hz, 2H), 7.49–7.46 (m, 1H), 7.40–7.35 (m,
4H), 7.32–7.28 (m, 2H), 7.23–7.20 (m, 1H), 6.90 (d,
J = 8.7 Hz, 2H), 5.31 (dd, J = 10.0, 3.5 Hz, 1H), 4.16
(dd, J = 17.8, 10.1 Hz, 1H), 4.07 (dd, J = 13.9,
7.0 Hz, 2H), 3.26 (dd, J = 17.8, 3.6 Hz, 1H), 1.42 (t,
J = 7.0 Hz, 3H). 13C NMR (100 MHz, CDCl3, δ,
ppm): 199.1, 196.6, 163.1, 138.8, 136.6, 132.9, 130.5,
129.4, 129.2, 128.9, 128.5, 128.3, 127.3, 114.2, 63.8,
48.7, 43.6, 14.7. HRMS (ESI+): calcd for C24H22O3
[M + H]+: 359.1642, found 359.1646.
[7] a) Z.‐L. Shen, K. K. K. Goh, H.‐L. Cheong, C. H. A. Wong, Y.‐C.
Lai, Y.‐S. Yang, T.‐P. Loh, J. Am. Chem. Soc. 2010, 132, 15852.
b) B. B. Parida, P. P. Das, M. Niocel, J. K. Cha, Org. Lett.
2013, 15, 1780. c) D. W. Custar, H. Le, J. P. Morken, Org. Lett.
2010, 1, 3760.
[8] Y. Ito, T. Konoike, T. Harada, T. Saegusa, J. Am. Chem. Soc.
1977, 99, 1487.
[9] J. Xuan, Z.‐J. Feng, J.‐R. Chen, L.‐Q. Lu, W.‐J. Xiao, Chem. –
Eur. J. 2014, 20, 3045.
ACKNOWLEDGMENTS
[10] For examples of Sigman's work, see a) T. S. Mei, E. W. Werner,
A. J. Burckle, M. S. Sigman, J. Am. Chem. Soc. 2013, 135, 6830.
b) C. Zhang, C. B. Santiago, L. Kou, M. S. Sigman, J. Am. Chem.
Soc. 2015, 137, 7290. c) H. H. Patel, M. S. Sigman, J. Am. Chem.
Soc. 2015, 137, 3462. d) T. S. Mei, H. H. Patel, M. S. Sigman,
Nature 2014, 508, 340. e) M. J. Hilton, B. Cheng, B. R. Buckley,
L. Xu, O. Wiest, M. S. Sigman, Tetrahedron 2015, 71, 6513. f) M.
J. Hilton, L. Xu, P. Norrby, Y. Wu, O. Wiest, M. S. Sigman,
J. Org. Chem. 2014, 79, 11841. g) E. W. Werner, T. S. Mei, A.
J. Burckle, M. S. Sigman, Science 2012, 338, 1455.
We are grateful to the National Natural Science Founda-
tion of China (51603192, 21172200) and Natural Science
Foundation of Henan Province (182300410211) for
financial support of this research.
ORCID
Yangjie Wu http://orcid.org/0000-0002-0134-0870
[11] M. Chen, J. Wang, Z. Y. Chai, C. You, A. W. Lei, Adv. Synth.
Catal. 2012, 354, 341.
REFERENCES
[12] J.‐H. Liao, Z.‐M. Zhang, X.‐D. Tang, W.‐Q. Wu, W. Guo, H.‐F.
Jiang, J. Org. Chem. 2015, 80, 8903.
[1] For examples of bioactive compounds containing 1,4‐
diketones, see a) G. Valot, C. S. Regens, D. P. O'Malley, E.
Godineau, H. Takikawa, A. Fürstner, Angew. Chem. Int. Ed.
2013, 52, 9534. b) S. H. Li, J. Wang, X. M. Niu, Y. H. Shen,
H. J. Zhang, H. D. Sun, M. L. Li, Q. E. Tian, Y. Lu, P. Cao,
Q. Z. Zheng, Org. Lett. 2004, 6, 4327. c) T. Fujisawa, K. Igeta,
S. Odake, Y. Morita, J. Yasuda, T. Morikawa, Bioorg. Med.
Chem. 2002, 10, 2569.
[13] a) M. Vellakkaran, M. M. S. Andappan, N. Kommu, Green
Chem. 2014, 16, 2788. b) M. Vellakkaran, M. M. S. Andappan,
N. Kommu, Eur. J. Org. Chem. 2012, 25, 4694.
[14] E. Alacid, C. Najera, Adv. Synth. Catal. 2007, 349, 2572.
[15] H. Yin, D. U. Nielsen, M. K. Johansen, A. T. Lindhardt, T.
Skrydstrup, ACS Catal. 2016, 6, 2982.
[2] For examples of 1,4‐diketones as synthons for heterocycles, see
a) E. O'Reilly, C. Iglesias, D. Ghislieri, J. Hopwood, J. L.
Galman, R. C. Lloyd, N. J. Turner, Angew. Chem. Int. Ed.
2014, 53, 2447. b) F. Guo, L. C. Konkol, R. J. Thomson,
J. Am. Chem. Soc. 2011, 133, 18. c) C. S. Li, Y. H. Tsai, W. C.
Lee, W. J. Kuo, J. Org. Chem. 2010, 75, 4004. d) G. Hua, J. B.
Henry, Y. Li, A. R. Mount, A. M. Z. Slawin, J. D. Woollins,
Org. Biomol. Chem. 2010, 8, 1655. e) J. B. Chaires, J. Ren, D.
Hammelberg, A. Kumar, V. Pandya, D. W. Boykin, W. D. Wil-
son, J. Med. Chem. 2004, 47, 5729. f) H. S. P. Rao, S.
Jothilingam, J. Org. Chem. 2003, 68, 5392. g) M. Biava, G. C.
[16] C.‐D. Pan, Q.‐T. Ni, Y. Fu, J.‐T. Yu, J. Org. Chem. 2017, 82,
7683.
[17] Y. Sasson, A. Zoran, J. Blum, J. Mol. Catal. 1979, 6, 289.
[18] For representative examples of substitute migration rear-
rangement for allyl alcohols, see a) J.‐C. Zhao, H. Fang, R.‐
C. Song, J. Zhou, J.‐L. Han, Y. Pan, Chem. Commun. 2015,
51, 599. b) Y. Li, B. Liu, H.‐B. Li, Q. Wang, J.‐H. Li, Chem.
Commun. 2015, 51, 1024. c) X.‐Q. Chu, H. Meng, Y. Zi, X.‐
P. Xu, S.‐J. Ji, Chem. – Eur. J. 2014, 20, 17198. d) X. Mi, C.‐
Y. Wang, M.‐M. Huang, Y.‐S. Wu, Y.‐J. Wu, Org. Biomol.

LI ET AL.
11 of 11
Chem. 2014, 12, 8394. e) H. Li, F.‐M. Zhang, Y.‐Q. Tu, Q.‐W.
SUPPORTING INFORMATION
Zhang, Z.‐M. Chen, Z.‐H. Chen, J. Li, Chem. Sci. 2011, 2,
1839. f) Z.‐M. Chen, W. Bai, S.‐H. Wang, B.‐M. Yang, Y.‐Q.
Tu, F.‐M. Zhang, Angew. Chem. Int. Ed. 2013, 52, 9781. g)
X.‐W. Liu, F. Xiong, X.‐P. Huang, L. Xu, P.‐F. Li, X.‐X. Wu,
Angew. Chem. Int. Ed. 2013, 52, 6962. h) W. Hu, S. Sun, J.
Cheng, J. Org. Chem. 2016, 81, 4399.
Additional supporting information may be found online
in the Supporting Information section at the end of the
article.
How to cite this article: Li Y, Leng Y, Wang S,
et al. Oxidative acylation of α,α‐diarylallylic
alcohols: Synthesis of 1,2,4‐triarylbutane‐1,4‐
diones. Appl Organometal Chem. 2018;e4407.
https://doi.org/10.1002/aoc.4407
[19] X.‐Q. Chu, H. Meng, Y. Zi, X.‐P. Xu, S.‐J. Ji, Chem. Commun.
2014, 50, 9718.
[20] a) N. Marion, R. Gealageas, S. P. Nolan, Org. Lett. 2007, 9, 2653.
b) S. Hayashi, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc.
2009, 131, 2052.