Mn(III)-based reaction of alkenes with quinolinones. Formation of peroxyquinolinones and quinoline-related derivatives

Article abstract of DOI:10.1016/j.tet.2014.01.013

The reactions of 1,1-disubstituted alkenes with 4-hydroxyquinolin-2(1H)- ones under both Mn(III)-catalyzed aerobic oxidation conditions at room temperature and Mn(III)-mediated oxidation conditions at reflux temperature are described. The Mn(III)-catalyzed aerobic oxidation afforded bis(hydroperoxyethyl)quinolinones and azatrioxa[4.4.3]propellanes, while the oxidation with Mn(OAc)₃·2H₂O produced furo[3,2-c]quinolin-4-one analogues. The existence of a substituent at the 3-position of the 4-hydroxyquinolin-2(1H)-ones prevented a double reaction with the alkenes, and (endoperoxy)quinolinones and/or (hydroperoxyethyl)quinolinones were obtained under the Mn(III)-catalyzed aerobic conditions, while furo[3,2-c]quinolinone hemiacetals and vinylquinolinones were selectively produced under the Mn(III)-mediated oxidation conditions depending on the reaction temperature and times. Cyclic assembly of quinolinone-related 1,3-dicarbonyl compounds such as dihydropyridinones, pyranones, and dimedone derivatives was also examined under elevated temperature conditions.

Full text of DOI:10.1016/j.tet.2014.01.013

Accepted Manuscript
Mn(III)-based reaction of alkenes with quinolinones. Formation of peroxyquinolinones
and quinoline-related derivatives
Hiroshi Nishino, Ryoukou Kumabe, Ryoichi Hamada, Mehtap Yakut
PII:
S0040-4020(14)00029-5
10.1016/j.tet.2014.01.013
TET 25187
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 19 September 2013
Revised Date: 30 December 2013
Accepted Date: 1 January 2014
Please cite this article as: Nishino H, Kumabe R, Hamada R, Yakut M, Mn(III)-based reaction of alkenes
with quinolinones. Formation of peroxyquinolinones and quinoline-related derivatives, Tetrahedron
(2014), doi: 10.1016/j.tet.2014.01.013.
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Mn(III)-based reaction of alkenes with
quinolinones. Formation of
peroxyquinolinones and quinoline-related
derivatives
Leave this area blank for abstract info.
Ar
Ar
1
Ar1
Ar
Ar
1
Ar2
HOO
O
2
2
O
O
O
O
Ar
Ar
1
2
O
Ar
Ar
1
Ar
Ar2
1
2
O
N
R
O OOH
N
R
O
N
R
O
a
a
a
b
Hiroshi Nishino,* Ryoukou Kumabe, Ryoichi Hamada, Mehtap Yakut
Ar
Ar
Ar
Ar
cat. Mn(OAc)
r.t., air
3
O
HO
a
O
R = H
Ar1
Department of Chemistry, Graduate School of Science and Technology,
OH
R
Kumamoto University, Kurokami 2-39-1, Chûou-Ku, Kumamoto 860-8555,
Japan
N
R
O
Mn(OAc)
reflux
3
R
O
Mn(OAc)
reflux
3
N
O
Ar
+
H
O
Ar2
O
N
Ar
H
b
Ar
Ar
cat. Mn(OAc)3
r.t., air
R = alky
R
O
Department of Chemistry, Faculty of Science, Ankara University,
N
H
N
R
O
0
6100 Tandoğan, Ankara, Turkey
O
Ar
Ar
HOO Ar
O
O
Ar
HO
R
R
O
N
H
O
N
H

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Mn(III)-based reaction of alkenes with quinolinones.
Formation of peroxyquinolinones and quinoline-related derivatives
a,
a
a
b
Hiroshi Nishino ∗ , Ryoukou Kumabe , Ryoichi Hamada , Mehtap Yakut
a
Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, Kurokami 2-39-1, Chûou-Ku, Kumamoto 860-8555, Japan
Department of Chemistry, Faculty of Science, Ankara University, 06100 Tandoğan, Ankara, Turkey
b
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The reactions of 1,1-disubstituted alkenes with 4-hydroxyquinolin-2(1H)-ones under both
Mn(III)-catalyzed aerobic oxidation conditions at room temperature and Mn(III)-mediated
oxidation conditions at reflux temperature are described. The Mn(III)-catalyzed aerobic
oxidation afforded bis(hydroperoxyethyl)quinolinones and azatrioxa[4.4.3]propellanes,
while the oxidation with Mn(OAc) •2H O produced furo[3,2-c]quinolin-4-one analogues.
Available online
3
2
The existence of a substituent at the 3-position of the 4-hydroxyquinolin-2(1H)-ones
prevented a double reaction with the alkenes, and (endoperoxy)quinolinones and/or
Keywords:
Hydroperoxides
Endoperoxides
Quinolines
Propellanes
Aerobic oxidation
Mn(III)
(
hydroperoxyethyl)quinolinones were obtained under the Mn(III)-catalyzed aerobic
conditions, while furo[3,2-c]quinolinone hemiacetals and vinylquinolinones were
selectively produced under the Mn(III)-mediated oxidation conditions depending on the
reaction temperature and times. Cyclic assembly of quinolinone-related 1,3-dicarbonyl
compounds such as dihydropyridinones, pyranones, and dimedone derivatives was also
examined under elevated temperature conditions.
Oxidation
2
013 Elsevier Ltd. All rights reserved.
—
——
∗
Corresponding author. Tel.: +81-96-342-3374; fax: +81-96-342-3374; e-mail: nishino@sci.kumamoto-u.ac.jp

2
Tetrahedron
1
. Introduction
R = Me) must form an endoperoxide such as 4,4a,6,10b-
ACCEPTED MANUSCRIPT
tetrahydro-10b-hydroxy-6-methyl-3,3-diphenyl-1,2-dioxino[4,3-
c]quinolin-5(3H)-one (Scheme 1). The reaction did not occur in
Quinoline alkaloids are some of the most important natural
products and the synthesis of heterocycles containing the
quinoline core is interesting from the standpoint of searching for
new biologically active compounds. Mn(III)-assisted oxidation
is one of the useful tools for formation of the carbon-carbon bond
to a heterocyclic ring such as addition and substitution. For
example, the aerobic oxidation of pyrazolidine-3,5-diones,
tetronic acids and tetramic acids using Mn(OAc) •2H O as a
catalyst in the presence of alkenes gave hydroperoxides and
endoperoxides such as bis(hydroperoxyethyl)pyrazolidinediones,
the absence of Mn(OAc) (Table 1, entry 1), and the use of 1
mmol of Mn(OAc)3 gave an intractable mixture (entry 2).
Surprisingly, a bis(hydroperoxide) 3a was isolated from the
3
1
,2
reaction mixture when a catalytic amount of Mn(OAc) was used
3
,4
3
in air (Scheme 1 and Table 1, entry 3). In order to prevent the
double substitution, the reaction was carried out using two
equivalents of quinolinone 2 toward the alkene 1 (entries 4-6).
However, the reaction resulted in the bis(hydroperoxide) 3a as an
isolable product, and the monohydroperoxide and the desired
endoperoxide as well as 1 unchanged were not obtained. In
addition, use of excess amount of 1 toward quinolinone 2 caused
5
6
7
8
3
2
1
-hydroxy-2,3,8-trioxabicyclo[4.3.0]nonan-7-ones, and 8-aza-1-
hydroxy-2,3-dioxabicyclo[4.3.0]nonan-7-ones, while the direct
hydroperoxidation to a heterocyclic ring occurred by a similar
reaction using substituted cyclic diamides in the absence of
alkenes. On the other hand, the oxidation of alkenes with the
Mn(III)-enolate complex as an oxidant caused oxidative
cyclization, producing dihydrofurans and lactones. In order to
construct a complex quinoline core, 4-hydroxyquinolin-2(1H)-
ones are a suitable reagent for the Mn(III)-based peroxidation and
dihydrofuranation. We initially demonstrated the Mn(III)-
catalyzed aerobic oxidation of 1,1-diarylethenes in the presence
of the 4-hydroxyquinolinones at room temperature to produce
1
the reaction complicated. Another combination of alkenes 1 (Ar
2
=
Ar = 4-ClC H , 4-Me-C H ) and quinolinones 2 (X = H, R =
9
6
4
6
4
Et, Bn, H, Me) also underwent the aerobic oxidation to afford
similar bis(hydroperoxide)s 3b-h (entries 7-13). When
a
1
0
11
1
2
combination of the alkene 1 (Ar = Ar = Ph) and the quinolinone
(X = H, R = Et) was used, the best yield of bis(hydroperoxide)
2
12
(
hydroperoxyethyl)quinolinediones and [4.4.3]propellane-type
13
endoperoxides. A similar reaction using a stoichiometric
amount of Mn(III) at elevated temperature formed furo[3,2-
c]quinolin-4(2H)-ones and 3-vinylquinoline-2,4-diones. In this
14
paper, we describe the results of the oxidation of a mixture of
1
,1-disubstituted alkenes and 4-hydroxyquinolinones, and the
synthetic application of the dihydrofuranation using the
quinolinones and related 1,3-dicarbonyl compounds together
with the full experimental results of these reactions.
2
. Results and discussion
2
.1. Aerobic oxidation of a mixture of alkenes 1 and 4-
13
hydroxyquinolin-2(1H)-ones 2 (X = H)
5a
Based on our study of the Mn(III)-catalyzed peroxidation, it
1
Scheme 1. Mn(III)-based aerobic oxidation of a mixture of 1,1-disubstituted
ethenes 1 and quinolinones 2 (X = H).
was predicted that the reaction of 1,1-diphenylethene 1 (Ar =
2
Ar = Ph) with 1-methyl-4-hydroxyquinolin-2(1H)-one 2 (X = H,
Table 1
a
Mn(III)-based aerobic oxidation of a mixture of 1,1-disubstituted ethenes 1 and quinolinones 2 (X = H)
Entry
Alkene 1
Quinolinone 2
Molar ratio
Time
b
Product (yield/%)
1
2
Ar
Ar
R
3 2
1:2:Mn(OAc) •2H O
h
1
2
3
4
5
6
7
8
9
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Me
Me
Me
Me
Me
Me
Me
Me
Et
1:1:0
4
no reaction
1:2:1
4
intractable mixture
3a (32)
Ph
2:1:0.5
1:2:0.1
1:2:0.5
1:2:0.5
1:2:0.5
1:2:0.5
1:2:0.5
1:2:0.5
1:2:0.5
1:2:0.5
1:2:0.5
2:1:0.5
2:1:3
12
4
Ph
3a (29)
Ph
12
4
3a (43)
Ph
3a (71)
4a (13)
4-Cl-C
6
H
4
4-Cl-C
6
H
4
12
4
3b (76)
4b (10)
4c (10)
4d (5)
4-Me-C
Ph
6
H
4
4-Me-C
Ph
6
H
4
3c (59)
15
12
24
4
3d (91)
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
Ph
Ph
Bn
Bn
Bn
H
3e (52)
4e (trace)
4f (trace)
4g (trace)
4h (34)
4i (7)
4-Cl-C
4-Me-C
Ph
6
H
4
4-Cl-C
4-Me-C
Ph
6
H
4
3f (48)
6
H
4
6
H
4
3g (44)
4
3h (trace)
3i (trace)
Ph
2-thienyl
2-thienyl
2-thienyl
2-thienyl
2-thienyl
Me
Me
Me
Me
Me
18
12
12
12
18
5i (28)
5i (27)
5i (39)
5j (32)
5k (47)
Ph
4i (39)
Ph
2:1:3
4i (22)
4-F-C
6
H
4
2:1:3
4j (22)
4k (22)
4-Me-C
6
H
4
2:1:3
a
The reaction of alkene 1 (1 mmol) with quinoline 2 (2 mmol) was carried out in glacial acetic acid (25 mL) at room temperature in air.
The yield was based on the amount of the alkene 1 used.
b

3
3
d was achieved (entry 9). In order to search f
we scrutinized the reaction and found another product,
4.4.3]propellanes 4b-h (entries 6-13). The structure of
A
or
C
ot
C
he
E
r p
P
r
T
od
E
uc
D
ts, MAan
N
d
U
5i-
S
k
C
(T
R
ab
I
le 1, entries 15-18).
P
T
[
bis(hydroperoxide)s 3 and [4.4.3]propellanes 4 was determined
by spectroscopic methods as well as X-ray crystallography for a
single crystal of bis(hydroperoxide) 3b and [4.4.3]propellane 4a
1
3
(
see Supplementary material). Although it is known that the
aerobic oxidation of cyclic diamides in the presence of alkenes
does not give 9the corresponding endoperoxides, but
bis(hydroperoxide)s,
it is remarkable that the dual
hydroperoxidation was favored even using cyclic keto-amides
such as 2 (enol form of quinoline-2,4-diones). In addition, it is
surprising that the propellane 4, which was cyclized at the amide
12d
carbonyl group, was also isolated as a by-product. The reaction
using 2 (R = X = H) with no N-protection actually gave the
bis(hydroperoxide) 3h with a trace amount (entry 13). However,
most of the bis(hydroperoxide) 3h seemed to be further oxidized
under the conditions and we could not separate the fragments.
1
When the reaction using 2-(1-phenylvinyl)thiophene 1 (Ar = Ph,
2
10f,i,o
Ar = 2-thienyl)
was carried out under similar conditions, the
reaction was rather sluggish and gave the corresponding
propellane 4i together with another propellane 5i as an
inseparable stereoisomeric mixture (entry 14). The propellane 5i
was distinguishable from the other propellane 4i based on the
Scheme 2. Mn(III)-based aerobic oxidation pathway for the formation of 3, 4
and/or 5.
13
absence of the ketocarbonyl carbon in the C NMR spectrum.
The yield was improved by increasing the amount of thiophene 1
and oxidant (entries 15 and 16). The reaction of other 2-(1-
1
2
arylvinyl)thiophenes 1 (Ar = 4-F-C H and 4-Me-C H , Ar = 2-
6
4
6
4
2
.2. Aerobic oxidation of a mixture of alkenes 1 and 3-
13
thienyl) also led to a similar result (entries 17 and 18).
substituted quinolinones 6
In order to investigate the interconversion between the
In order to investigate the possibility of the synthesis of
endoperoxides, we designed the reaction using 3-substituted
quinolinones 6 (Scheme 3). When a substituent is present at the
bis(hydroperoxide) 3 and the propellane 4 during the reaction, the
1
2
bis(hydroperoxide) 3a (R = Me, Ar = Ar = Ph) and the
1
2
propellane 4a (R = Me, Ar = Ar = Ph), respectively, were then
treated both in the absence and presence of Mn(OAc)3 (see
Experimental section). As a result, it was confirmed that the
bis(hydroperoxide) 3a and the propellane 4a were not converted
into each other during the reaction. Therefore, we proposed the
3
-position of the 2-hydroxyquinolinones 2, the SET reduction of
the peroxy radical intermediate C’ would preferentially proceed
because the intramolecular hydrogen abstraction, such as the
peroxy radical C in Scheme 2, could not occur and the formation
of endoperoxides 7 or monohydroperoxides 8 would be expected
6,7
aerobic oxidation pathway as shown in Scheme 2. The Mn(III)-
enolate complex A produced in situ by the reaction of Mn(OAc)3
with quinolinone 2 (X = H) undergoes single-electron transfer
(Scheme 3). The reaction of 3-methylquinolinone 6 (R = Me)
was then carried out under similar aerobic oxidation conditions.
The alkene 1 was completely consumed and the desired
endoperoxide 7a was obtained (Table 2, entry 1). However, 7a
seemed to interconvert into the corresponding hydroperoxide 8a
(
SET) oxidation with the alkene 1 to form the corresponding
tertiary radical B which captures the dissolved molecular oxygen
followed by hydrogen abstraction, affording the
(
R = Me, Ar = Ph) even in the NMR time scale because the
6,7
monohydroperoxyethyl radical D. The radical intermediate D
undergoes a similar aerobic oxidation via an alkyl radical
intermediate E to furnish the bis(hydroperoxide)s 3. The radical
intermediate E would also be oxidized by the oxidant to produce
the corresponding cation F which undergoes double cyclization
to afford the propellanes 4 and/or 5. The use of an excess amount
of the catalyst accelerated the oxidation of the tertiary radical E
which resulted in the exclusive production of the propellanes 4i-k
13
methyl and methylene carbons were unclear in the C NMR
spectrum (see supplementary material). In fact, for the
quinolinones 6 bearing a bulky substituent, such as the propyl,
butyl, and phenyl group, hydroperoxides 8b-d were
predominantly produced along with the endoperoxides 7b-d
15
(
entries 2-4). Since it was difficult to separate endoperoxides 7
and hydroperoxides 8 by chromatographic separation, the
1
product yield was calculated based on the crude H NMR
Table 2
a
Mn(III)-based aerobic oxidation of a mixture of 1,1-disubstituted ethenes 1 and 3-substituted quinolinones 6
Alkene 1
Ar
Qunolinone 6
Molar ratio
2
1:6:Mn(OAc) •2H O
Time
h
b
Entry
Product (yield/%)
R
3
1
2
3
4
5
6
Ph
Me
Pr
1:2:0.5
1:2:0.5
1:2:0.5
1:2:0.5
1:2:0.5
1:2:0.5
15
18
15
15
18
15
7a (89)
c
c
c
Ph
7b (22)
7c (24)
7d (32)
7e (88)
7f (38)
8b (60)
8c (52)
8d (43)
Ph
Bu
Ph
Ph
4-Cl-C
6
H
4
Me
Me
c
4-Me-C
6
H
4
8f (58)
a
b
c
The reaction was carried out at room temperature in air.
The yield was based on the amount of the alkene 1 used.
The yield was calculated by crude NMR analysis.

4
Tetrahedron
MAte
1
0
11a,b
spectrum as shown in Table 2. The cycl
A
iza
C
tio
C
n
E
m
P
ig
T
ht
E
b
D
e
N
mp
lactones,
applied the reaction to a combination of alkenes 1 and 4-
hydroxyquinolinones 2, and obtained the desired
U
er
S
atu
C
reRItoPTproduce dihydrofurans, spirolactones,
γ-
1
1c,e-g
4c,11h-j
4d
difficult because the steric repulsion would exist between the
diphenyl group and the bulky R group or quinolinone skeleton in
the transition state of the conversion of G into H as well as the
intermediate H itself. In addition, the use of alkene 1 (Ar = 4-
MeC H ) also led to the formation of the hydroperoxide 8f as the
major product (entry 6). Although the tendency was also
observed for the reaction of tetronic acid with 1 (Ar = 4-
MeC H ), the reason was not clear. In either event, the peroxy
lactams,
and dihydroquinolinones. We then
thermodynamically stable angular products, 3,5-dihydrofuro[3,2-
c]quinolin-4-ones 9, along with a small amount of linear
byproducts, i.e., 3,9-dihydrofuro[2,3-b]quinolin-4-ones 10 (upper
part in Scheme 4 and Table 3).
stoichiometric amount of Mn(OAc) •2H O (2 equiv.) led to the
6
4
1
0c,14
Since the use of
7
6
4
3
2
anion G did not cyclize at the amide carbonyl group probably
due to the weak electrophilicity of the amide carbonyl carbon.
moderate yield of the product 9a (R = Me, X = H, Ar = Ph)
(Table 3, entry 1), an excess amount of the oxidant was necessary
to improve the product yield (entry 2). Although other
combinations of 1 and 2 also gave a similar result (entries 3-13),
the product yield from the quinolinones 2 bearing a substituent at
the 6-position was not improved (entries 9 and 11). The reaction
of conjugated butadienes 1’ with quinolinones 2 is quite
interesting (lower part in Scheme 4). The 1,4-addition did not
occur
but
1,2-addition,
giving
vinyl-substituted
dihydrofuroquinolinones 9m-p (entries 14-17) similar to copper-
mediated reaction of 2,2-dibromodimedone with conjugated
16
dienes.
Scheme 3. Mn(III)-based aerobic oxidation of a mixture of substituted
ethenes 1 and quinolinones 6.
2
4
.3. Mn(III)-mediated oxidation of alkenes in the presence of
-hydroxyquinolin-2(1H)-ones and other related
14
compounds
4
-Hydroxyquinolin-2(1H)-ones 2 as a reagent are very good
candidates not only as a radical source in the Mn(III)-mediated
3
oxidation, but also as a starting material for the synthesis of
quinolinone alkaloids such as atanine, araliopsine, and
Scheme 4. Mn(III)-mediated oxidation of substituted ethenes 1 and 1’ in the
presence of quinolinones 2.
10c
isoplatydesmine. The 1,3-dicarbonyl compounds, such as 2,4-
pentanedione, malonic acid, malonate esters, acetic anhydride,
malonamides, and 3-oxobutanoates, undergo oxidative
cyclization with alkene using Mn(OAc) •2H O at elevated
The mechanism for the formation of 9 and 10 has been
10c
reported by Parsons et al.
1,1-Diarylethene 2 should be
3
2
Table 3
Mn(III)-mediated oxidation of substituted ethenes 1 and 1’ in the presence of quinolinones 2
a
Alkene 1
Ar
Quinolinone 2
Time
min
2
b
Entry
1:2:Mn(OAc)
3
•2H
2
O
Product (yield/%)
R
X
H
1
2
3
4
5
6
7
8
9
1: Ph
1: Ph
1: Ph
1: Ph
1: Ph
1: Ph
Me
Me
Et
1:1.5:2
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
9a (60)
9a (87)
9b (73)
9c (76)
9d (85)
9e (73)
9f (87)
9g (93)
9h (44)
9i (67)
9j (58)
9k (98)
9l (74)
9m (71)
9n (58)
9o (69)
9p (71)
10a (4)
H
3
10a (7)
H
1.5
1.5
3
10b (trace)
Pr
H
Bn
H
H
10d (trace)
H
2
1: 4-Cl-C
6
H
4
Me
Me
H
H
3
10f (12)
1: 4-Me-C
1: Ph
6
H
4
H
5
10g (trace)
6-Me
8-Me
6-Cl
8-Cl
6-F
H
30
3
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
1: Ph
H
1: Ph
H
4
1: Ph
H
3
1: Ph
H
30
2
1’: Ph
Me
Me
Me
Me
1:1:3
1:1:3
1:1:3
1:1:3
1’: 4-F-C
6
H
4
H
3
1’: 4-Cl-C
6
H
4
H
4
1’: 4-Me-C
6
H
4
H
2
a
The reaction was carried out in glacial acetic acid at reflux temperature in air.
b
The yield was based on the amount of the alkene 1 or 1’ used.

5
oxidized by the Mn(III)-enolate complex A to
A
gi
C
ve
C
th
E
e
P
ex
TED
ed MANUSCRIPT
pe
ct
tertiary carbon radical B which underwent the SET oxidation
under the conditions to produce the tertiary cation I (Scheme 5).
Although Parsons reported the product yield of 9a and 10a as
10c
3
9% and 41%, respectively, the reaction conditions (heat at 60
°
C in an ultrasonic bath in the presence of KMnO as the co-
4
oxidant) are different from those of ours (heat under reflux)
compared to Table 3, entry 2), therefore, it is obvious that the
(
cyclization is prone to occur at the enolic ketocarbonyl group in
the cation I and a thermodynamically more stable angular
product 9 would be exclusively produced in our case.
14
Scheme 5. Reaction pathway for the formation of 9 and/or 10.
Gratifyingly, the 4-hydroxyquinolinone analogue, such as 4-
hydroxy-5,6,7,8-tetrahydroquinolin-2(1H)-one (11), 1-benzyl-4-
4
a
hydroxy-5,6-dihydropyridin-2(1H)-one (13),
4-hydroxy-2H-
chromen-2-one (15), and 4-hydroxy-6-methyl-2H-pyran-2-one
17) also underwent the oxidative cyclization with alkenes 1 to
afford the corresponding 2,3-dihydrofuro[3,2-c]pyridin-4-ones
2, 14 and furo[3,2-c]pyran-4-ones 16a-c, 18 in moderate to high
10h
and 21 were also subjected to the reaction with butadienes 2’ and
17
the corresponding benzofuran-4(5H)-ones 20a-c and propellane
(
12
2
2
were obtained (Table 4, entries 7-10). In this case, the
reaction with butadienes 1’ led to 1,2-addition similar to the
reaction of 1’ with quinolinone 2 in Scheme 4.
1
yields (Table 4, entries 1-6). The cyclization only took place at
the enolic ketocarbonyl group, and no products cyclized at the
amide and ester carbonyl groups were isolated. Dimedones 19
2
3
.4. Mn(III)-mediated oxidation of a mixture of alkenes 2 and
-substituted quinolinones 6
14
Table 4
a
Mn(III)-mediated oxidation of substituted ethenes 1 and 1’ in the presence of quinolinone-related compounds
b
Entry
Alkene 1 or 1’/Ar
Reagent
Time/min
Product (yield/%)
1
1: Ph
1
12 (53)
14 (52)
1
1
2
3
1: Ph
1: Ph
1
5
13
16a (89)
16b (87)
15
4
5
1: 4-Cl-C
6
H
4
15
15
2
4
1: 4-Me-C
6
H
4
16c (82)
6
7
1: Ph
1
1
18 (56)
17
1’: Ph
20a (78)
19
8
1’: 4-F-C
6
H
4
19
19
1
1
1
20b (55)
20c (63)
9
1’: 4-Cl-C
1’: Ph
6 4
H
c
d
1
0
22 (58)
2
1
a
b
c
d
The reaction was heated under reflux in air at the molar ratio of alkene 1 or 1’:reagent:Mn(OAc)
3 2
•2H O = 1:2:3.
The yield was based on the amount of the alkene 1 or 1’ used.
The molar ratio of the alkene 1’:reagent 21:Mn(OAc)
3
•2H
2
O = 1:1:2.
1
A 7:1 diastereomixture based on the H NMR spectrum.

6
Tetrahedron
ACCEPTED MANUSCRIPT
Table 5
a
Mn(III)-mediated oxidation of 1,1-disubstituted ethenes 1 in the presence of 3-substituted quinolinones 6
b
Alkene 1
Ph
Quinolinone 6
Molar ratio
Temperature
°C
Time
min
1.5
2.5
30
Product (yield/%)
Entry
Ar
3 2
1:6:Mn(OAc) •2H O
c
c
1
2
3
4
5
6
7
8
9
Ph
Me
Me
Me
Me
Me
1:2:3
1:2:3
1:2:3
1:2:3
reflux
reflux
reflux
80
23a (56)
23a (48)
24a (25)
24a (37)
Ph
Ph
24a (79)
24a (97)
Ph
24 h
3.5 h
2
d
c
Ph
1:2:2:2
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
23
23a (72)
23b (51)
23c (36)
23c (trace)
23d (35)
24a (trace)
c
Ph
Pr
reflux
reflux
reflux
reflux
reflux
24b (32)
c
Ph
Bu
Bu
Me
Me
6
24c (27)
c
4-Cl-C
6
H
4
30
24c (78)
c
4-Me-C
Ph
6
H
4
2
24d (37)
1
0
0.5
24e (55)
a
b
c
d
The reaction was carried out under heated conditions in air except for entry 5.
The yield was based on the amount of the alkene 1 used.
The yield was calculated by crude NMR analysis.
2
Cu(OAc) was added as a co-oxidant and the reaction was conducted under an argon atmosphere.
We were next interested in the Mn(III)-mediated oxidation of
quinolinones having a substituent at the 3-position since the
deprotonation could not occur at the intermediate cation I stage
in Scheme 5. The oxidation of a mixture of alkene 1 (Ar = Ph)
and 3-substituted quinolinone 6 (R = Me) with Mn(OAc) •2H O
3
2
was then carried out at the reflux temperature. After 1.5 minutes,
the dark-brown color of the reaction mixture turned transparent
and we recognized the complete consumption of the oxidant, and
the absence of the oxidant was finally confirmed by a KI-starch
test paper. After the usual work-up, furo[3,2-c]quinolinone
hemiacetal 23a was obtained along with the vinyl-substituted
quinolinone 24a (Scheme 6 and Table 5, entry 1). Since the
hemiacetal 23a might be unstable under the high temperature
conditions, an additional heating for 1 minute was conducted
after the oxidation. As a result, we found that the yield of 23a
Scheme 7. Oxidation pathway for the formation of 23 and 24.
amount of the Mn(III) catalyst in the case of 2-(1-
arylvinyl)thiophene led to the azatrioxa[4.4.3]propellanes 4 and
5
. A similar reaction using 3-substituted quinolinones 6 afforded
the endoperoxides 7 and/or hydroperoxides 8 depending on the
bulkiness of the substituent at the 3-position of 6. The oxidation
of alkenes 1 with Mn(III)-quinolinone enolate complexes A at
elevated temperature furnished the 3,5-dihydrofuro[3,2-
c]quinolin-4-ones 9a-l in high yields, and the reaction with
conjugated butadienes 1’ proceeded in a 1,2-fashion to afford
Scheme 6. Mn(III)-mediated oxidation of a mixture of 1,1-disubstituted
ethenes 1 and 3-substituted quinolinones 6.
vinyl-substituted
dihydrofuroquinolinones
9m-p.
The
quinolinone analogues 11, 13, 15, 17, and 21 also produced the
corresponding 2,3-dihydrofuro[3,2-c]pyridin-4-ones 12, 14,
furo[3,2-c]pyran-4-ones 16, 18, benzofuran-4(5H)-ones 20, and
propellane 22 in moderate to high yields. The hemiacetals 23 and
vinylquinolinones 24 could be synthesized depending on the
reaction conditions. The new quinolinone derivatives and the
related compounds obtained in the reactions will be screened for
their biological activities such as antimalarial, insecticidal,
bactericidal, cytotoxic, and antifeeding activities.
decreased and that of 24a increased (entry 2). Further additional
heating led to only the production of 24a (entry 3), and the
oxidation at 80 °C for 24 hours quantitatively gave 24a (entry 4).
These results suggested that the pathway of the hemiacetal 23a and
the vinyl-substituted quinolinone 24a were in equilibrium under
the stated oxidation conditions and the additional heating after the
oxidation resulted in the thermodynamically stable 24a (Scheme
3c
7
). Interestingly, the use of Cu(OAc) as a co-oxidant at 23 °C led
2
4
4
. Experimental section
to the exclusive production of the hemiacetal 23a (entry 5).
.1. Measurements
Melting points were taken using a micromelting point
3
. Conclusions
apparatus and are uncorrected. The NMR spectra were recorded
1
13
at 300 or 500 MHz for H and 75 or 125 MHz for C, with
tetramethylsilane as the internal standard. The chemical shifts are
We obtained various type of quinolinone derivatives from the
simple Mn(III)-based reaction depending on the reaction
conditions. The Mn(III)-catalyzed aerobic oxidation of alkenes 1
in the presence of 4-hydroxyquinolin-2(1H)-ones 2 formed the
bis(hydroperoxyethyl)quinolinones 3, and the use of an excess
reported in
δ values (ppm) and the coupling constants in Hz. The
IR spectra were measured in CHCl or KBr and expressed in
3
−1
cm . The EI MS spectra were obtained by a gas chromatograph-
mass spectrometer at an ionizing voltage of 70 eV. The high-

7
resolution mass spectra and the elementa
performed at the Instrumental Analysis Center, Kumamoto
University, Kumamoto, Japan.
A
l
C
an
C
al
E
ys
P
esTEwe
D
re MAar
N
om
U
C
S
),
C
13
R
9.
I
3 (2C, arom C), 136.8 (C-7), 133.6 (4C, arom C),
P
T
128.1 (8C, arom CH), 127.9 (C-5), 127.8 (4C, arom CH), 127.6
(4C, arom CH), 123.0 (C-6), 120.9 (arom C), 114.2 (C-8), 85.9
(
2C, COOH x 2), 53.7 (C-3), 48.6 (CH x 2), 29.9 (Me) ppm.
2
4
.2. Materials
FAB HRMS (acetone/NBA): calcd for C H Cl NO 736.0827
38
30
4
6
(
2
M+H); found 736.0839. CCDC reference number, CCDC
17001.
Manganese(II) acetate tetrahydrate, Mn(OAc) •4H O, was
2
2
purchased from Wako Pure Chemical Ind., Ltd. Manganese(III)
acetate dihydrate, Mn(OAc) •2H O, was prepared according to
3
2
4.3.3.
3,3-Bis[2-hydroperoxy-2,2-bis(4-methylphenyl)ethyl]-1-
1 2
18,19
the modified method described in the literature.
4-Hydroxy-2-
methylquinoline-2,4(1H,3H)-dione (3c: R = Me, Ar = Ar = 4-
Me-C H ). Pale yellow microcrystals (from MeOH), m.p. 134-
quinolinones 2, 6, 4-hydroxy-5,6,7,8-tetrahydroquinolin-2(1H)-
6
4
20
-
1
one (11) and 1-benzyl-4-hydroxy-5,6-dihydropyridin-2(1H)-one
136 °C. IR (KBr):
ν
3300-3000 (OOH), 1668, 1600 (C=O) cm .
4a
1
(
13) were also prepared according to the methods reported in
H NMR (300 MHz, CDCl3): 9.15 (2H, s, OOH), 7.51-7.46 (1H,
δ
the literature. The 1,1-disubstituted alkenes 1 were prepared by
the Grignard reaction of the corresponding acetophenones with
arylmagnesium bromides followed by dehydration. 4-Hydroxy-
m, arom H), 7.13-6.96 (10H, m, arom H), 6.88-6.77 (5H, m,
arom H)ꢀ6.61-6.58 (4H, m, arom H), 3.61 (4H, s, CH x 2),
2
3.08 (3H, s, NCH ), 2.28 (6H, s, Me x 2), 2.04 (6H, s, Me x 2)
3
13
2
H-chromen-2-one (15), 4-hydroxy-6-methyl-2H-pyran-2-one
ppm. C NMR (75 MHz, CDCl3):
δ 196.7, 174.8 (C=O), 142.4
(17), and dimedone (19) were purchased from Tokyo Kasei Co.,
(2C, arom C), 140.3 (1C, arom C), 138.6 (2C, arom C), 136.7
Ltd., and Wako Pure Chemical Ind., Ltd., respectively, and used
as received. The 2-(2-oxoethenyl)cyclohexane-1,3-dione 21 was
(2C, arom C), 136.5 (2C, arom C), 135.8 (C-7), 128.4 (8C, arom
C), 127.8 (6C, arom C), 127.0 (C-5), 126.4 (C-4), 126.1, 121.7
prepared by the reaction of dimedone (19) with
α-
(2C, arom C), 121.0 (arom C), 114.0 (C-8), 86.4 (2C, COOH x 2),
bromoacetophenone.
53.7 (C-3), 49.2 (CH x 2), 29.7 (Me), 20.9 (Me x 2), 20.6 (Me x
2
2
6
) ppm. FAB HRMS (acetone/NBA): calcd for C H NO
42 40 4
22.2957 (M-OOH); found 622.2924.
4
.3. Mn(III)-catalyzed aerobic oxidation of a mixture of
alkenes 2 and 4-hydroxyquinolin-2(1H)-ones
4
.3.4. 1-Ethyl-3,3-bis(2-hydroperoxy-2,2-
1
2
1
2
To a mixture of 1,1-diphenylethene 1 (Ar = Ar = Ph) (179.0
mg; 1 mmol) and quinolinone 2 (R = Me) (362.7 mg; 2.1 mmol)
diphenylethyl)quinoline-2,4(1H,3H)-dione (3d: R = Et, Ar = Ar
=
Ph). Yellow microcrystals (from MeOH), m.p. 138-140 °C. IR
-1 1
in glacial acetic acid (25 mL), Mn(OAc) •2H O (131.9 mg; 0.53
3
2
(KBr):
ν
3300-3057(OOH), 1666, 1608 (C=O) cm . H NMR
9.39 (2H, s, OOH), 7.47-7.41 (1H, m, arom
H), 7.34-7.09 (13H, m, arom H), 6.94-6.71 (10H, m, arom H),
.79 (2H, q, J = 6.7 Hz, CH ), 3.66 (4H, s, CH x 2), 0.88 (3H, t,
mmol) was added. The mixture was stirred at 23 °C in air for 4 h,
and then the reaction was quenched by adding water (40 mL) to
the reaction mixture. The aqueous solution was extracted five
(300 MHz, CDCl3): δ
3
2
2
13
times with CH Cl (10 mL x 5) and the combined extracts were
2
2
J = 6.7 Hz, CH ) ppm. C NMR (75 MHz, CDCl3):
δ
195.6,
75.4 (C=O), 143.7 (2C, arom C), 141.1 (2C, arom C), 140.9
arom C), 135.7 (C-7), 128.2 (2C, arom C), 128.1 (2C, arom C),
27.9 (4C, arom C), 127.7 (C-5), 127.6, 127.3, 127.1 (3C, arom
C), 127.0 (4C, arom C), 126.5 (arom C), 126.3 (4C, aromC),
3
washed twice with water, a saturated aqueous solution of sodium
hydrogencarbonate, dried over anhydrous sodium sulfate, and
concentrated to dryness. The residue was separated by silica gel
1
(
1
flash column chromatography eluting with CH Cl -hexane (7:3
2
2
v/v), giving bis(hydroperoxide) 3a (210.1 mg; 71% yield based
on the alkene 1 used) (Table 1, entry 6). Molar ratio and reaction
times of other aerobic oxidation are shown in Table 1 and 2. The
products 3-5, 7, and 8 were further purified by recrystallization
from an appropriate solvent for the analytical sample, and their
physical data are given below.
1
5
22.6 (C-6), 121.4 (arom C), 113.9 (C-8), 86.7 (2C, COOH x 2),
3.7 (C-3), 49.4 (2C, CH x 2), 38.3 (CH ), 11.4 (Me) ppm. FAB
2
2
HRMS (acetone/NBA): calcd for C H NO 580.2488 (M-
OOH); found 580.2499.
39
34
4
4
.3.5.
1-Benzyl-3,3-bis(2-hydroperoxy-2,2-
1 2
diphenylethyl)quinoline-2,4(1H,3H)-dione (3e: R = Bn, Ar = Ar
Ph). Yellow microcrystals (from MeOH), m.p. 105-110 °C. IR
4
.3.1.
3,3-Bis(2-hydroperoxy-2,2-diphenylethyl)-1-
1 2
=
-
1
1
methylquinoline-2,4(1H,3H)-dione (3a: R = Me, Ar = Ar = Ph).
(
KBr):
ν
3400-3026 (OOH), 1650, 1638 (C=O) cm . H NMR
9.40 (2H, s, OOH), 7.98-6.57 (29H, m,
Colorless microcrystals (from MeOH), m.p. 134-135 °C. IR
(300 MHz, CDCl3):
δ
-
1
1
1
3
(
(
KBr):
300 MHz, CDCl3):
ν
3400-3050 (OOH), 1668, 1624 (C=O) cm . H NMR
9.14 (2H, s, OOH), 7.52-7.46 (1H, m, arom
arom H), 5.04 (2H, s, CH ), 3.74 (4H, s, CH x 2) ppm. C NMR
(75 MHz, CDCl3):
1
(C-5), 128.1 (6C, arom CH), 128.1 (arom CH), 127.7 (2C, arom
CH), 127.3 (arom CH), 127.1 (2C, arom CH), 127.0 (6C, arom
CH), 126.8 (2C, arom CH), 126.5 (2C, arom CH), 126.2 (3C,
arom CH), 122.7 (C-6), 121.2 (arom C), 115.2 (C-8), 86.7 (2C,
COOH x 2), 54.0 (CH ), 49.6 (C-3), 49.1 (CH x 2) ppm. FAB
2
2
δ
δ 194.5, 177.3 (C=O), 143.9 (3C, arom C),
41.4, 140.7(2C, arom C), 135.9 (arom C), 135.3 (C-7), 129.1
H), 7.24-7.10 (11H, m, arom H), 6.97-6.80 (12H, m, arom H),
13
3
.66 (4H, s, CH x 2), 3.00 (3H, s, NMe) ppm. C NMR (75
2
MHz, CDCl3):
δ
197.3, 174.5 (C=O), 142.8 (2C, arom C), 142.5
(arom C), 141.8 (2C, arom C), 136.1 (C-7), 127.7 (8C, arom CH),
1
27.5 (C-5), 127.3 (8C, arom CH), 126.5 (2C, arom CH), 126.3
(
(
2C, arom CH), 122.8 (C-6), 121.2 (arom C), 114.2 (C-8), 86.6
2C, COOH x 2), 53.8 (C-3), 49.1 (2C, CH x 2), 29.9 (Me) ppm.
2
2
2
HRMS (acetone/NBA): calcd for C H NO 676.2699 (M+H);
44 38 6
FAB HRMS (acetone/NBA): calcd for C H NO 566.2331 (M-
38
32
4
found 676.2701.
.3.6.
OOH); found 566.2332.
4
1-Benzyl-3,3-bis[2,2-bis(4-chlorophenyl)-2-
1
4
.3.2. 3,3-Bis[2,2-bis(4-chlorophenyl)-2-hydroperoxyethyl]-1-
hydroperoxyethyl]quinoline-2,4(1H,3H)-dione (3f: R = Bn, Ar =
Ar = 4-Cl-C H ). Yellow microcrystals (from MeOH), m.p. 115-
1
2
2
methylquinoline-2,4(1H,3H)-dione (3b: R = Me, Ar = Ar = 4-
Cl-C H ). Colorless microcrystals (from CH Cl /hexane), m.p.
6
4
-
1
6
4
2
2
118 °C. IR (KBr):
ν
3400-3060 (OOH), 1662, 1597 (C=O) cm .
H NMR (300 MHz, CDCl3): 9.43 (2H, s, OOH), 7.88-6.59
(25H, m, arom H), 5.11 (2H, s, CH ), 3.68 (2H, d, J = 13.6 Hz,
1
2
15-216 °C. IR (KBr):
ν
3440-3100 (OOH), 1670,1629 (C=O)
cm . H NMR (300 MHz, CDCl ): 9.20 (2H, s, OOH), 7.63-
.58 (1H, m, arom H), 7.29-7.01 (10H, m, arom H), 6.91-6.76
9H, m, arom H), 3.60 (2H, d, J = 14.1 Hz, HCH), 3.54 (2H, d, J
δ
-
1
1
δ
3
2
13
7
(
=
HCH), 3.59 (2H, d, J = 13.6 Hz, HCH) ppm. C NMR (75 MHz,
CDCl3): 194.3, 177.1 (C=O), 141.8 (4C, arom C), 141.2, 138.3
2C, arom C), 136.1 (C-7), 135.5 (arom C), 133.7 (2C, arom C),
133.5 (2C, arom C), 131.3 (2C, arom CH), 129.2 (C-5), 128.7
δ
13
14.1 Hz, HCH), 3.16 (3H, s, Me) ppm. C NMR (75 MHz,
196.5, 174.6 (C=O), 142.0 (2C, arom C), 141.0 (3C,
(
CDCl3):
δ

8
Tetrahedron
(
2C, arom CH), 128.4 (4C, arom CH), 128.2
2C, arom CH), 127.7 (4C, arom CH), 127.2 (4C, arom CH),
27.0 (2C, arom CH), 122.9 (C-6), 115.2 (C-8), 86.1 (2C, COOH
x 2), 53.9 (CH ), 49.2 (C-3), 49.0 (CH x 2) ppm. FAB HRMS
A
(ar
C
om
C
C
E
H
P
)
T
, 1
E
28
D
.0 MACD
NU
C
l )
S
:
C
δ
1
R
9
I
3
P
.9 (C=O), 148.3, 136.8 (2C), 136.6 (2C), 136.2
T
3
(
1
(2C), 136.1 (2C, arom C), 136.6, 130.2, 129.3 (2C), 128.9 (2C),
128.7 (2C), 128.4 (2C), 128.4 (2C), 128.2 (2C), 126.6 (2C),
125.4 (2C), 118.2, 113.3 (arom CH), 117.0, 114.5 (C-5a and C-
2
2
(
acetone/NBA): calcd for C H Cl NO 812.1140 (M+H); found
10a), 92.0 (C-3), 87.0 (C-12), 51.0 (C-4a), 39.1, 38.4 (CH ), 30.3
44
34
4
6
2
8
12.1149.
(Me), 21.0 (Me), 20.9 (Me
x
3) ppm. FAB HRMS
(
acetone/NBA): calcd for C H NO 622.2957 (M+H); found
42
40
4
4
.3.7.
1-Benzyl-3,3-bis[2-hydroperoxy-2,2-bis(4-1
622.2958.
methylphenyl)ethyl]quinoline-2,4(1H,3H)-dione (3g: R = Bn, Ar
=
2
Ar = 4-Me-C H ). Pale yellow microcrystals (from MeOH),
4.3.11.
10-Ethyl-3,4-dihydro-3,3,12,12-tetraphenyl-10a,4a-
6
4
m.p. 58-60 °C. IR (KBr):
(
7
ν
3400-3000 (OOH), 1665, 1654
C=O) cm . H NMR (300 MHz, CDCl ): 9.39 (2H, s, OOH),
.71-6.39 (25H, m, arom H), 5.10 (2H, s, CH Ph), 3.70 (4H, s,
(epoxyethano)-1,2-dioxino[3,4-b]quinolin-5(10H)-one (4d: R =
-
1
1
1 2
δ
Et, Ar = Ar = Ph). Yellow microcrystals (from MeOH), m.p.
-1 1
3
159-161 °C. IR (KBr):
ν 1674 (C=O) cm . H NMR (300 MHz,
2
13
CH x 2), 2.28 (6H, s, Me x 2), 1.95 (6H, s, Me x 2) ppm.
C
CDCl3): 7.82-7.79 (1H, m, arom H), 7.61-7.57 (4H, m, arom H),
δ
2
NMR (75 MHz, CDCl3):
1
1
δ
194.3, 177.6 (C=O), 141.6 (arom C),
41.2 (2C, arom C), 137.6 (2C, arom C), 136.8 (2C, arom C),
36.4 (2C, arom C), 136.0 (arom C), 135.1 (C-7), 130.2 (arom
7.51-7.45 (4H, m, arom H), 7.37-7.28 (4H, m, arom H), 7.19-
7.00 (8H, m, arom H), 6.89-6.85 (2H, m, arom H), 6.75-6.70 (1H,
m, arom H), 4.09-3.83 (2H, m, CH ), 3.24 (1H, d, J = 12.5 Hz,
2
CH), 129.1 (2C, arom CH), 128.8 (2C, arom CH), 128.7 (4C,
arom CH), 127.7 (C-6), 127.5 (4C, arom CH), 126.9 (2C, arom
CH), 126.1 (arom C), 126.6 (2C, arom CH), 126.2 (4C, arom C),
HCH), 3.10 (1H, d, J = 14.5 Hz, HCH), 2.78 (1H, d, J = 12.5 Hz,
HCH), 2.46 (1H, d, J = 14.5 Hz, HCH), 1.49 (3H, t, J = 7.0 Hz,
13
Me) ppm. C NMR (75 MHz, CDCl3):
δ 193.6 (C=O), 147.3,
1
21.4 (C-5), 115.2 (C-8), 86.6 (2C, COOH x 2), 54.0 (C-3), 49.6
145.5, 144.2, 142.8, 142.2 (arom C), 136.2, 132.4, 130.1, 128.7,
128.4 (2C), 128.3 (2C), 127.9, 127.7 (2C), 127.6 (2C), 126.9,
126.6 (2C), 126.2 (2C), 125.9 (2C), 125.8 (2C), 118.0, 113.5
(arom CH), 117.0, 114.9 (C-5a and C-10a), 87.0 (C-3), 84.2 (C-
(2C, CH x 2), 49.3 (CH ), 20.9 (2C, Me x 2), 20.5 (2C, Me x 2)
2
2
ppm. FAB HRMS (acetone/NBA): calcd for C H NO
6
48
44
4
98.3270 (M-OOH); found 698.3268.
1
2), 53.6 (C-4a), 42.6, 38.6, 38.2 (CH ), 13.3 (Me) ppm. FAB
2
4
.3.8. 3,4-Dihydro-10-methyl-3,3,12,12-tetraphenyl-10a,4a-
HRMS (acetone/NBA): calcd for C H NO 580.2488 (M+H);
found 580.2487.
39
34
4
(epoxyethano)-1,2-dioxino[3,4-b]quinolin-5(10H)-one (4a: R =
1 2
Me, Ar
=
Ar
= Ph). Colorless microcrystals (from
-1
CH Cl /hexane), m.p. 134-135 °C. IR (KBr):
ν
1658 (C=O) cm .
7.82-7.79 (2H, m, arom H), 7.58-
.92 (21H, m, arom H), 6.77-6.72 (1H, m, arom H), 3.33 (3H, s,
4.3.12.
3,4-Dihydro-3,3,12,12-tetraphenyl-10a,4a-
2
2
1
H NMR (300 MHz, CDCl3):
δ
(epoxyethano)-1,2-dioxino[3,4-b]quinolin-5(10H)-one (4h: R =
H, Ar = Ar = Ph). Yellow microcrystals (from MeOH), m.p.
-1 1
190-192 °C. IR (KBr):
1 2
6
Me), 3.25 (1H, d, J = 12.9 Hz, HCH), 3.10 (1H, d, J = 14.4 Hz,
HCH), 2.80 (1H, d, J = 12.9 Hz, HCH), 2.54 (1H, d, J = 14.4 Hz,
ν
3200-2940 (NH), 1660 (C=O) cm . H
7.82-7.79 (2H, m, arom H), 7.57-
NMR (300 MHz, CDCl3):
δ
13
HCH) ppm. C NMR (75 MHz, CDCl3):
45.2, 143.9, 142.5, 142.4 (arom C), 136.3, 132.4, 130.1, 128.4
2C), 128.3 (2C), 128.2 (2C), 127.8 (2C), 127.6 (2C), 127.3,
27.1, 126.9, 126.6 (2C), 126.4 (2C), 126.0 (2C), 118.4, 113.4
arom CH), 117.1, 114.6 (C-5a and C-10a), 87.1 (C-3), 84.3 (C-
2), 53.4 (C-4a), 43.2 (CH ), 38.3 (CH ), 30.3 (Me) ppm. Anal.
δ
193.7 (C=O), 148.2,
7.44 (5H, m, arom H), 7.35-6.91 (15H, m, arom H), 6.75-6.70
(2H, m, arom H), 5.76 (1H, s, NH), 3.25 (1H, d, J = 13.2 Hz,
HCH), 3.15 (1H, d, J = 14.4 Hz, HCH), 2.84 (1H, d, J = 13.2 Hz,
HCH), 2.57 (1H, d, J = 14.4 Hz, HCH) ppm. C NMR (75 MHz,
CDCl3): 193.9 (C=O), 146.3, 145.1, 142.4, 142.1, 137.6 (arom
C), 135.9, 132.4, 130.1 (2C), 128.4, 128.3 (2C), 128.2 (2C),
128.0, 127.8 (2C), 127.6, 126.9, 126.6 (2C), 126.3 (2C), 126.0
(2C), 125.9 (2C), 119.5, 115.9 (arom CH), 116.3, 112.7 (C-5a
and C-10a), 87.5 (C-3), 84.4 (C-12), 53.2 (C-4a) , 43.0, 37.9
1
(
1
(
13
δ
1
2
2
Calcd for C H NO ꢁ1/4H O: C, 80.05; H,5.57; N, 2.46.
Found: C, 80.13; H, 5.63; N, 2.52. CCDC reference number,
CCDC 218561.
38
31
4
2
(
5
CH ) ppm. FAB HRMS (acetone/NBA): calcd for C H NO
52.2175 (M+H); found 552.2092.
2
37 30
4
4
1
.3.9. 3,3,12,12-Tetrakis(4-chlorophenyl)-3,4-dihydro-10-methyl-
0a,4a-(epoxyethano)-1,2-dioxino[3,4-b]quinolin-5(10H)-one
1
2
(4b: R = Me, Ar = Ar = 4-Cl-C H ). Yellow microcrystals
4.3.13. 3,4-Dihydro-10-methyl-3,12-diphenyl-3,12-bis(2-thienyl)-
10a,4a-(epoxyethano)-1,2-dioxino[3,4-b]quinolin-5(10H)-one
(4i: R = Me, Ar = Ph, Ar = 2-thienyl). The diastereomixture
could not be purified and the physical data of one of the
diasteromers are shown as follows. Colourless needles (from
EtOAc/hexane), m.p. 185-187 °C (decompd). IR (CHCl ): 1672
(C=O) cm . H NMR (300 MHz, CDCl ): δ 7.78-6.76 (20H, m,
3
arom H), 3.40 (1H, d, J = 13.0 Hz, HCH), 3.33 (3H, s, Me), 3.05
(1H, d, J = 15.0 Hz, HCH), 2.90 (1H, d, J = 13.0 Hz, HCH), 2.52
(1H, d, J = 15.0 Hz, HCH) ppm. C NMR (75 MHz, CDCl3):
6
4
-
1
(
from MeOH), m.p. 115-116 °C. IR (KBr):
ν
1651 (C=O) cm .
7.58-6.75 (20H, m, arom H), 3.33
3H, s, Me), 3.27 (1H, d, J = 12.2 Hz, HCH), 3.10 (1H, d, J =
4.0 Hz, HCH), 2.80 (1H, d, J = 12.2 Hz, HCH), 2.54 (1H, d, J =
1
1
2
H NMR (300 MHz, CDCl3):
(
δ
1
1
1
1
1
1
4
13
4.0 Hz, HCH) ppm. C NMR (75 MHz, CDCl3):
δ
193.6 (C=O),
ν
3
–1 1
48.2 (2C), 145.2 (2C), 143.9 (2C), 142.4 (2C, arom C), 136.3,
28.4 (2C), 128.3 (2C), 127.9, 127.7 (2C), 127.5 (2C), 126.9,
26.6 (2C), 126.4 (2C), 126.0 (4C), 118.4, 113.4 (arom CH),
17.1, 114.6 (C-5a and C-10a), 87.1 (C-3), 84.3 (C-12), 53.5 (C-
a), 43.2, 38.4 (CH2), 30.3 (Me) ppm. FAB HRMS
13
δ
192.9 (C=O), 150.2, 147.3, 145.4, 143.4, 141.8 (arom C), 136.4,
128.2 (2C), 128.0 (2C), 127.7, 127.4 (2C), 126.7, 126.6, 126.3,
126.2 (2C), 126.1, 125.9, 125.8 (2C), 125.7, 118.6, 113.4 (arom
CH), 117.0, 114.7 (C-5a and C-10a), 84.7 (C-3), 83.0 (C-12),
(acetone/NBA): calcd for C H Cl NO 702.0772 (M+H); found
38 28 4 4
7
02.0768.
4
.3.10.
3,4-Dihydro-3,3,12,12-tetrakis(4-methylphenyl)-10-
5
3.3 (C-4a) , 45.3, 39.6 (CH ), 30.3 (Me) ppm. FAB HRMS
2
methyl-10a,4a-(epoxyethano)-1,2-dioxino[3,4-b]quinolin-
5
1
2
(acetone/NBA/NaI): calcd for
C H27NO S Na 600.1279
34 4 2
(10H)-one (4c: R = Me, Ar = Ar = 4-Me-C H ). Pale yellow
6 4
(M+Na); found 600.1284.
microcrystals (from MeOH), m.p. 174-175 °C. IR (KBr):
ν
1672
7.75-6.64 (20H, m,
arom H), 3.29(3H, s, Me), 3.17 (1H, d, J = 13.0 Hz, HCH), 3.04
-
1 1
(C=O) cm . H NMR (500 MHz, CDCl ):
δ
4.3.14.
3,12-Bis(4-fluorophenyl)-3,4-dihydro-10-methyl-3,12-
3
bis(2-thienyl)-10a,4a-(epoxyethano)-1,2-dioxino[3,4-b]quinolin-
5(10H)-one(4j: R = Me, Ar = 4-F-C H , Ar = 2-thienyl). The
1
2
(1H, d, J = 11.0 Hz, HCH), 2.83 (1H, d, J = 13.0 Hz, HCH), 2.48
6 4
(
2
1H, d, J = 11.0 Hz, HCH), 2.37 (3H, s, Me), 2.26 (3H, s, Me),
.20 (3H, s, Me), 2.17 (3H, s, Me) ppm. C NMR (125 MHz,
diastereomixture could not be purified and the physical data of
one of the diasteromers are shown as follows. Amorphous. IR
13

9
-
1
1
(
CHCl3):
ν
1670 (C=O) cm . H NMR (30
7.72-6.74 (18H, m, arom H), 3.33 (3H, s, Me), 3.08 (1H, d, J =
5.0 Hz, HCH), 2.98 (1H, d, J = 12.6 Hz, HCH), 2.80 (1H, d, J =
A
0
C
M
C
Hz
E
,
P
C
T
D
E
Cl
D
): MA4.
N
3.1
U
8.SC
3
R
,4-
I
D
P
i
T
hydro-3,12-bis(4-methylphenyl)-6-methyl-3,12-
3
δ
1
1
bis(2-thienyl)-10b,4a-(epoxyethano)-1,2-dioxino[4,3-c]quinolin-
5(6H)-one (5k: R = Me, Ar = 4-Me-C H , Ar = 2-thienyl). The
diastereomixture could not be purified and the physical data of
one of the diasteromers are shown as follows. Amorphous. IR
1
2
6
4
1
3
2.6 Hz, HCH), 2.58 (1H, d, J = 15.0 Hz, HCH) ppm. C NMR
192.9 (C=O), 160.8, 160.3, 149.6, 148.1,
46.8, 141.4, 138.9 (arom C), 136.7, 136.5, 128.7, 128.6, 128.4
(75 MHz, CDCl3): δ
-
1
1
1
(CHCl3):
ν1652 (C=O) cm . H NMR (300 MHz, CDCl3):
(2C), 127.7 (2C), 127.1, 126.7, 126.4 (2C), 126.3 (4C), 118.8,
δ 8.01-7.98 (1H, m, arom H), 7.67-6.94 (15H, m, arom H), 6.76-
1
8
13.6 (arom CH), 116.9, 114.7 (C-5a and C-10a), 84.4 (C-3),
6.72 (1H, m, arom H), 6.53-6.47 (1H, m, arom H), 3.45 (2H, s,
2.9 (C-12), 53.6 (C-4a) , 44.5, 39.4 (CH ), 30.3 (Me) ppm.
CH ), 3.20 (1H, d, J = 15.0 Hz, HCH), 2.91 (3H, s, Me), 2.32
2
2
FAB HRMS (acetone/NBA): calcd for C H F NO S 614.1271
(1H, d, J = 15.0 Hz, HCH), 2.27 (3H, s, Me), 2.20 (3H, s, Me)
34
26
2
4 2
13
(M+H); found 614.1269.
ppm. C NMR (75 MHz, CDCl3):
1
1
δ
169.3 (C=O), 149.9, 140.5,
37.7, 137.0 (arom C), 130.6, 129.2, 128.9, 128.1, 127.9, 126.6,
26.4, 126.3, 126.2, 126.1, 125.9, 125.8, 125.7, 125.2, 123.6,
4
.3.15.
3,4-Dihydro-3,12-bis(4-methylphenyl)-10-methyl-3,12-
bis(2-thienyl)-10a,4a-(epoxyethano)-1,2-dioxino[3,4-b]quinolin-
1
2
120.8, 114.4 (arom CH), 106.5 (C-10b), 86.9 (C-3), 83.4 (C-12),
1.5 (C-4a), 46.1 (C-4), 40.2 (C-13), 29.8 (N-CH ), 21.1 (Me)
5
(10H)-one (4k: R = Me, Ar = 4-Me-C H , Ar = 2-thienyl). The
6 4
5
3
diastereomixture could not be purified and the physical data of
one of the diasteromers are shown as follows. Amorphous. IR
ppm. FAB HRMS (acetone/NBA): calcd for C H NO S
3
6
31
4 2
-
1
1
606.1773 (M+H); found 606.1765.
(CHCl3):
ν
1670 (C=O) cm . H NMR (300 MHz, CDCl3):
δ
1
1
7.76-6.71 (18H, m, arom H), 3.30 (3H, s, Me), 3.26 (1H, d, J =
4.3.19. 4,4a,6,10b-Tetrahydro-10b-hydroxy-3,3-diphenyl-4a-
2.9 Hz, HCH), 3.06 (1H, d, J = 15.0 Hz, HCH), 2.90 (1H, d, J =
2.9 Hz, HCH), 2.56 (1H, d, J = 15.0 Hz, HCH), 2.29 (3H, s,
methyl-1,2-dioxino[4,3-c]quinolin-5(3H)-one (7a: R = Me, Ar =
Ph). Colorless microcrystals (from CH Cl /hexane), m.p. 195 °C
2
2
13
Me), 2.19 (3H, s, Me) ppm. C NMR (75 MHz, CDCl3):
δ
193.1
(decomp). IR (KBr):
cm . H NMR (300 MHz, CDCl ): 10.1 (1H, s, NH), 7.73-7.70
ν
3382-2929 (OH and NH), 1678 (C=O)
-
1 1
(C=O), 147.5, 138.1, 137.4, 136.9, 136.5, 136.4, 136.4 (arom C),
δ
3
1
1
1
4
36.3, 129.2, 128.9, 128.4, 128.2, 128.1, 126.7 (2C), 126.0 (2C),
25.9 (2C), 125.7 (2C), 125.5 (2C), 118.4, 113.5 (arom CH),
17.0, 114.7 (C-5a and C-10a), 84.6 (C-3), 82.9 (C-12), 53.7 (C-
a), 45.0, 39.6 (CH ), 30.3 (N-CH ), 21.0, 20.9 (Me) ppm. FAB
(1H, m, arom H), 7.57 (1H, br. S, arom H), 7.46-7.43 (3H, m,
arom H), 7.34-7.01 (8H, m, arom H), 6.77-6.75 (1H, m, arom H),
3.47 (1H, br s, OH), 3.34 (1H, br, HCH), 2.75 (1H, d, J = 13.5
13
Hz, HCH), 1.10 (3H, s, Me) ppm. C NMR (75 MHz, CDCl3):
171.2 (C=O), 144.8, 142.0 (2C, arom C), 136.7 (2C, arom C),
130.4 (arom C), 128.0 (4C, arom CH), 127.2 (2C, arom CH),
27.1 (arom C), 127.0 (2C, arom CH), 126.3 (arom CH), 125.4
2C, arom CH), 122.0 (arom CH), 99.0 (C-10b), 84.4 (C-3), 44.0
(C-4a), 30.3 (CH ), 22.3 (Me) ppm. Anal. Calcd for C24
C, 74.40; H, 5.46; N, 3.62. Found: C, 74.20; H, 5.41; N, 3.59.
2
3
HRMS (acetone/NBA): calcd for C H NO S 606.1773 (M+H);
found 606.1782.
δ
36
32
4 2
1
(
4
1
.3.16. 3,4-Dihydro-6-methyl-3,12-diphenyl-3,12-bis(2-thienyl)-
0b,4a-(epoxyethano)-1,2-dioxino[4,3-c]quinolin-5(6H)-one (5i:
1
2
2
H21NO :
4
R = Me, Ar = Ph, Ar = 2-thienyl). The diastereomixture could
not be purified and the physical data of one of the diasteromers
are shown as follows. Colourless needles (from EtOAc/hexane),
m.p. 244-246 °C (decompd). IR (CHCl3):
NMR (300 MHz,
4.3.20. 4,4a,6,10b-Tetrahydro-10b-hydroxy-3,3-diphenyl-4a-
–1 1
ν
1662 (C=O) cm . H
CDCl3):
propyl-1,2-dioxino[4,3-c]quinolin-5(3H)-one (7b: R = Pr, Ar =
Ph). Colorless microcrystals (from MeOH), m.p. 145-147 °C. IR
-
1 1
δ
� � � � � � � � � � � � � � � � � � � � � � � � � , 7.49-6.70
19H, m, arom H), 3.07 (3H, s, Me), 3.23 (1H, d, J = 14.7 Hz,
HCH), 3.18 (1H, d, J = 15.0 Hz, HCH), 2.90 (1H, d, J = 15.0 Hz,
(KBr):
(300 MHz, DMSO-d6):
ν
3392-2873 (OH and NH), 1662 (C=O) cm . H NMR
10.02 (1H, s, NH), 7.70-7.66 (1H, m,
(
δ
arom H), 7.49-7.40 (2H, m, arom H), 7.32-6.98 (10H, m arom H),
6.70-6.68 (1H, m, arom H), 3.79 (1H, d, J = 13.1 Hz, HCH), 2.59
(1H, d, J = 13.1 Hz, HCH), 2.50 (1H, s, OH), 1.52 (2H, t, J = 5.8
Hz, CH ), 1.09-0.91 (2H, m, CH ), 0.68 (3H, t, J = 7.0 Hz, Me)
13
HCH), 2.33 (1H, d, J = 14.7 Hz, HCH) ppm. C NMR (75 MHz,
CDCl3): 169.2 (C=O), 149.7, 148.7, 147.2, 146.9, 144.8, 143.3,
30.7, 130.6, 128.6, 128.3, 128.2, 128.0, 127.9, 127.7, 127.5,
δ
1
1
1
1
2
2
13
27.3, 126.7, 126.5, 126.4, 126.3, 126.2, 126.0, 125.9, 125.8,
25.5, 125.4, 125.3, 125.1, 124.9, 123.6, 123.5, 120.7, 120.5,
14.4, 106.8 (C-10b), 86.9 (C-3), 83.5 (C-12), 51.5 (C-4a), 46.2
ppm. C NMR (75 MHz, DMSO-d6): δ 169.8 (C=O), 145.4,
142.0, 136.9 (arom C), 130.6, 128.1, 127.3, 127.0, 126.7, 125.4,
122.0 (arom CH), 121.1 (arom C), 114.3 (arom CH), 98.7 (C-
(
(
(
C-4), 40.2 (C-13), 29.8 (N-CH3) ppm. FAB HRMS
10b), 84.4 (C-3), 47.4 (C-4a), 39.4, 34.6, 16.5 (CH ), 14.4 (Me)
2
acetone/NBA/NaI): calcd for C H NO S Na 600.1279
ppm. FAB HRMS (acetone/NBA): calcd forC H NO 416.1862
34
27
4
2
26 26
4
M+Na); found 600.1357.
(M+H); found 416.1862.
4
.3.17. 3,12-Bis(4-fluorophenyl)-3,4-dihydro-6-methyl-3,12-
4.3.21. 4a-Butyl-4,4a,6,10b-Tetrahydro-10b-hydroxy-3,3-
bis(2-thienyl)-10b,4a-(epoxyethano)-1,2-dioxino[4,3-c]quinolin-
diphenyl-1,2-dioxino[4,3-c]quinolin-5(3H)-one (7c: R = Bu, Ar
= Ph). The product 7c could not be separated from 8c by silica
gel chromatography. Yellow microcrystals (from CH Cl /hexane),
1
2
5
(6H)-one (5j: R = Me, Ar = 4-F-C H , Ar = 2-thienyl). The
6 4
diastereomixture could not be purified and the physical data of
one of the diasteromers are shown as follows. Colourless needles
2
2
m.p.148-152 °C. IR (KBr):
(C=O) cm . H NMR (300 MHz, CDCl ): 10.05 (1H, s, NH),
ν
3600-2900 (OH and NH), 1658
-
1 1
(
from EtOAc/hexane), m.p. 172-173 °C. IR (CHCl ):
ν
1668
δ
3
3
-
1 1
(C=O) cm . H NMR (300 MHz, CDCl ):
δ
8.00-6.44 (18H, m,
7.81-6.61 (14H, m, arom H), 5.43 (1H, s, OH), 3.81 (1H, d, J =
14.1 Hz, HCH), 2.73 (1H, d, J = 14.1 Hz, HCH), 2.13 (2H, m,
CH ), 1.34-1.16 (4H, m, CH x 2), 0.74 (3H, t, J = 6.9 Hz, Me)
3
arom H), 3.45 (2H, s, CH ), 3.18 (1H, d, J = 14.4 Hz, HCH), 2.95
2
13
(
3H, s, Me), 2.30 (1H, d, J = 14.4 Hz, HCH) ppm. C NMR (75
MHz, CDCl3): 169.0 (C=O), 163.7, 160.3, 149.4, 146.8, 139.2
arom C), 130.8, 130.7, 128.7, 128.6, 127.9, 127.8, 127.7, 127.6,
2
2
13
δ
ppm. C NMR (75 MHz, CDCl3): δ 171.6 (C=O), 143.5, 141.9,
(
140.3 (arom C), 135.9, 128.5, 127.8, 127.6, 127.4, 126.6, 123.3,
115.0 (arom CH), 99.5 (C-10b), 86.0 (C-3), 48.3 (C-4a), 36.7,
35.2, 25.3, 23.1 (CH2), 13.8 (Me) ppm. FAB HRMS
(acetone/NBA): calcd for C H NO 430.2018 (M+H); found
1
27.5, 127.4, 126.8, 126.5, 126.4, 126.3, 126.2, 126.0, 123.8
(arom CH), 120.5 (arom C), 115.6, 115.3, 115.2, 114.9, 114.5,
1
5
14.4, 114.1 (arom CH), 106.5 (C-10b), 86.5 (C-3), 83.2 (C-12),
27
28
4
1.7 (C-4a), 46.2 (C-4), 40.2 (C-13), 29.8 (N-CH ) ppm. FAB
430.2021.
3
HRMS (acetone/NBA): calcd for C H F NO S 614.1271
34
26
2
4 2
4
.3.22. 4,4a,6,10b-Tetrahydro-10b-hydroxy-4a,3,3-triphenyl-1,2-
(M+H); found 614.1288.
dioxino[4,3-c]quinolin-5(3H)-one (7d: R = Ar = Ph). The

1
0
Tetrahedron
product 7d could not be separated from
chromatography. Colorless microcrystals (from MeOH), m.p.
51 °C. IR (KBr): 3400-2940 (OH and NH), 1697, 1659 (C=O)
cm . H NMR (300 MHz, CDCl ): 10.32 (1H, s, NH), 7.52-
.01 (17H, m, arom H), 6.83-6.80 (1H, m, arom H), 6.44-6.41
1H, m, arom H), 5.27 (OH), 4.16 (1H, d, J = 14.1 Hz, HCH),
A
8dCCby
E
s
P
ili
T
ca
E
g
D
el MA6.
NU
61
(1
S
4H
C
,
R
m
I
,
P
ar
T
om H), 3.59 (1H, d, J = 14.7 Hz, HCH), 3.53
(1H, d, J = 14.7 Hz, HCH), 1.78-1.16 (6H, m, CH x 3), 0.74,
2
13
1
ν
(3H, t, J = 7.0 Hz, Me) ppm. C NMR (75 MHz, CDCl3):
δ 197.4, 176.9 (C=O), 143.5, 141.9, 140.9, 140.3 (arom C), 135.9,
128.5, 127.8, 127.6, 127.4, 127.3, 127.2, 126.6, 126.3, 125.7,
123.3, 116.3 (arom CH), 86.9 (COOH), 57.0 (C-3), 45.5, 44.8,
25.3, 22.8 (CH2
-
1
1
δ
3
7
(
13
3
.25 (1H, d, J = 14.1 Hz, HCH) ppm. C NMR (75 MHz,
170.4 (C=O), 143.4, 142.2, 140.3, 139.8 (arom C),
31.2, 129.1, 128.5, 128.3, 128.2, 128.0, 127.8, 127.6, 127.4,
27.0, 126.9, 126.7, 126.6, 126.4, 126.1, 123.7, 123.5, 116.5
x 4), 13.5 (Me) ppm. FAB HRMS
CDCl3):
1
1
δ
(acetone/NBA): calcd for C H NO 430.2018 (M+H); found
430.2021.
27
28
4
4
2
.3.27. 3-(2-Hydroperoxy-2,2-diphenylethyl)-3-phenylquinoline-
,4(1H,3H)-dione (8d: R = Ar =Ph). The product 8d could not be
(arom CH), 118.7 (arom C), 99.0 (C-10b), 86.0 (C-3), 52.4 (C-
4
a), 36.4 (CH ) ppm. FAB HRMS (acetone/NBA): calcd for
2
separated from 7d by silica gel chromatography. Colorless
microcrystals (from CH Cl /hexane), m.p. 151 °C. IR (KBr):
C H NO 450.1705 (M+H); found 450.1650.
29
24
4
ν
2
2
-
1 1
4
.3.23.
hydroxy-4a-methyl-1,2-dioxino[4,3-c]quinolin-5(3H)-one (7e: R
Me, Ar = 4-Cl-C H ). Pale yellow microcrystals (from MeOH),
3,3-Bis(4-chlorophenyl)-4,4a,6,10b-tetrahydro-10b-
3400-2940 (OOH and NH), 1697, 1659 (C=O) cm . H NMR
(300 MHz, CDCl3): 9.87 (1H, s, NH), 9.02 (1H, s, OOH), 7.77-
δ
=
7.74 (1H, m, arom H), 7.65-7.63 (1H, m, arom H), 7.52-7.01
6
4
m.p. 155-157 °C. IR (KBr):
1
ν
3400-3060 (OH), 3300-2900 (NH),
678 (C=O) cm . H NMR (300 MHz, CDCl ): 10.0 (1H, s,
NH), 7.85-7.76 (1H, m, arom H), 7.49-6.89 (10H, m, arom H),
(17H, m, arom H), 4.10 (1H, d, J = 14.1 Hz, HCH), 3.91 (1H, d,
-
1
1
13
δ
J = 14.1 Hz, HCH) ppm. C NMR (75 MHz, CDCl3):
δ
194.3,
3
175.3 (C=O), 143.8, 141.0, 138.1, 135.7 (arom C), 129.1, 128.5,
128.3, 128.2, 128.0, 127.8, 127.6, 127.4, 127.0, 126.9, 126.7,
126.6, 126.4, 126.1, 123.7, 123.5, 115.5 (arom CH), 120.5 (arom
6
1
.79-6.77 (1H, m, arom H), 5.45 (1H, s, OH), 3.54 (1H, d, J =
3.1 Hz, HCH), 2.78 (1H, d, J = 13.1 Hz, HCH), 1.15 (3H, s,
13
Me) ppm. C NMR (75 MHz, CDCl3):
arom C), 139.0 (2C, arom C), 135.6 (arom C), 130.5 (2C, arom
C), 129.3 (2C, arom CH), 128.0 (C-5), 126.9 (2C, arom CH),
δ
170.2 (C=O), 141.6
C), 87.2 (COOH), 60.8 (C-3), 42.6 (CH ). FAB HRMS
2
(
(acetone/NBA): calcd for C H NO 450.1705 (M+H); found
29
24
4
450.1650.
1
1
5
26.2 (2C, arom CH), 126.1 (acom CH), 125.8 (2C, arom CH),
22.3 (arom CH), 114.8 (arom CH), 98.0 (C-10b), 83.1 (C-3),
2.6 (C-4a), 43.0 (CH2), 21.4 (Me) ppm. FAB HRMS
4
.3.28.
3-[2-Hydroperoxy-2,2-bis(4-methylphenylethyl)]-3-
methylquinoline-2,4(1H,3H)-dione (8f: R = Me, Ar = 4-Me-
C H ). The product 8f could not be separated from 7f by silica
gel chromatography. IR (KBr):
6
4
(acetone/NBA): calcd for C H Cl NO 456.0769 (M+H); found
24 20 2 4
ν
3400-2877 (OOH and NH),
-
1
1
4
56.0779.
1
683 (C=O) cm . H NMR (300 MHz, CDCl ): 9.80 (1H, s,
δ
3
NH), 9.43 (1H, s, OOH), 7.83-6.67 (12H, m, arom H), 3.75 (1H,
d, J = 14.4 Hz, HCH), 3.70 (1H, d, J = 14.47 Hz, HCH), 2.04
4
.3.24.
4,4a,6,10b-Tetrahydro-10b-hydroxy-3,3-bis(4-
methylphenyl)-4a-methyl-1,2-dioxino[4,3-c]quinolin-5(3H)-one
7f: R = Me, Ar = 4-Me-C H ). The product 7f could not be
1
3
(
(
1
3H, s, Me), 1.93 (3H, s, Me), 1.28 (3H, s, Me) ppm. C NMR
75 MHz, CDCl3): 195.8, 175.5 (C=O), 141.1, 141.0, 140.5,
37.0, 136.6, 136.5 (arom C), 135.9, 130.2, 129.1, 128.9, 128.7,
128.5, 128.3, 127.4, 123.5, 122.5 (arom CH), 84.0 (COOH), 53.4
C-3), 44.6 (CH ), 22.1 (Me), 21.0 (Me), 16.2 (Me) ppm. FAB
(
6
4
δ
separated from 8f by silica gel chromatography. Orange
microcrystals (from MeOH), m.p. 192-193 °C; IR (KBr): 3400-
877 (OH and NH), 1683 (C=O) cm . H NMR (300 MHz,
CDCl3): 10.2 (1H, s, NH), 7.54-6.64 (12H, m, arom H), 5.22
1H, s, OH), 3.84 (1H, d, J = 14.4 Hz, HCH), 2.75 (1H, d, J =
ν
-
1
1
2
(
2
δ
HRMS (acetone/NBA): calcd for C H NO 382.1807 (M-
26
24
2
(
OOH); found 382.1847.
1
4.4 Hz, HCH), 2.15, 2.11 (6H, s, Me x 2), 1.53 (3H, s, Me) ppm.
C NMR (75 MHz, CDCl3):
13
δ 173.2 (C=O), 141.2, 140.9, 138.2,
4.4. Approach to the interconversion between 3a and 4a
1
1
37.8, 136.1, 136.0 (arom C), 129.9, 129.0 128.9, 128.1, 128.0,
27.4, 127.3, 126.9, 126.2, 126.6, 124.8, 122.9 (arom CH), 99.5
1
2
The bis(hydroperoxide) 3a (R = Me, Ar = Ar = Ph) and the
1
2
propellane 4a (R = Me, Ar = Ar = Ph) (0.1 mmol), respectively,
(C-10b), 86.0 (C-3), 52.4 (C-4a), 45.4 (CH ), 20.8 (Me), 20.7
2
were stirred in glacial acetic acid (10 mL) at room temperature in
(Me), 8.4 (Me) ppm. FAB HRMS (acetone/NBA): calcd for
the absence and the presence of Mn(OAc) (0.1 mmol) for 4
C H NO 382.1807 (M-OOH); found 382.1847.
3
26
24
2
hours. After the usual work-up, the bis(hydroperoxide) 3a and
the propellane 4a were recovered in 99% and 91%, respectively,
in the absence of the oxidant, while 3a in 48% and 4a in 83%
4
2
.3.25. 3-(2-Hydroperoxy-2,2-diphenylethyl)-3-propylquinoline-
,4(1H,3H)-dione (8b: R = Pr, Ar = Ph). The product 8b could
not be separated from 7b by silica gel chromatography. Colorless
microcrystals (from MeOH), m.p. 145-147 °C. IR (KBr): 3392-
873 (OOH and NH), 1680, 1662 (C=O) cm . H NMR (300
MHz, CHCl3): 9.68 (1H, s, NH), 9.33 (1H, s, OOH), 7.81-6.62
14H, m, arom H), 3.58 (1H, d, J = 14.7 Hz, HCH), 3.51 (1H, d,
J = 14.7 Hz, HCH), 2.12-2.08 (2H, t, J = 5.2 Hz, CH ), 1.23-0.96
recoveries in the presence of Mn(OAc) . No isolable products
were obtained from both reactions.
3
ν
-
1
1
2
4
4
.5. Mn(III)-mediated oxidation of alkenes in the presence of
-hydroxyquinolin-2(1H)-ones and the related substrates at
δ
(
reflux temperature
2
1
3
(
2H, m, CH ), 0.792 (3H, t, J = 7.0 Hz, Me) ppm. C NMR (75
2
A mixture of 1,1-diphenylethene 1 (Ar = Ph) (181.3 mg; 1
mmol), 4-hydroxy-2-quinolinone 2 (R = Me, X = H) (351.4 mg;
MHz, CHCl3):
δ 197.2, 176.9 (C=O), 143.5, 140.4, 136.2 (arom
C), 127.5, 127.4, 127.0, 126.5, 126.3, 125.5, 120.1, 119.8 (arom
2
mmol), and Mn(OAc) •2H O (814.4 mg; 3 mmol) in glacial
3 2
CH), 86.0 (COOH), 57.2 (C-3), 39.3, 36.0, 16.7 (CH ), 14.5 (Me)
2
acetic acid (25 mL) was heated under reflux until the brown color
of Mn(III) disappeared (normally for 3 minutes). The solvent was
removed in vacuo and water (25 mL) was added to the reaction
mixture. The aqueous solution was then extracted three times
with dichloromethane (20 mL). The combined extracts were
ppm. FAB HRMS (acetone/NBA): calcd forC H NO 416.1862
26
26
4
(M+H); found 416.1862.
4
2
.3.26.
3-Butyl-3-(2-hydroperoxy-2,2-diphenylethyl)quinoline-
,4(1H,3H)-dione (8c: R = Bu, Ar =Ph). The product 8c could
washed with
a
saturated aqueous solution of sodium
not be separated from 7c by silica gel chromatography. Yellow
hydrogencarbonate, dried over anhydrous sodium sulfate, and
then concentrated to dryness. The residue was separated on silica
gel TLC developed with 5% methanol/dichloromethane, giving
microcrystals (from CH Cl /hexane), m.p. 148-152 °C. IR (KBr):
2
2
-
1 1
ν
3500-2770 (OOH and NH), 1680, 1658 (C=O) cm . H NMR
(
300 MHz, CDCl3): 9.65 (1H, s, NH), 9.17 (1H, s, OOH), 7.81-
δ

1
1
the products 9a (310.6 mg; 87%) and 10a (23.6
A
m
C
g;
C
7%
E
)
P
(T
T
a
E
ble
D
3,MA
m
N
, a
U
romSCH)
R
, 7
I
.
P
41-7.25 (10H, m, arom H), 3.90 (2H, s, CH ),
2
13
T
entry 2). Molar ratio and reaction times of other oxidation are
shown in Tables 3, 4, and 5. The products were further purified
by recrystallization from an appropriate solvent for the analytical
sample, and their physical data are given below.
3.69 (3H, s, Me) ppm. C NMR (75 MHz, CDCl3):
δ 160.8,
160.7 (C=O and C=C), 142.5, 140.8, 134.0 (arom C), 131.2,
128.7, 127.3, 122.9, 121.8, 114.7 (arom CH), 112.3, 107.4 (arom
C), 94.7 (C-2), 42.6 (CH ), 29.1 (Me) ppm. Anal. Calcd for
2
C H Cl NO : C, 68.26; H, 4.06; N, 3.32. Found: C, 68.29; H,
4.17; N, 3.59.
24
17
2
2
4
4
.5.1.
3,5-Dihydro-5-methyl-2,2-diphenylfuro[3,2-c]quinolin-
10c
(2H)-one (9a: R = Me, X = H, Ar = Ph). Yield 87% (Table 3,
entry 2).
4.5.8.
2,2-Bis(4-chlorophenyl)-3,9-dihydro-9-methylfuro[2,3-
b]quinolin-4(2H)-one (10f: R = Me, X = H, Ar = 4-Cl-C H ).
6
4
4
4
2
.5.2.
3,9-Dihydro-9-methyl-2,2-diphenylfuro[2,3-b]quinolin-
10c
Yield 12% (Table 3, entry 7). Colorless microcrystals (from
(2H)-one (10a: R = Me, Ar = Ph). Yield 7% (Table 3, entry
).
-1 1
MeOH), m.p. 124-125 °C. IR (KBr):
NMR (300 MHz, CDCl3): 8.43 (1H, d, J = 7.8 Hz, arom H),
7.63-7.28 (11H, m, arom H), 3.95 (2H, s, CH ), 3.82 (3H, s, Me)
191.7 (C=O), 159.5 (C=C),
141.5, 138.6, 134.3 (arom C), 131.3, 128.7, 127.2, 126.4, 123.4,
114.3 (arom CH), 98.3 (C-9a), 95.0 (C-2), 40.9 (CH ), 31.5 (Me)
NO
ν 1589 (C=O) cm . H
δ
4
4
.5.3.
5-Ethyl-3,5-dihydro-2,2-diphenylfuro[3,2-c]quinolin-
2
13
(2H)-one (9b: R = Et, X = H, Ar = Ph). Yield 73% (Table 3,
ppm. C NMR (75 MHz, CDCl ): δ
3
entry 3). Colorless microcrystals (from MeOH), m.p. 181-182 °C.
-
1
1
IR (KBr):
8.01-7.99 (1H, m, arom H), 7.59-7.25 (13H, m, arom H), 4.35
2H, q, J = 7.0 Hz, CH ), 3.97 (2H, s, CH ), 1.33 (3H, t, J = 7.0
ν
1666 (C=O) cm . H NMR (300 MHz, CDCl ):
2
3
δ
(
ppm. FAB HRMS (acetone/NBA): calcd for C24
422.0715 (M+H); found 422.0720.
H18Cl
2
2
2
2
13
Hz, Me) ppm. C NMR (75 MHz, CDCl3):
and C=C), 144.5, 139.8 (arom C), 130.9, 128.3, 127.7, 125.8,
1
2
δ 161.0, 160.6 (C=O
4
.5.9.
3,5-Dihydro-2,2-bis(4-methylphenyl)-5-methylfuro[3,2-
c]quinolin-4(2H)-one (9g: R = Me, X = H, Ar = 4-Me-C H ).
6
4
23.3, 121.4, 114.5 (arom CH), 112.8, 107.7 (arom C), 95.7 (C-
), 42.8, 36.9 (CH2 x 2), 13.1 (Me) ppm. FAB HRMS
Yield 93% (Table 3, entry 8). Colorless microcrystals (from
-1
1
MeOH), m.p. 148-150 °C. IR (KBr):
NMR (300 MHz, CDCl3): 7.907.88 (1H, m, arom H), 7.43-7.08
11H, m, arom H), 3.93 (2H, s, CH ), 3.58 (3H, s, Me), 2.25 (6H,
ν 1640 (C=O) cm . H
(acetone/NBA): calcd for C H NO 368.1651 (M+H); found
25 22 2
δ
3
68.1688.
(
2
13
4
4
.5.4.
3,5-Dihydro-2,2-diphenyl5-propylfuro[3,2-c]quinolin-
s, Me x 2) ppm. C NMR (75 MHz, CDCl ) δ 160.7, 160.6 (C=O
3
(2H)-one (9c: R = Pr, X = H, Ar = Ph). Yield 76% (Table 3,
and C=C), 141.4, 140.2, 137.1 (arom C), 130.6, 128.7, 125.4,
122.6, 121.2, 114.1 (arom CH), 112.1, 107.3 (arom C), 95.5 (C-
entry 4). Colorless needles (from MeOH), m.p. 161 °C. IR (KBr):
ν
-
1
1
1662 (C=O) cm . H NMR (300 MHz, CDCl ):
δ
8.07-7.98
2), 42.3 (CH ), 28.6 (Me), 20.6 (2C, Me x 2) ppm. FAB HRMS
2
3
(
3
=
1H, m, arom H), 7.57-7.11 (13H, m, arom H), 4.23 (2H, m, CH2),
(acetone/NBA): calcd for C26
382.1852.
H24NO 382.1807 (M+H); found
2
.97 (2H, s, CH ), 1.76-1.55 (2H, m, CH CH CH ), 1.03 (3H, t, J
2 2 2 3
13
7.3 Hz, Me) ppm. C NMR (75 MHz, CDCl3): δ 161.0, 160.9
4
4
.5.10. 3,5-Dihydro-8-methyl-2,2-diphenylfuro[3,2-c]quinolin-
(2H)-one (9h: R = H, X = 8-Me, Ar = Ph). Yield 44% (Table 3,
(
1
(
C=O and C=C), 144.6, 140.0 (arom C), 130.8, 128.4, 128.3,
27.7, 127.5, 125.8, 123.2, 114.6 (arom CH), 121.4, 112.7, 107.6
arom C), 95.6 (C-2), 43.5, 42.8, 21.1 (CH ), 11.4 (Me) ppm.
entry 9). Colorless microcrystals (from MeOH), m.p. 269-270 °C.
2
-1
1
IR (KBr):
MHz, DMSO-d6):
H), 3.88 (2H, s, CH ), 2.59 (3H, Me) ppm. C NMR (75 MHz,
ν
3000-2729 (NH), 1654 (C=O) cm . H NMR (300
FAB HRMS (acetone/NBA): calcd for C H NO 382.1807
26
24
2
δ
11.5 (1H, s, NH), 7.89-7.35 (13H, m, arom
(M+H); found 382.1834.
13
2
4
4
.5.5.
5-Benzyl-3,5-Dihydro-2,2-diphenylfuro[3,2-c]quinolin-
DMSO-d
(arom C), 132.3, 128.5, 127.7, 125.3, 121.2, 115.5 (arom CH),
110.5, 107.7 (arom C), 95.0 (C-2), 41.6 (CH ), 20.4 (Me) ppm.
354.1494
6
): δ 161.0, 160.3 (C=O and C=C), 144.6, 137.8, 130.9
(2H)-one (9d: R = Bn, X = H, Ar = Ph). Yield 85% (Table 3,
entry 5). Pale orange microcrystals (from MeOH), m.p. 221 °C.
IR (KBr):
δ
2
-
1
1
ν
1656 (C=O) cm . H NMR (300 MHz, CDCl ):
FAB HRMS (acetone/NBA): calcd for C24
(M+H); found 354.1505.
H20NO
2
3
7.99-7.97 (1H, m, arom H), 7.53-7.17 (18H, m, arom H), 5.52
13
(2H, br. s, CH ), 4.04 (2H, s, CH ) ppm. C NMR (75 MHz,
2
2
4
4
.5.11. 3,5-Dihydro-6-methyl-2,2-diphenylfuro[3,2-c]quinolin-
(2H)-one (9i: R = H, X = 6-Me, Ar = Ph). Yield 67% (Table 3,
CDCl3):
δ 161.5, 161.3 (C=O and C=C), 144.5, 140.2, 136.8
(arom C), 131.1, 128.7, 128.5, 127.9, 127.1, 126.5, 125.8, 123.2,
entry 10). Only slightly soluble in organic solvents. Colorless
microcrystals (from MeOH), m.p. 263-267 °C. IR (KBr): 3300-
1
4
21.9, 115.6 (arom CH), 112.7 107.4 (arom C), 95.9 (C-2), 45.6,
2.7 (CH ) ppm. FAB HRMS (acetone/NBA): calcd for
ν
2
-1 1
3
000 (NH), 1670 (C=O) cm . H NMR (500 MHz, DMSO-d ):
6
C H NO 430.1807 (M+H); found 430.1815.
30
24
2
δ
10.7 (1H, s, NH), 7.90-7.18 (13H, m, arom H), 3.83 (2H, s,
13
4
.5.6.
3,5-Dihydro-2,2-diphenylfuro[3,2-c]quinolin-4(2H)-one
CH ), 2.39 (3H, Me) ppm. C NMR (125 MHz, DMSO-d ):
2
6
(9e: R = X = H, Ar = Ph). Yield 73% (Table 3, entry 6).
δ 169.5, 165.4 (C=O and C=C), 144.4, 140.2, 139.1, 138.0, 137.0,
Colorless microcrystals (from MeOH), m.p. 242 °C (decompd).
133.7, 132.2, 128.8, 128.4, 127.7, 127.6, 127.1, 126.1, 125.2,
124.4, 124.0, 121.9, 121.5, 119.8, 97.9, 95.1, 41.5, 17.6 ppm.
-
1 1
IR (KBr):
MHz, DMSO-d6):
ν
3200-2740 (NH), 1654 (C=O) cm . H NMR (300
11.5 (1H, s, NH), 8.30-7.79 (2H, m, arom H),
δ
FAB HRMS (acetone/NBA): calcd for C24
(M+H); found 354.1495.
H20NO 354.1494
2
13
7
.64-7.22 (12H, m, arom H), 3.80 (2H, CH ) ppm. C NMR (75
2
MHz, DMSO-d6):
δ
161.1, 160.5 (C=O and C=C), 144.5, 139.7
4
4
.5.12. 8-Chloro-3,5-dihydro-2,2-diphenylfuro[3,2-c]quinolin-
(2H)-one (9j: R = H, X = 8-Cl, Ar = Ph). Yield 58% (Table 3,
(arom C), 131.0, 128.8, 1.28.5, 127.7, 127.2, 126.2, 125.3, 121.9,
1
21.7, 115.6 (arom CH), 110.6, 107.8 (arom C), 95.2 (C-2), 41.6
entry 11). Colorless microcrystals (from MeOH), m.p. 281-
(
CH ) ppm. Anal. Calcd for C H NO •2H O: C, 79.29; H, 5.21;
-1
1
2
23 17
2
2
2
83 °C. IR (KBr):
NMR (300 MHz, DMSO-d6):
arom H), 7.61-7.58 (5H, m, arom H), 7.35-7.28 (7H, m, arom H),
ν
3150-2721 (NH), 1680 (C=O) cm . H
N, 4.02. Found: C, 79.45; H, 4.87; N, 4.04.
δ
11.6 (1H, s, NH), 7.96 (1H, m,
4
.5.7. 2,2-Bis(4-chlorophenyl)-3,5-dihydro-5-methylfuro[3,2-
13
c]quinolin-4(2H)-one (9f: R = Me, X = H, Ar = 4-Cl-C H ).
3.81 (2H, CH ) ppm. C NMR (75 MHz, DMSO-d ): δ 160.2,
2
6
6
4
Yield 87% (Table 3, entry 7). Colorless microcrystals (from
160.1 (C=O and C=C), 144.4, 138.4, 125.8 (arom C), 131.0,
128.5, 127.7, 125.3, 121.0, 117.5 (arom CH), 111.7, 109.0 (arom
-
1 1
EtOH), m.p. 194-195 °C. IR (KBr):
ν 1645 (C=O) cm . H NMR
(
300 MHz, CDCl3): 7.94-7.92 (1H, m, arom H), 7.59-7.57 (1H,
δ

1
2
Tetrahedron
C), 95.6 (C-2), 41.5 (CH ) ppm. FAB HRM
A
S
C
(ac
C
et
E
on
P
e/
T
NB
E
A
D
): MA3.
N
39
U
(1
S
H
C
, d
R
d,
I
J
P
= 15.4, 9.5 Hz, -CH -), 3.12 (1H, dd, J = 15.4, 7.7
2
13
T
2
calcd for C H ClNO 374.0948 (M+H); found 374.0952.
Hz, -CH -) ppm. C NMR (75 MHz, CDCl3):
δ
162.0, 161.1
23
17
2
2
(
(
(
(
C
4
C=O and -CO=), 143.8 (Ph >C=), 140.5, 139.2, 136.5, 134.3
arom C), 131.2, 131.0, 129.0, 128.8, 128.5, 127.4, 123.1, 121.6
arom CH), 114.5 (=CH-), 112.4 (arom C), 107.8 (>C=), 83.0
2
4
4
.5.13. 6-Chloro-3,5-dihydro-2,2-diphenylfuro[3,2-c]quinolin-
(2H)-one (9k: R = H, X = 6-Cl, Ar = Ph). Yield 99% (Table 3,
entry 12). Only slightly soluble in organic solvents. Colorless
microcrystals (from MeOH), m.p. 254-255 °C. IR (KBr): 3200-
3
>CH-), 35.1 (-CH -), 29.1 (Me) ppm. Anal. calcd for
2
ν
-
1
1
26
H19Cl
2
NO
2
: C, 69.65; H, 4.27; N, 3.12. Found: C, 69.37; H,
000 (NH), 1660 (C=O) cm . H NMR (500 MHz, DMSO-d ):
6
.18; N, 3.04.
δ
10.8 (1H, s, NH), 7.95-7.28 (13H, m, arom H), 3.85 (2H, s,
13
CH ) ppm. C NMR (125 MHz, DMSO-d6):
δ
161.0, 160.2
4.5.18.
3,5-Dihydro-2-[2,2-bis(4-methylphenyl)ethenyl]-5-
2
(
1
C=O and C=C), 144.3, 136.0, 131.3 (arom C), 128.6, 127.2,
26.2, 125.4, 122.6, 121.3, 118.9 (arom CH), 112.4, 108.9 (arom
methylfuro[3,2-c]quinolin-4(2H)-one (9p: R = Me, X = H, Ar =
4-Me-C H ). Yield 71% (Table 3, entry 17). R = 0.30 (Et O-
6
4
f
2
C), 95.8 (C-2), 41.5 (CH ) ppm. FAB HRMS (acetone/NBA):
hexane 8:2 v/v). Colorless microcrystals (from Et O), mp 160 °C.
2
-1 1
2
calcd for C H ClNO 374.0948 (M+H); found 374.0945.
IR (KBr):
ν
1657 (C=O), 1636 (C=C) cm . H NMR (300 MHz,
7.79-7.76 (1H, m, arom H), 7.57-7.52 (1H, m, arom H),
.35-7.08 (10H, m, arom H), 6.23 (1H, d, J = 9.5 Hz, =CH-),
.52 (1H, dt, J = 7.7, 9.5 Hz, >CH-), 3.68 (3H, s, N-Me), 3.39
-), 3.12 (1H, dd, J = 15.4, 7.7 Hz,
23
17
2
CDCl3):
7
5
δ
4
4
.5.14. 8-Fluoro-3,5-dihydro-2,2-diphenylfuro[3,2-c]quinolin-
(2H)-one (9l: R = H, X = 8-F, Ar = Ph). Yield 74% (Table 3,
entry 13). Colorless microcrystals (from MeOH), m.p. 248 °C
-
1
1
(1H, dd, J = 15.4, 9.5 Hz, -CH
CH -), 2.40 (3H, s, Me), 2.33 (3H, s, Me) ppm. C NMR (75
2
(
decompd). IR (KBr):
NMR (300 MHz, DMSO-d6):
m, arom H), 3.81 (2H, CH ) ppm. C NMR (75 MHz, DMSO-
ν
3180-2900 (NH), 1670 (C=O) cm . H
13
-
2
δ
11.6 (1H, s, NH), 7.84-7.25 (13H,
13
MHz, CDCl
3
):
δ 162.2, 161.2 (C=O and -CO=), 145.9 (Ph >C=),
2
2
1
1
1
40.5, 138.5, 138.0, 137.7, 135.8 (arom C), 130.8, 129.9, 129.0,
28.9, 127.8, 125.4, 123.2, 121.5 (arom CH), 114.4 (=CH-),
d6):
δ
160.5, 160.2 (C=O and C=C), 155.3 (C-8), 144.4, 136.5
(arom C), 128.5, 127.7, 125.3, 119.3, 117.6, 107.2 (arom CH),
12.6 (arom C), 108.0 (>C=), 83.8 (>CH-), 35.2 (-CH -), 29.0
2
1
09.0 (arom C), 95.4 (C-2), 41.6 (CH ) ppm. FAB HRMS
2
(
N-Me), 21.3 (Me), 21.1 (Me) ppm. Anal. calcd for C H NO :
28 25 2
(
acetone/NBA): calcd for C H FNO 358.1243 (M+H); found
23 17 2
C, 82.53; H, 6.18; N, 3.44. Found: C, 82.24; H, 6.19; N, 3.33.
3
58.1244.
.5.15. 3,5-Dihydro-5-methyl-2-(2,2-diphenylethenyl)furo[3,2-
4
4
.5.19. 3,5,6,7,8,9-Hexahydro-2,2-diphenylfuro[3,2-c]quinolin-
(2H)-one (12). Yield 53% (Table 4, entry 1). Only slightly
4
c]quinolin-4(2H)-one (9m: R = Me, X = H, Ar = Ph). Yield 71%
Table 3, entry 14). R = 0.16 (Et O-hexane 8:2 v/v). Colorless
soluble in organic solvents. Colorless cubics (from MeOH), m.p.
(
-1 1
f
2
2
81-283 °C. IR (KBr):
ν
3200-2900 (NH), 1651 (C=O) cm . H
): 11.05 (1H, s, NH), 7.50-7.48 (4H,
microcrystals (from Et O), mp 161 °C. IR (KBr):
ν
1659 (C=O),
7.78-7.76 (1H,
m, arom H), 7.57-7.17 (13H, m, arom H), 6.29 (1H, d, J = 9.5 Hz,
CH-), 5.50 (1H, dt, J = 7.7, 9.5 Hz, >CH-), 3.67 (3H, s, Me),
.39 (1H, dd, J = 15.4, 9.5 Hz, -CH -), 3.13 (1H, dd, J = 15.4, 7.7
2
-
1
1
NMR (500 MHz, DMSO-d
6
δ
1
638 (C=C) cm . H NMR (300 MHz, CDCl ): δ
3
m, arom H), 7.38-7.35 (4H, m, arom H), 7.29-7.26 (2H, m, arom
H), 3.63 (2H, s, CH ), 2.45 (2H, s, CH ), 1.69 (6H, s, CH ) ppm.
2
2
2
=
13
C NMR (125 MHz, DMSO-d6):
δ 165.4, 160.1 (C=O and -
3
2
13
CO=), 144.9, 144.6 (arom C), 128.4, 127.5, 125.3 (arom CH),
04.4, 101.3 (arom C), 94.1 (C-2), 41.1 (CH ), 26.0 (CH ), 21.34
Hz, -CH -) ppm. C NMR (75 MHz, CDCl3):
δ 162.2 (C=O),
2
1
2
2
1
1
1
8
61.2 (-CO=), 146.0 (Ph >C=), 141.1, 140.5, 138.6 (arom C),
30.9, 129.9, 128.4, 128.3, 128.1, 128.0, 127.8, 126.5, 123.2,
21.5 (arom CH), 114.4 (=CH-), 112.6 (arom C), 108.0 (>C=),
2
(
CH ), 21.30 (CH ), 20.4 (CH ) ppm. Anal. Calcd for C H NO :
2 2 2 23 21 2
C, 80.44; H, 6.16; N, 4.08. Found: C, 80.47; H, 6.16; N, 3.98.
3.5 (>CH-), 35.2 (-CH -), 29.0 (Me). Anal. calcd for
4.5.20. 5-Benzyl-3,5,6,7-tetrahydro-2,2-diphenylfuro[3,2-
2
4a
C H NO : C, 82.30; H, 5.58; N, 3.69. Found: C, 82.08; H,
c]pyridin-4(2H)-one (14). Yield 52% (Table 4, entry 2). Yellow
26
21
2
-
1
1
5
.53; N, 3.60.
oil; IR (CHCl ): ν 1680 (C=O) cm . H NMR (300 MHz,
3
CDCl ): δ 7.40-7.20 (15H, m, arom H), 4.58 (2H, s, Ph-CH ),
3
2
4
.5.16.
2-[2,2-Bis(4-fluorophenyl)ethenyl]-3,5-dihydro-5-
3
.67 (2H, t, J = 2.2 Hz, H-3), 3.35 (2H, t, J = 7.2 Hz, H-6), 2.55
13
methylfuro[3,2-c]quinolin-4(2H)-one (9n: R = Me, X = H, Ar =
-F-C H ). Yield 58% (Table 3, entry 15). R = 0.12 (Et O-
(2H, tt, J = 7.2, 2.2 Hz, H-7) ppm. C NMR (75 MHz, CDCl ): δ
3
4
6
4
f
2
1
65.6, 164.7 (C=O and C-7a), 144.8, 137.9 (arom C), 128.6,
128.4, 128.0, 127.7, 127.3, 125.7 (arom CH), 104.8 (C-3a), 95.4
C-2), 48.9 (Ph-CH ), 44.3 (C-6), 42.0 (C-3), 23.3 (C-7). FAB
hexane 8:2 v/v). Colorless microcrystals (from Et O), mp 179-
1
2
-
1
1
81 °C. IR (KBr):
ν
δ
1659 (C=O), 1636 (C=C) cm . H NMR
7.79-7.77 (1H, m, arom H), 7.60-7.58 (1H,
(
2
(300 MHz, CDCl3):
HRMS (acetone/NBA): calcd for C H NO 382.1807 (M+H);
26
23
2
m, arom H), 7.55-6.97 (10H, m, arom H), 6.23 (1H, d, J = 9.5 Hz,
CH-), 5.47 (1H, dt, J = 7.7, 9.5 Hz, >CH-), 3.70 (3H, s, Me),
.41 (1H, dd, J = 15.4, 9.5 Hz, -CH -), 3.13 (1H, dd, J = 15.4, 7.7
found 382.1812.
=
3
4.5.21. 2,3-Dihydro-2,2-diphenyl-4H-furo[3,2-c][1]benzopyran-
4-one (16a). Yield 89% (Table 4, entry 13). Colorless
microcrystals (from EtOH), m.p. 185-186 °C. H NMR (300
2
13
Hz, -CH -) ppm. C NMR (75 MHz, CDCl3):
δ 164.4, 161.2
2
(C=O and C=C), 162.1 (C-F), 144.2 (Ph >C=), 140.6, 137.2,
2
1
1
37.1, 134.4, 134.3 (arom C), 131.7, 131.6, 131.0, 129.6, 129.5,
26.7, 123.2, 121.6, 115.7, 115.4, 115.1 (arom CH), 114.5 (=CH-
MHz, CDCl3):
δ 7.87-7.84 (1H, m, arom H), 7.61-7.56 (1H, m,
arom H), 7.47-7.25 (12H, m, arom H), 3.91 (2H, s, CH ) ppm.
2
13
), 112.5 (arom C), 107.9 (>C=), 83.3 (>CH-), 35.2 (-CH -), 29.1
C NMR (75 MHz, CDCl3): δ 165.0 (C=O), 155.1 (C=C), 143.5
2
(
Me) ppm. Anal. calcd for C H F NO : C, 75.17; H, 4.61; N,
(arom C), 132.4, 128.6, 128.2, 125.7, 124.0, 122.7, 117.0 (arom
26
19
2
2
3
.37. Found: C, 75.16; H, 4.73; N, 3.36.
CH), 112.4 (C-9a), 101.7 (C-3a), 97.4 (C-2), 41.5 (CH ) ppm.
2
FAB HRMS (acetone/NBA): calcd for C H O 341.1178
23
17
3
4
.5.17. 2-[2,2-Bis(4-chlorophenyl)ethenyl]-3,5-dihydro-5-
(M+H); found 341.1207.
methylfuro[3,2-c]quinolin-4(2H)-one (9o: R = Me, X = H, Ar =
-Cl-C H ). Yield 69% (Table 3, entry 16). R = 0.13 (Et O-
4
4.5.22.
2,2-Bis(4-chlorophenyl)-2,3-dihydro-4H-furo[3,2-
6
4
f
2
hexane 8:2 v/v). Colorless microcrystals (from Et O), mp 123-
c][1]benzopyran-4-one (16b). Yield 87% (Table 4, entry 4).
2
-
1
1
1
24 °C. IR (KBr):
ν
δ
1659 (C=O), 1636 (C=C) cm . H NMR
7.76-7.74 (1H, m, arom H), 7.59-7.53 (1H,
Colorless microcrystals (from EtOH), m.p. 196-197 °C. IR
-
1
1
(300 MHz, CDCl3):
(KBr):
CDCl3):
7.41-7.32 (10H, m, arom H), 3.84 (2H, s, CH ) ppm. C NMR
ν
1717 (C=O), 1651 (C=C) cm . H NMR (500 MHz,
m, arom H), 7.43-7.18 (10H, m, arom H), 6.27 (1H, d, J = 9.5 Hz,
CH-), 5.45 (1H, dt, J = 7.7, 9.5 Hz, >CH-), 3.68 (3H, s, Me),
δ 7.83-7.81 (1H, m arom H), 7.61-7.58 (1H, m arom H),
1
3
=
2

1
3
(
125 MHz, CDCl3):
C-O), 141.6, 134.4 (arom C), 132.7, 128.9, 127.1, 124.1, 122.6,
17.1 (arom CH), 112.2 (C-9a), 101.5 (C-3a), 96.3 (C-2), 41.3
δ
164.7 (O-C=C), 159.9 (C
A
=O
C
)
C
, 1
E
55
P
.1
T
(a
E
ro
D
m
MA
=
N
9.5
U
H
S
z
C
, =
R
C
I
H-), 5.23 (1H, dt, J = 7.7, 9.5 Hz, >CH-), 3.01
P
T
(1H, dd, J = 14.7, 9.9 Hz, -CH -, H-3), 2.73 (1H, dd, J = 14.7, 7.7
Hz, -CH -, H-3), 2.30 (2H, s, -CH -, H-5), 2.23 (2H, s, -CH -, H-
7), 1.12 (3H, s, Me), 1.09 (3H, s, Me) ppm. C NMR (75 MHz,
CDCl3): 194.6 (C=O), 175.9 (-CO=), 143.9, 139.1 (arom C),
36.4 (Ph >C=), 134.3 (arom C), 131.2, 129.0, 128.8, 128.5
2
1
2
2
2
13
(CH ) ppm. Anal. Calcd for C H Cl O •1/9H O: C, 67.17; H,
2
23 14
2
3
2
3
.49. Found: C, 67.03; H, 3.37.
δ
1
(
2
4
.5.23.
2,3-Dihydro-2,2-bis(4-methylphenyl)-4H-furo[3,2-
arom CH), 127.2 (=CH-), 111.5 (>C=), 83.0 (>CH-), 50.9 (-
CH -, C-5), 37.9 (-CH -, C-7), 34.1 (>C<), 32.9 (-CH -, C-3),
c][1]benzopyran-4-one (16c). Yield 82% (Table 4, entry 5).
Colorless needles (from EtOH), m.p. 121 °C. IR (KBr):
2
2
2
ν
1719
7.83-
-
1
1
28.7 (2Me) ppm. Anal. calcd for C24
Found: C, 69.44; H, 5.26.
H22Cl
2
O
2
: C, 69.74; H, 5.36.
(C=O), 1649 (C=C) cm . H NMR (500 MHz, CDCl ): δ
3
7
.82 (1H, m, arom H), 7.57-7.54 (1H, m arom H), 7.39-7.37 (1H,
m, arom H), 7.33-7.31 (5H, m, arom H), 7.17-7.15 (4H, m, arom
4.5.28.
7a,3a-(Epoxyethano)-6,7-dihydro-6,6-dimethyl-9-(2,2-
7:1
13
H), 3.86 (2H, s, CH ), 2.33 (6H, s, Me x 2) ppm. C NMR (125
diphenylethenyl)-2-phenylbenzofuran-4(5H)-one (22).
A
2
MHz, CDCl3):
40.8, 138.0 (arom C), 132.3, 129.1, 125.7, 123.9, 122.7, 116.9
arom CH), 112.5 (C-9a), 101.7 (C-3a), 97.6 (C-2), 41.45 (CH2),
δ
165.0 (O-C=C), 160.3 (C=O), 155.0 (arom C-O),
diastereomixture was obtained and the diasteromers could not be
1
(
isolated each other. Yield 58% (Table 4, entry 10). R = 0.43
f
(Et O-hexane 3:7 v/v). Colorless amorphous. IR (CHCl ):
ν
1705
7.66-7.07 (15H, m,
arom H), 5.98 (1H, d, J = 8.8 Hz, =CH-), 5.24 (1H, s, =CH-),
.70-4.62 (1H, m, >CH-), 2.43-2.09 (6H, m, -CH - x 3), 1.05 (3H,
2
3
-
1 1
2
1.0 (Me x 2) ppm. Anal. Calcd for C H O •1/8H O: C, 81.01;
(C=O) cm . H NMR (300 MHz, CDCl ): δ
25
20
3
2
3
H, 5.51. Found: C, 80.94; H, 5.34.
4
2
4
4
.5.24. 2,3-Dihydro-6-methyl-2,2-diphenyl-4H-furo[3,2-c]pyran-
-one (18). Yield 56% (Table 4, entry 6). Colorless microcrystals
1716 (C=O), 1273
7.38-7.29 (10H, m, arom H),
13
s, Me), 0.97 (3H, s, Me) ppm. C NMR (75 MHz, CDCl3):
δ
2
09.9 (C=O), 156.5 (Ph-CO=), 146.2 (acom C), 141.8 (Ph >C=),
2
(from MeOH), m.p. 151-152 °C. IR (KBr): ν
-1 1
138.7 (arom C), 129.7, 129.1, 128.3, 128.1, 127.8, 126.7 (arom
CH), 125.5 (Ph >C=CH-), 118.5 (C-7a), 98.0 (C-3), 76.3 (C-9),
7.3 (C-3a), 51.7, 46.8, 43.9 (-CH - x 3), 32.0 (C-6), 29.2, 28.7
cm . H NMR (500 MHz, CDCl ):
6
δ
3
13
2
.08 (1H, s, =CH), 3.74 (2H, s, CH ), 2.26 (3H, s, Me) ppm. C
2
6
2
NMR (125 MHz, CDCl3):
δ 169.7 (C-7a), 165.5 (C=O), 161.7
(
Me) ppm. FAB HRMS (acetone-NBA) calcd for C H O
32 30 3
(C-6), 143.6 (arom C), 128.4, 1278.0, 125.6 (arom CH), 98.9 (C-
4
62.2195 (M). Found 462.2196.
3,3a,5,9b-Tetrahydro-9b-hydroxy-3a-methyl-2,2-
3
a), 96.8 (C-2), 95.6 (C-7), 40.2 (CH ), 20.4 (Me) ppm. FAB
2
HRMS (acetone/NBA): calcd for C H O 305.1178 (M+H);
4.5.29.
20
17
3
found 305.1211.
diphenylfuro[3,2-c]quinolin-4(2H)-one (23a: R = Me, Ar = Ph).
Colorless microcrystals (from MeOH), m.p. 217-225 °C
4
.5.25.
6,6-Dimethyl-2-(2,2-diphenylethenyl)-2,3,6,7-
(
(
7
decompd). IR (KBr):
ν
3500-3400 (NH), 3400-3060 (OH), 1649
C=O) cm . H NMR (300 MHz, CDCl ): 10.2, (1H, s, NH),
.92-7.90 (1H, m, arom H), 7.54-7.51 (2H, m, arom H), 7.32-
6.91 (10H, m, arom H), 6.64 (1H, m, arom H), 3.73 (1H, d, J =
tetrahydrobenzofuran-4(5H)-one (20a). Yield 78% (Table 4,
entry 7). R = 0.22 (Et O-hexane 5:5 v/v). Colorless needles
-1 1
δ
3
f
2
(from EtOH), mp 139-141 °C. IR (KBr):
ν
1647, 1626 (C=C-
-
1 1
C=O) cm . H NMR (300 MHz, CDCl ):
δ 7.40-7.21 (10H, m,
3
1
2
1.9 Hz, Ha-3), 3.42 (1H, s, OH), 2.96 (1H, d, J = 11.9 Hz, Hb-3),
arom H), 6.15 (1H, d, J = 9.5 Hz, =CH-), 5.28 (1H, dt, J = 7.7,
.5 Hz, >CH-), 3.01 (1H, dd, J = 14.3, 9.5 Hz, -CH -, H-3), 2.74
13
.07 (3H, s, Me) ppm. C NMR (75 MHz, CDCl3):
δ 172.1
9
2
(
C=O), 149.6, 147.0 (arom C), 135.7, 129.5, 127.8, 127.6, 126.8,
26.7, 126.1, 125.9, 125.5, 125.0, 123.5, 121.9, 102.7, 85.9 (C-2),
53.6 (C-3a), 46.7 (CH ), 18.4 (Me) ppm. Anal. Calcd for
C H NO : C, 77.61; H, 5.70; N, 3.77. Found: C, 77.46; H, 5.52;
(1H, dd, J = 14.3, 7.7 Hz, -CH -, H-3), 2.29 (2H, s, -CH -, H-5),
2
2
1
2
.22 (2H, s, -CH -, H-7), 1.11 (3H, s, Me), 1.08 (3H, s, Me) ppm.
2
C NMR (75 MHz, CDCl ):
13
2
δ
194.6 (C=O), 176.1 (-CO=), 146.1
3
24
21
3
(arom C), 141.0 (Ph >C=), 138.5 (arom C), 129.8, 128.3, 128.2,
2
N, 3.80.
1
28.1, 127.9, 127.8 (arom CH), 126.2 (=CH-), 111.5 (>C=), 83.6
(
>CH-), 50.9 (-CH -, C-5), 37.9 (-CH -, C-7), 34.0 (>C<), 32.9 (-
4.5.30.
3,3a,5,9b-Tetrahydro-9b-Hydroxy-2,2-diphenyl-3a-
2
2
CH -, C-3), 28.7 (2Me) ppm. Anal. calcd for C H O : C, 83.69;
H, 7.02. Found: C, 83.43; H, 7.01.
propylfuro[3,2-c]quinolin-4(2H)-one (23b: R = Pr, Ar = Ph).
The compound 23b could not be separated from 24b. Colorless
2
24 24
2
microcrystals (from MeOH), m.p. 220-222 °C. IR (KBr):
2
ν
3454-
875 (OH and NH), 1689 (C=O) cm . H NMR (300 MHz,
CDCl3): 9.76 (1H, s, NH), 7.71-6.66 (14H, m, arom H), 3.45
(2H, s, CH ), 2.08-1.01 (4H, m, CH x 2), 2.01 (1H, s, OH), 0.86
3H, t, J = 7.0 Hz, Me) ppm. FAB HRMS (acetone/NBA): calcd
for C H NO 399.1834 (M); found 399.1836.
4
.5.26. 2-[2,2-Bis(4-fluorophenyl)ethenyl]-6,6-dimethyl-2,3,6,7-
-1
1
tetrahydrobenzofuran-4(5H)-one (20b). Yield 55% (Table 4,
entry 8). R = 0.18 (Et O-hexane 5:5 v/v). Colorless amorphous.
IR (KBr):
7
5
δ
f
2
-
1
1
2
2
ν
1634 (C=O) cm . H NMR (300 MHz, CDCl ): δ
3
(
.29-6.96 (8H, m, arom H), 6.10 (1H, d, J = 9.5 Hz, =CH-),
.240 (1H, dt, J = 7.7, 9.5 Hz, >CH-), 3.02 (1H, dd, J = 14.3, 9.9
26
25
3
Hz, -CH -, H-3), 2.73 (1H, dd, J = 14.3, 7.7 Hz, -CH -, H-3),
4.5.31.
3a-Butyl-3,3a,5,9b-tetrahydro-9b-hydroxy-2,2-
2
2
2
.31 (2H, s, -CH -, H-5), 2.24 (2H, s, -CH -, H-7), 1.12 (3H, s,
diphenylfuro[3,2-c]quinolin-4(2H)-one (23c: R = Bu, Ar = Ph).
The compound 23c could not be separated from 24c. Pale yellow
2
2
13
Me), 1.01 (3H, s, Me) ppm. C NMR (75 MHz, CDCl3):
δ
194.6
C=O), 176.0 (-CO=), 164.4, 164.2, 161.1, 160.9 (arom C), 144.2
Ph >C=), 137.1, 134.3, 134.2 (arom C), 131.6, 131.5, 129.6,
(
(
microcrystals (from MeOH), m.p. 166 °C. IR (KBr):
ν
3400-
-
1 1
2900 (OH, NH), 1657 (C=O) cm . H NMR (300 MHz, CDCl ):
2
3
1
1
3
29.4 (arom CH), 126.5 (=CH-), 115.6, 115.4, 115.1 (arom CH),
11.5 (>C=), 83.3 (>CH-), 50.9 (-CH -, C-5), 37.9 (-CH -, C-7),
δ 9.92 (1H, s, NH), 7.61-6.84 (14H, m, arom H), 2.88 (1H, d, J =
13.8 Hz, HCH), 2.39 (1H, d, J = 13.8 Hz, HCH), 2.37 (1H, s,
2
2
4.1 (>C<), 33.0 (-CH -, C-3), 28.7 (2Me) ppm. FAB HRMS
OH), 1.28-1.07 (6H, m, CH x 3), 0.78 (3H, t, J = 7.0 Hz, Me)
2
2
(
acetone-NBA) calcd for C H F O 380.1666 (M+1). Found
ppm.
24
23
2
2
3
81.1669.
4
.5.32.
2,2-Bis(4-chlorophenyl)-3,3a,5,9b-tetrahydro-9b-
4
.5.27. 2-[2,2-Bis(4-chlorophenyl)ethenyl]-6,6-dimethyl-2,3,6,7-
hydroxy-3a-methylfuro[3,2-c]quinolin-4(2H)-one (23d: R = Me,
Ar = 4-Cl-C H ). The compound 23d could not be separated
tetrahydrobenzofuran-4(5H)-one (20c). Yield 63% (Table 4,
entry 9). R = 0.22 (Et O-hexane 5:5 v/v). Colorless plates (from
EtOH); mp 144-146 °C. IR (KBr):
6
4
from 24d. Colorless microcrystals (from MeOH); mp 221-223 °C.
f
2
-
1
1
-1
1
ν
1630 (C=O) cm . H NMR
IR (KBr):
NMR (300 MHz, DMSO-d6): δ
ν
3400-2877 (OH and NH), 1697 (C=O) cm . H
10.7 (1H, s, NH), 7.83-6.72 (12H,
(300 MHz, CDCl3): 7.40-7.14 (8H, m, arom H), 6.14 (1H, d, J
δ

1
4
Tetrahedron
), MAN
m, arm H), 3.40 (1H, s, OH), 3.53 (1H, d, J
.17 (1H, d, J = 13.0 Hz, HCH), 1.36 (3H, s, Me) ppm. FAB
HRMS (acetone/NBA): calcd for C H Cl NO 439.0742 (M);
A
=
C
13
C
.0
E
H
P
z,
T
H
E
CH
D
T
U
his
S
r
C
es
R
ea
I
rch was supported by Grants-in-Aid for Scientific
P
T
3
Research (C), No. 22550041 and No. 25410049, from the Japan
Society for the Promotion of Science, and also by a 2013-Core
Research Program, “Integrated Science for Molecular Chirality in
Biology and Chemistry,” Graduate School of Science and
Technology, Kumamoto university, Japan. We gratefully
acknowledge Professor Teruo Shinmyouzu and Dr. Mikio
Yasutake, Institute for Materials Chemistry and Engineering,
Kyushu University, Japan, for the measurement of the X-ray
analysis. We also acknowledge Nissan Chemical Industries, Ltd.,
and M. Y. thanks the Scientific and Technological Research
Council of Turkey, TUBITAK No. 2214, for their financial
support.
24
19
2
3
found 439.0648.
4
.5.33. 3-Methyl-3-(2,2-diphenylethenyl)quinoline-2,4(1H,3H)-
dione (24a: R = Me, Ar = Ph). Colorless microcrystals (from
MeOH), m.p. 160-161 °C. IR (KBr): 3550-3400 (NH), 1701,
655 (C=O) cm . H NMR (300 MHz, CDCl ): 9.97 (1H, s,
NH), 7.73-7.71 (1H, m, arom H), 7.39-7.21 (6H, m, arom H),
.02-6.80 (7H, m, arom H), 6.42 (1H, s, HC=), 1.79 (3H, s, Me)
ν
-
1
1
1
δ
3
7
13
ppm. C NMR (75 MHz, CDCl3):
δ
196.9, 175.9 (C=O),
44.5,140.8, 140.7, 138.7 (arom C), 135.6, 131.1, 129.9, 128.1,
27.7,127.6, 127.5, 127.4, 127.2, 123.0 (arom CH), 118.2
1
1
(
CH=C), 116.2 (CH=C), 56.3 (C-3), 27.6 (Me) ppm. Anal. Calcd
References and notes
for C H NO : C, 81.56; H, 5.42; N, 3.96. Found: C, 81.57; H,
24
19
2
5
4
.31; N, 3.91. FAB HRMS (acetone/NBA): calcd for C H NO
29 22 2
16.1651 (M+H); found 416.1638.
1
.
For review, see: a) Sainsbury, M. In Rodd’s Chemistry of Carbon
Compounds, 2nd ed.; Coffey, S., Ed.; Elsevier: Amsterdam, 1978;
Vol. 4, pp 171–255; b) Grundon, M. F. Nat. Prod. Rep. 1984, 1,
4
.5.34. 3-(2,2-Diphenylethenyl)-3-propylquinoline-2,4(1H,3H)-
1
95–200; c) Grundon, M. F. Nat. Prod. Rep. 1985, 2, 393–400; d)
dione (24b: R = Pr, Ar = Ph). The compound 24b could not be
separated from 23b. Colorless microcrystals (from MeOH), m.p.
Grundon, M. F. Nat. Prod. Rep. 1987, 4, 225–236; e) Grundon, M.
F. Nat. Prod. Rep. 1988, 5, 293–307; f) Grundon, M. F. The
Alkaloids: Quinoline Alkaloids Related to Anthranilic Acid,
Academic Press: London, 1988; Vol. 32, pp 341–439; g) Grundon,
M. F. Nat. Prod. Rep. 1990, 7, 131-138; h) Michael, J. P. Nat.
Prod. Rep. 1999, 16, 697–709; h) Larsen, R. D. Sci. Synth. 2005,
-
2
.
(
20-222 °C. IR (KBr):
ν
3200-2875 (NH), 1689, 1647 (C=O) cm
H NMR (300 MHz, CDCl3):
14H, m, arom H), 6.39 (1H, s, HC=), 2.37-2.34 (2H, m, CH2),
1
1
δ 9.90 (1H, s, NH), 7.71-6.86
1
.50-1.00 (2H, m, CH ), 0.79 (3H, t, J = 5.5 Hz, Me) ppm. FAB
2
1
5, 551–660; i) Hradil, P.; Hlavác, J.; Soural, M.; Hajdúch, M.;
HRMS (acetone/NBA): calcd for C H NO 382.1807 (M+H);
found 382.1885.
26
24
2
Kolái, M.; Veceiova, R. Mini-Rev. Med. Chem. 2009, 9, 696–702;
j) Mphahlele, M. J. J. Heterocycl. Chem. 2010, 47, 1–14.
2
.
a) Ahsan, M.; Gray, A. I.; Waterman, P. G. J. Nat, Prod. 1994,
57, 670–672; b) He, J.; Lion, U.; Sattler, I.; Gollmick, F. A.;
Grabley, S.; Cai, J.; Meiners, M.; Schünke, H.; Schaumann, K.;
Dechert, U.; Krohn, M. J. Nat, Prod. 2005, 58, 1387–1399; c)
Detsi, A.; Bouloumbasi, D.; Prousis, K. C.; Koufaki, M.;
Athanasellis, G.; Melagraki, G.; Afantitis, A.; Igglessi-
Markopoulou, O.; Kontogiorgis, C.; Hadjipavlou-Litina, D. J. J.
Med. Chem. 2007, 50, 2450–2458; d) Butenschön, I.; Möller, K.;
Hänsel, W. J. Med. Chem. 2001, 44, 1249–1256; e) Marques, E.
F.; Bueno, M. A.; Duarte, P. D.; Silva, L. R. S. P.; Martinelli, A.
M.; dos Santos, C. Y.; Severino, R. P.; Bruomme, D.; Vieira, P.
C.; Corrêa, A. G. Eur. J. Med. Chem. 2012, 54, 10–21; f) Asahara,
M.; Takayama, T.; Tohda, Y.; Nishiwaki, N.; Ariga, M. Chem.
Pharm. Bull. 2004, 52, 1334–1338; g) Liu, X.; Xin, X.; Xiang, D.;
Zhang, R.; Kumar, S.; Zhou, K.; Dong, D. Org. Biomol. Chem.
4
.5.35. 3-Butyl-3-(2,2-diphenylethenyl)quinoline-2,4(1H,3H)-
dione (24c: R = Bu, Ar = Ph). The compound 24c could not be
separated from 23c. Pale yellow microcrystals (from MeOH),
m.p. 166 °C. IR (KBr):
ν
3250-2869 (NH), 1697, 1656 (C=O)
cm . H NMR (300 MHz, CDCl ): 9.92 (1H, s, NH), 7.71-7.68
1H, m, arom H), 7.34-7.32 (1H, m, arom H), 7.26-7.21 (5H, m,
arom H), 7.01-6.98 (1H, m, arom H), 6.92-6.84 (5H, m, arom H),
-
1 1
δ
3
(
6
5
.73-6.70 (1H, m, arom H), 6.40 (1H, s, vinyl H), 2.39 (2H, t, J =
.8 Hz), 1.28-1.19 (4H, m, CH x 2), 0.757 (3H, t, J = 6.4 Hz,
2
Me) ppm. HRMS (acetone/NBA): calcd for C267H NO2
3
26
96.1964 (M+H); found 396.1884.
4
2
.5.36. 3-[2,2-bis(4-Chlorophenyl)ethenyl]-3-methylquinoline-
2
012, 10, 5643–5646.
,4(1H,3H)-dione (24d: R = Me, Ar = 4-Cl-C H ). The
3. For review, see: a) de Klein, W. J. In Organic Syntheses by
Oxidation with Metal Compounbds, Mijis, W. J.; de Jonge, C. R.
H. I., Eds.; Plenum Press: New York, 1986; pp 261–314; b) Iqbal,
J.; Bhatia, B.; Nayyar, N. K. Chem. Rev. 1994, 94, 519–564; c)
Snider, B. B. Chem. Rev. 1996, 96, 339–363; d) Melikyan, G. G.
Org. React. 1997, 49, 427–675; e) Melikyan, G. G. Aldrichimica
Acta 1998, 31, 50–98; f) Demir, A. S.; Emrullahoglu, M. Current
Organic Synthesis 2007, 4, 321–351; g) Pan, X.-Q.; Zou, J.-P.;
Zhang, W. Mol. Divers. 2009, 13, 421–438. h) Burton, J. W. In
Encyclopedia of Radicals in Chemistry, Biology and Materials,
Chatgilialoglu, C.; Studer A., Eds.; Wiley: New York, 2012, pp
6
4
compound 24d could not be separated from 23d. Colorless
microcrystals (from MeOH), m.p. 221-223 °C. IR (KBr): 3200-
877 (NH), 1697, 1658 (C=O) cm . H NMR (300 MHz,
DMSO-d6): 10.2 (1H, s, NH), 7.83-6.72 (12H, m, arom H),
.46 (1H, s, =CH), 1.60 (3H, s, Me) ppm. HRMS (acetone/NBA):
calcd for C H Cl NO 422.0715 (M+H); found 422.0715.
ν
-
1
1
2
δ
6
24
18
2
2
4
.5.37.
3-[2,2-Bis(4-methylphenyl)ethenyl]-3-
methylquinoline-2,4(1H,3H)-dione (24e: R = Me, Ar = 4-Me-
C H ). Colorless microcrystals (from MeOH), m.p. 160-161
9
01–941.
6
4
-
1
1
4. a) Asahi, K.; Nishino, H. Tetrahedron 2005, 61, 11107–11124; b)
Cong, Z.-Q.; Nishino, H. Synthesis 2008, 2686–2694; c) Asahi,
K.; Nishino, H. Synthesis 2009, 409–423; d) Tsubusaki, T.;
Nishino, H. Tetrahedron 2009, 65, 9448–9459.
5. For review, see: a) Nishino, H. In Bioactive Heterocycles I,
Eguchi, S., Ed.; Springer: Berlin, 2006, pp 39–76; b) Zmitek, K.;
Zupan, M.; Iskra, J. Org. Biomol. Chem. 2007, 5, 3895–3908; c)
Lesce, M. R.; DellaGreca, M. Sci. Synth. 2009, 38, 231–274.
°
C.IR (KBr):
ν
3260-2868 (NH), 1678, 1654 (C=O) cm . H
9.96 (1H, s, NH), 7.66-7.64 (1H,
NMR (300 MHz, CDCl ):
δ
3
m, arom H), 7.39-7.34 (1H, m, arom H), 7.19-7.16 (2H, m,
arom H), 7.05-6.95 (3H, m, arom H), 6.80-6.73 (3H, m, arom
H), 6.66-6.63 (2H, m, arom H), 6.39 (1H, s, HC=), 2.30 (3H,
1
3
s, Me), 1.98 (3H, s, Me), 1.78 (3H, s, Me) ppm. C NMR (75
MHz, CDCl ): 197.0, 176.3 (C=O), 144.3 (C=CH), 140.8,
38.0, 137.5, 137.0, 136.0 (arom C), 135.2, 130.8, 129.9,
δ
3
6
.
a) Rahman, M. T.; Nishino, H.; Qian, C.-Y. Tetrahedron Lett.
2003, 44, 5225–5228; b) Rahman, M. T.; Nishino, H. Tetrahedron
2003, 59, 8383–8392.
Haque, M. D.; Nishino, H. Heterocycles 2011, 83, 1783–1805.
Haque, M. D.; Nishino, H. J. Heterocycl. Chem. 2013, 50, in
press.
a) Qian, C.-Y.; Nishino, H.; Kurosawa, K.; Korp, J. D. J. Org.
Chem. 1993, 58, 4448–4451; b) Rahman, M. T.; Nishino, H. Org.
Lett. 2003, 5, 2887–2890; c) Rahman, M. T.; Haque, M. A.;
Igarashi, H.; Nishino, H. 2011, 16, 9562–9581.
1
1
1
28.7, 128.3, 127.4, 127.0, 122.8 (arom CH), 118.3 (arom C),
16.0 (CH=C), 56.3 (C-3), 27.4, 21.1, 20.9 (Me) ppm. Anal.
7
8
.
.
Calcd for C H NO : C, 81.86; H, 6.08; N, 3.67. Found: C,
8
2
6
23
2
1.78; H, 6.01; N, 3.70.
9
.
Acknowledgments

1
5
1
0. a) Heiba, E. I.; Dessau, R. M. J. Org. Chem. 1974, 39, 3456–3457;
14. Kumabe, R.; Nishino, H. Heterocycl. Commun. 2004, 10, 135–
ACCEPTED MANUSCRIPT
b) Nishino, H. Bull. Chem. Soc. Jpn. 1985, 58, 1922–1927; c) Bar,
G.; Parsons, A. W.; Thomas, C. B. Tetrhedron 2001, 57, 4719–
138.
15. The energy calculations of 7b (R = Pr, Ar = Ph) and 8b (R = Pr,
Ar = Ph) were performed at the ground state based on Hartree-
Fock 3-21G, and it was found that the energy of 7b and 8b was
very similar.
4
3
4
728; d) Huang, J.-W.; Shi, M. J. Org. Chem. 2005, 70, 3859–
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Pekel, A. T.; Öktemer, A. Tetrahedron 2007, 63, 7229–7239; h)
Yilmaz, M.; Yakut, M.; Pekel, A. T. Synth. Commun. 2008, 38,
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17. a) Nair, V.; Mathew, J. J. Chem. Soc., Perkin Trans. 1, 1995, 187-
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3464-3469. e) Wang, G.-W.; Li, F.-B. Org. Biomol. Chem. 2005,
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Bolte, M. L.; Crow, W. D.; Yoshida, S. Aust. J. Chem. 1982, 35,
1411-1419.
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14–927; i) Yilmaz, M.; Uzunalioglu, N.; Yakut, M.; Pekel, A. T.
Turk. J. Chem. 2008, 32, 411–422; j) Ito, Y.; Yoshinaga, T.;
Nishino, H. Tetrahedron 2010, 66, 2683–2694; k) Loğoğlu, E.;
Yilmaz, M.; Katircioğlu, H.; Yakut, M.; Mercan, S. Med. Chem.
Res. 2010, 19, 490–497; l) Yilmaz, M.; Pekel, A. T. J. Fluorine
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T.; Uemura, K.; Ushimizu, Y.; Nishino, H. Org. Biomol. Chem.
2
011, 9, 1491–1507; n) Ito, Y.; Jogo, S.; Fukuda, N.; Okumura,
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Tetrahedron 2011, 67, 8255–8263; p) Deliomeroglu, M. K.;
Dengiz, C.; Caliskan, R.; Balci, M. Tetrahedron 2012, 68, 5838–
5
844. Also refer the oxidative cyclization using CAN; q) Yokoe,
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1. a) Ito, N.; Nishino, H.; Kurosawa, K. Bull. Chem. Soc. Jpn. 1983,
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1
1
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H.; Kurosawa, K. Synthesis 1996, 888–896.
Supplementary Material
1
2
X ray data of 3b (R = Me, Ar = Ar = 4-Cl-C H ) and 4a (R =
6 4
1
2
1
13
Me, Ar = Ar = Ph), H NMR, C NMR, and also DEPT-135
spectra of the products. Supplementary data associated with this
article can be found in the online version.
1
1
2. a) Asahi, K.; Nishino, H. Tetrahedron Lett. 2006, 47, 7259–7262;
b) Asahi, K.; Nishino, H. Heterocycl. Commun. 2008, 14, 21–26.
c) Asahi, K.; Nishino, H. Tetrahedron 2008, 64, 1620–1634. d)
Asahi, K.; Nishino, H. Eur. J. Org. Chem. 2008, 2404–2416.
3. Kumabe, R.; Nishino, H. Tetrahedron Lett. 2004, 45, 703–706.

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Mn(III)-based reaction of alkenes with quinolinones.
Formation of peroxyquinolinones and quinoline-related derivatives
a,
a
a
b
Hiroshi Nishino ∗, Ryoukou Kumabe , Ryoichi Hamada , Mehtap Yakut
a
Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, Kurokami 2-39-1, Chûou-Ku, Kumamoto 860-8555,
Japan
b
Department of Chemistry, Faculty of Science, Ankara University, 06100 Tandoğan, Ankara, Turkey
Supplementary Material
1
2
1
2
1
13
X ray data of 3b (R = Me, Ar = Ar = 4-Cl-C
6 4
H ) and 4a (R = Me, Ar = Ar = Ph), H NMR, C NMR, and also DEPT-135
spectra of the products. Supplementary data associated with this article can be found in the online version.
∗
Corresponding author. Tel.: +81-96-342-3374; fax: +81-96-342-3374; e-mail: nishino@sci.kumamoto-u.ac.jp

ACCEPTED MANUSCRIPT
1
X ray data of 3,3-Bis[2,2-bis(4-chlorophenyl)-2-hydroperoxyethyl]-1-methylquinoline-2,4(1H,3H)-dione (3b: R = Me, Ar =
2
Ar = 4-Cl-C
6
H
4
): CCDC reference number, CCDC 217001.

ACCEPTED MAN
1
USCRIPT
2
A. Crystal Data of 3b ( R = Me, Ar = Ar = 4-Cl-C H )
6
4
Empirical Formula
C
H
Cl NO
3
8 29
737.46
colorless, platelet
4
6
Formula Weight
Crystal Color, Habit
Crystal Dimensions
Crystal System
0.03 X 0.40 X 0.50 mm
triclinic
Lattice Type
Primitive
No. of Reflections Used for Unit
o
Cell Determination (2θ range)
Indexing Images
Camera Radius
20550 ( 6.4 - 135.5
)
2 oscillations at 2.0 minutes
127.40 mm
Lattice Parameters
a = 15.095(6) Å
b = 22.04(1) Å
c = 11.093(4) Å
o
α = 90.04(2)
o
β = 111.48(2)
o
γ = 101.71(1)
3
V = 3351(2) Å
Space Group
Z value
P-1 (#2)
4
3
D
1.461 g/cm
calc
F
1520.00
0
00
-
1
µ(CuKα)
36.28 cm
1
2
B. Intensity Measurements of 3b ( R = Me, Ar = Ar = 4-Cl-C
6
H
4
)
Diffractometer
Radiation
Rigaku RAXIS-RAPID Imaging Plate
CuKα (λ = 1.54178 Å)
graphite monochromated
o
Temperature
-150.0 C
Voltage, Current
Collimator Size
Detector Aperture
Data Images
40 kV, 100 mA
0.5 mm
450.0 mm x 256.0 mm
45 exposures at 0.3 minutes per degree
o
o
o
o
Oscillation Range (φ=0.0 ,χ=50.0 )
ω 50.0 - 230.0 with 20.0 step
o
o
o
o
Oscillation Range (φ=90.0 ,χ=50.0 )
ω 50.0 - 230.0 with 20.0 step
o
o
o
o
Oscillation Range (φ=180.0 ,χ=50.0 )
ω 50.0 - 230.0 with 20.0 step
o
o
o
o
Oscillation Range (φ=270.0 ,χ=50.0 )
ω 50.0 - 230.0 with 20.0 step
o
o
o
o
Oscillation Range (φ=0.0 ,χ=0.0 )
Camera Radius
ω 50.0 - 230.0 with 20.0 step
127.40 mm
Pixel Size
0.100 mm
o
2
θ
136.5
max
No. of Reflections Measured
Total: 14897
Unique: 10315 (R = 0.063)
int
Corrections
Lorentz-polarization
Absorption
(
trans. factors: 0.3949 - 0.8969)
1
2
6 4
C. Structure Solution and Refinement of 3b ( R = Me, Ar = Ar = 4-Cl-C H )
Structure Solution
Refinement
Direct Methods (SIR92)
Full-matrix least-squares (SHELXL-97)
2 2
2
Function Minimized
Σ w (Fo - Fc )
2
2
2
Least Squares Weights
w = 1/[σ (Fo ) + (0.1491P) + 0.0000P]
2
2
where P = (Fo + 2Fc )/3
o
No. of Reflections (All, 2σ < 136.49 )
No. Variables
3333
890
Reflection/Parameter Ratio
Residuals: R; Rw
Goodness of Fit Indicator
Max Shift/Error in Final Cycle
3.74
0.103 ; 0.340
0.92
-3.01
-
3
Maximum peak in Final Diff. Map
Minimum peak in Final Diff. Map
0.58 e /Å
-
3
-0.36 e /Å

ACCEPTED MANUSCRIPT
X ray data of 3,4-dihydro-10-methyl-3,3,12,12-tetraphenyl-10a,4a-(epoxyethano)-1,2-dioxino[3,4-b]quinolin-5(10H)-one (4a:
1
2
R = Me, Ar = Ar = Ph): CCDC reference number, CCDC 218561.

ACCEPTED MANU
1
SCRIPT
2
A. Crystal Data of 4a (R = Me, Ar = Ar = Ph)
Empirical Formula
C
O NH
9.50 4 31
3
Formula Weight
583.68
Crystal Color, Habit
Crystal Dimensions
Crystal System
colorless, platelet
0.20 X 0.10 X 0.10 mm
triclinic
Lattice Type
Primitive
No. of Reflections Used for Unit
o
Cell Determination (2θ range)
Indexing Images
Camera Radius
12168 ( 4.6 - 54.9
)
3 oscillations at 5.0 minutes
127.40 mm
Lattice Parameters
a = 9.207(1) Å
b = 14.317(2) Å
c = 23.581(3) Å
o
α = 77.550(5)
o
β = 82.279(4)
o
γ = 77.79(1)
3
V = 2953.8(6) Å
Space Group
Z value
P-1 (#2)
4
3
D
1.312 g/cm
calc
F
1228.00
0
00
-
1
µ(MoKα)
0.84 cm
1
2
B. Intensity Measurements of 4a (R = Me, Ar = Ar = Ph)
Diffractometer
Radiation
Rigaku RAXIS-RAPID Imaging Plate
MoKα (λ = 0.71069 Å)
graphite monochromated
o
Temperature
-160.0 C
Voltage, Current
Collimator Size
Detector Aperture
Data Images
50 kV, 32 mA
0.5 mm
270.0 mm x 256.0 mm
74 exposures at 10.8 minutes per degree
o
o
o
o
Oscillation Range (φ=0.0 ,χ=45.0 )
ω 130.0 - 190.0 with 3.0 step
o
o
o
o
Oscillation Range (φ=180.0 ,χ=45.0 )
Camera Radius
ω 0.0 - 162.0 with 3.0 step
127.40 mm
Pixel Size
0.100 mm
o
2
θ
55.0
max
No. of Reflections Measured
Total: 20843
Unique: 12021 (R = 0.080)
int
Corrections
Lorentz-polarization
Absorption
(
trans. factors: 0.6012 - 0.9916)
1
2
C. Structure Solution and Refinement of 4a (R = Me, Ar = Ar = Ph)
Structure Solution
Refinement
Direct Methods (SIR88)
Full-matrix least-squares
2
Function Minimized
Σ w (|Fo| - |Fc|)
2
2
2
2
Least Squares Weights
p-factor
1/σ (Fo) = 4Fo /σ (Fo )
0.1290
Anomalous Dispersion
All non-hydrogen atoms
o
No. of Observations (I>3.00σ(I), 2θ < 54.97 )
No. Variables
3336
802
Reflection/Parameter Ratio
Residuals: R; Rw
Residuals: R1
No. of Reflections to calc R1
Goodness of Fit Indicator
Max Shift/Error in Final Cycle
4.16
0.068 ; 0.105
0.068
3336
1.34
0.757
-
3
Maximum peak in Final Diff. Map
Minimum peak in Final Diff. Map
0.40 e /Å
-
3
-0.32 e /Å

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