Dimethyldioxirane oxidation of exocyclic (E,E)-cinnamylideneketones

Article abstract of DOI:10.1071/CH08216

Exocyclic (E,E)-cinnamylideneketones were oxidized by an excess of isolated dimethyldioxirane (DMDO, in acetone solution) at room temperature, providing diastereomeric mixtures of the ,:,-diepoxides. In the case of derivatives bearing an ortho-nitrocinnam

Full text of DOI:10.1071/CH08216

Full Paper
CSIRO PUBLISHING
Aust. J. Chem. 2009, 62, 82–89
www.publish.csiro.au/journals/ajc
Dimethyldioxirane Oxidation of Exocyclic
(E,E)-Cinnamylideneketones∗
Albert Lévai,A,E Artur M. S. Silva,B,E Clementina M. M. Santos,B,C
José A. S. Cavaleiro,B and József Jeko˝ D
ADepartment of Organic Chemistry, University of Debrecen, PO Box 20, H-4010 Debrecen, Hungary.
BDepartment of Chemistry and QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal.
CDepartment of Vegetal Production and Technology, Escola Superior Agrária de Bragança,
Campus de Santa Apolónia, 5301-855 Bragança, Portugal.
DDepartment of Chemistry, College of Nyíregyháza, Sóstói u. 31/b, H-4400 Nyíregyháza, Hungary.
ECorresponding authors. Email: alevai@puma.unideb.hu; artur.silva@ua.pt
Exocyclic (E,E)-cinnamylideneketones were oxidized by an excess of isolated dimethyldioxirane (DMDO, in acetone
solution) at room temperature, providing diastereomeric mixtures of the α,β:γ,δ-diepoxides. In the case of derivatives
bearing an ortho-nitrocinnamylidene moiety, α,β-monoepoxides were also isolated as minor products. The structures of
all new compounds and the stereochemistry of the monoepoxides and diepoxide diastereomers were established by NMR
studies.
Manuscript received: 21 May 2008.
Final version: 10 December 2008.
Introduction
(E,E)-Cinnamylideneacetophenones
few representatives has been described in the literature.[11]
For this reason, as a continuation of our work on (E,E)-
cinnamylideneacetophenones, wehaveundertakenstudiesonthe
synthesis and chemical transformations of such dienones. In our
present paper, the synthesis and dimethyldioxirane epoxidation
of exocyclic α,β,γ,δ-unsaturated ketones are reported. We have
decided to investigate the influence of various structural ele-
ments of the exocyclic α,β,γ,δ-unsaturated ketones used, namely
the ring size of the benzocyclanone ring and the influence of an
ortho-substituent in the cinnamylidene moiety, because this sub-
stituent is in the vicinity of one of the two double bonds to be
epoxidized.
(1,5-diphenyl-2,4-
pentadien-1-ones) are well known α,β,γ,δ-unsaturated ketones.
Certain of their bromoderivatives have been seen as excellent
candidates to design effective second-order non-linear optical
materials,[1] whereas other cinnamylideneketones exerted sig-
nificant antiproliferative effects on multiresistant cancer cell
lines.[2] Despite the scarce number of potential biologi-
cal or industrial applications of cinnamylideneacetophenones,
these compounds have been widely used as starting mate-
rials for the synthesis of various heterocyclic compounds,
such as 2-styryl-1,5-benzothiazepines,[3] styryl-2-pyrazolines
and styrylpyrazoles,[4] 2-benzoyl-1,5-diphenylpyrroles,[5] 2-
styrylchromones,[6] and 3-styrylchromones.[7] Previously, we
also investigated the epoxidation of (E,E)-cinnamylideneaceto-
phenones with different oxidizing agents.[8,9] When isolated
dimethyldioxirane was used as oxidant, diastereomeric mixtures
of α,β:γ,δ-diepoxides were obtained, in some cases together
with α,β-monoepoxides as minor by-products. When (E,E)-2ꢀ-
hydroxycinnamylideneacetophenones were oxidized under the
same reaction conditions, 2ꢀ-hydroxy-γ,δ-epoxycinnamylidene-
acetophenones could also be detected and isolated.[8] Hydrogen
peroxide or iodosylbenzene in combination with Jacobsen’s
salen MnIII catalyst have also been used; in such cases,
diastereomeric mixtures of α,β:γ,δ-diepoxides and also γ,δ-
monoepoxides were formed. It is worth mentioning that the
Julia asymmetric epoxidation procedure has provided α,β-
monoepoxide in one case.[10]
Results and Discussion
Synthesis
The benzocyclanones 3a–i were synthesized by the base-
catalyzed condensation of 1-indanone 1a, 1-tetralone 1b,
and 1-benzosuberone 1c with cinnamaldehydes 2a–c to
afford the appropriate dienones (Scheme 1). The (E,E)-
benzocyclanones 3a,d,e,g are known compounds,[11] whereas
(E,E)-cinnamylideneketones 3b,c,f,h,i are new compounds and
were obtained in very good yields (72–86%).
Isolated dimethyldioxirane proved to be a convenient oxi-
dant for the stereoselective epoxidation of a wide variety of
exocyclic α,β-unsaturated ketones.[12] This versatile oxidant was
beneficially used for the preparation of the α,β:γ,δ-diepoxides of
(E,E)-cinnamylideneacetophenones.[8] On the basis of all these
experiences, dimethyldioxirane was considered for the epoxida-
tion of exocyclic α,β,γ,δ-unsaturated ketones 3a–i (Scheme 2).
The related exocyclic α,β,γ,δ-unsaturated ketones have
hitherto received less attention and the synthesis of their
∗Dedicated to Professor Dr Branko Stanovnik on the occasion of his 70th birthday.
© CSIRO 2009
10.1071/CH08216
0004-9425/09/010082

Oxidation of (E,E)-Cinnamylideneketones
83
5؆
CHO
( )n
6؆
3؅
4؆
3؆
H
(n ꢁ 3)
(n ꢁ 6)
( )n
2
2؅
KOH (aq.)
EtOH
1؅
ꢁ
R
2a–c
2؆
O
1a–c
1
H
H
R
O
a n ꢀ 1
b n ꢀ 2
c n ꢀ 3
a R ꢀ H
3a–i
b R ꢀ OMe
c R ꢀ NO2
a n ꢀ 1, R ꢀ H
f
n ꢀ 2, R ꢀ NO2
b n ꢀ 1, R ꢀ OMe g n ꢀ 3, R ꢀ H
c n ꢀ 1, R ꢀ NO2 h n ꢀ 3, R ꢀ OMe
d n ꢀ 2, R ꢀ H
i
n ꢀ 3, R ꢀ NO2
e n ꢀ 2, R ꢀ OMe
Scheme 1. Synthesis of cinnamylideneketones 3a–i.
4؆؅
5؆؅
H
3؆؅
H
1؆
O
O
O
( )n
O
1؅
O
H
( )n
2
3؆
R
R
A
2؆
ꢁ
H
H
H
R
H
H
3؅
2؅
O
H
1
4a–i
O
3a–i
A: DMDO/acetone, CH2Cl2
Diastereomer A
4a–i
Diastereomer B
4؆؅
5؆؅
3؆؅
6؆؅
a n ꢀ 1, R ꢀ H
f n ꢀ 2, R ꢀ NO2
g n ꢀ 3, R ꢀ H
h n ꢀ 3, R ꢀ OMe
1؅
O
1؆
b n ꢀ 1, R ꢀ OMe
c n ꢀ 1, R ꢀ NO2
d n ꢀ 2, R ꢀ H
( )n
NO2
2؆
2
3؅
2؅
i
n ꢀ 3, R ꢀ NO2
H
1
e n ꢀ 2, R ꢀ OMe
O
5a–c
Scheme 2. Epoxidation of cinnamylideneketones 3a–i with dimethyldioxirane (DMDO).
(E,E)-2-Cinnamylidene-1-indanones (3a–c), (E,E)-2-cinnamy-
lidene-1-tetralones (3d–f) and (E,E)-2-cinnamylidene-1-benzo-
suberones (3g–i) were allowed to react with one molar equivalent
of isolated dimethyldioxirane in acetone (0.07–0.10 M)[13] at
room temperature and the progress of the reaction was mon-
itored by TLC. After a 24-h reaction time, the two main
components in the reaction mixture were the starting mate-
rial and the appropriate α,β,γ,δ-diepoxide, accompanied by
several by-products. Another molar equivalent of dimethyl-
dioxirane was added to the reaction mixture each day until
the complete conversion of the starting material (cf. Experi-
mental). Except for the nitro-substituted dienones 3c,f,i, only
α,β:γ,δ-diepoxides 4a,b,d,e,g,h were isolated after the com-
plete conversion of the starting dienones. The presence of
an ortho-nitro group considerably slowed down the reac-
tion and a complete conversion of the starting material
required a higher amount of oxidant and much longer reac-
tion times (cf. Experimental). In these cases, α,β-monoepoxides
5a–c were first detected by NMR spectroscopy and then isolated
by preparative TLC.
Based on our experimental results, it can be concluded
that the ring size of the benzocyclanone ring and the ortho-
methoxy substituent in the cinnamylidene moiety of the starting
material have no influence on this epoxidation reaction. In
the case of the unsubstituted and methoxysubstituted com-
pounds, no difference was observed in the reactivity of the
two double bonds under the reaction conditions used. How-
ever, the ortho-nitro group considerably reduced the reac-
tivity of the γ,δ-double bond to the electrophilic oxidant
dimethyldioxirane (DMDO), giving rise to the formation of
α,β-monoepoxides. These results agreed with those obtained
in the epoxidation of linear cinnamylideneacetophenones,[8]
where the γ,δ-monoepoxides isolated in the case of compounds
bearing a 2ꢀ-hydroxyl group involved intramolecular hydrogen
bonding with the carbonyl group, reducing the reactivity of
the α,β-double bond and enhancing the reactivity of the γ,δ-
double bond towards the electrophilic DMDO. In the present
case, the electron-withdrawing effects of the nitro and car-
bonyl groups are slightly compensated for by the α-alkyl chain
effect, making the Cα=Cβ double bond more reactive towards
the electrophilic DMDO. This effect results in the formation
of the α,β-monoepoxides 5a–c from the oxidation of ortho-
nitro-2-cinnamylidenebenzacyclanones 3c,f,i, as in the case
of the epoxidation of 4-nitrocinnamylideneacetophenone with
iodosylbenzene and a catalytic amount of salen MnIII.[9]
NMR Spectroscopy
The main features of the 1H NMR spectra of 2-cinnamylidene-
benzocyclanones3a–i aretheresonancesoftheirvinylicprotons.
H-3ꢀ appears as a doublet, as a result of the coupling with
H-2ꢀ at δH 7.0–7.2 ppm and the coupling constant 3JH3 –H2 15–
16 Hz indicates the trans configuration of the C2ꢀ=C3ꢀ double
bond. However, the complete stereochemistry of the α,β,γ,δ-
unsaturated carbonyl system was established with the aid of
the nuclear Overhauser effect (NOE) cross peaks observed in
the corresponding nuclear Overhauser effect correlation spectra
(NOESY) (Fig. 1a), which support the close proximity of H-2ꢀ
and the aliphatic protons of the cyclanone ring and also of H-1ꢀ
and H-3ꢀ and are only consistent with the structure presented in
Schemes 1 and 2. The deshielding mesomeric effect of the car-
bonyl group is responsible for the high resonance frequency of
H-1ꢀ and H-3ꢀ (δH 7.4–7.6 ppm) relative to that obtained for H-2ꢀ.
The comparison of the 1H NMR spectra of compounds 3c,f,i
with those of 5a–c allowed the detection of a signal, as a dou-
blet (J ∼7 Hz), at δH 3.92–4.12 ppm and the presence of only
two vinylic protons at δH 6.07–6.18 (double doublet, J ∼7 and
16 Hz) and 7.32–7.39 (doublet, J ∼16 Hz) ppm. These data are
ꢀ
ꢀ

84
A. Lévai et al.
(a) NOESY spectra
NOE
6؆؅
H
NOE
O
H
H
O
O
H
O
2؅
( )n
O
2؆
( )n
3؆
R
1؅
R
2؆
3؅
3؅
H
H
3؅
H
O
H
H
R
H
NOE
4a–i
Diastereomer A
O
NOE
3a–i
NOE
4a–i
Diastereomer B
(b) HMBC spectra
6؆؅
H
O
1؆؅
2؆
H
1؆؅
1؆؅
H 1؆
O
H
H
O
H
O
O
( )n
( )n
O
( )n
NO2
3؆ H
2؆
2؆
3؅
R
R
H
1
3؅
2
H
H
H
O
O
H
H
4a–i
4a–i
5a–c
Fig. 1. (a) Main nuclear Overhauser effect (NOE) correlation spectroscopy cross peaks found in the nuclear Over-
hauser effect correlation spectra (NOESY) of compounds 3a–i and 4a–i (diastereomers A and B). (b) Important
connectivities found in the heteronuclear multiple bond correlation (HMBC) spectra of compounds 5a–c and 4a–i.
only compatible with the formation of α,β-epoxides 5a–c, which
was also confirmed by the connectivities found in their heteronu-
clear multiple bond correlation (HMBC) spectra, namely the
connectivities of H-3ꢀ with those of the carbonyl carbons (δC
193.1–201.1 ppm) and also of H-1ꢀꢀ and H-2ꢀꢀ with those of C-
1ꢀꢀꢀ (δC 131.7–131.9 ppm) (Fig. 1b). In the NOESY spectra of
α,β-epoxides 5a–c, there are NOE crosspeaks between the sig-
nals H-1ꢀꢀ and H-2ꢀꢀ with those of H-3ꢀ and of the cyclanone
rings. These data and the absence of NOE crosspeaks between
the signal of H-3ꢀ and the signals of the remaining aliphatic pro-
tons confirms the stereochemistry of the oxirane ring depicted
in Scheme 2 and Fig. 1b, as expected for an epoxide obtained
from a trans-alkene with a concerted mechanism.
(doublet at δH 3.24–3.70), H-2ꢀꢀ (double doublet at δH
2.97–3.18), and H-3ꢀꢀ (doublet at δH 3.90–4.69). The coupling
ꢀꢀ
ꢀꢀ
constant values JH2 –H3 ∼1.7–2.1 Hz are consistent with a trans
configuration of the γ,δ-epoxide,[9,14] whereas those of JH3 –H2
ꢀ
ꢀꢀ
are dependent on the size of the cyclanone ring and on the stereo-
chemistry of the diastereomers (4a–c, J 3.8–4.9 Hz for A and
J 5.6–6.0 Hz for B; 4d–f, J 4.4–6.0 Hz for A and J 6.1–6.6 Hz
for B; 4g–i, J 5.0–6.3 Hz for A and J 6.8–7.2 Hz for B). The
1
aromatic region of the H NMR spectra of α,β:γ,δ-diepoxides
4a–i presents several multiplets, which were assigned with the
aid of all 2D NMR spectra.
The 13C NMR spectra of the diastereomeric mixture of
α,β:γ,δ-diepoxides 4a–i present a duplication of signals with
four distinct zones: those at lower-frequency values (δC 22.7–
32.2) assigned to the carbon resonances of the aliphatic protons
of the cyclanone rings; those at δC 51.6–63.7 belonged to the car-
bon resonances of the epoxide rings; those at δC 110.1–158.1 due
to the carbon resonances of aromatic rings, and those at higher
values of frequency (δC 192.4–200.9) attributed to the resonance
of the carbonyl carbons. The carbon resonances of the C-3ꢀꢀ,
C-2ꢀꢀ, C-3ꢀ, and C-2 of both diastereomers were assigned with
the aid of the heteronuclear single-quantum correlation (HSQC)
spectra, appearing at δC 51.6–58.1, 57.9–59.7, 59.6–62.2, and
62.0–63.7, respectively. The assignment of the carbon reso-
nances of all compounds was confirmed by the connectivities
found in the HMBC spectra (Fig. 1b).
The 13C NMR spectra of the α,β-epoxides 5a–c present the
signals of the epoxide carbon resonances at δC 61.6–66.6 ppm
and those of the vinylic system at δC 127.1–128.2 (C-1ꢀꢀ) and
131.8–132.2 (C-2ꢀꢀ) ppm.
1
The H NMR spectra of α,β:γ,δ-diepoxides 4a–i are quite
complex, presenting two distinct regions (aliphatic and aro-
matic regions). In the aliphatic region, the presence of two
groups of signals indicates that we have a diastereomeric mix-
ture of compounds, and the assignment of the signals of both
diastereomers for 4a–i was based on the correlations found
in the correlation spectra (COSY) of these compounds. The
NOE effects found in the NOESY spectra of these compounds
led us to establish the stereochemistry of both diastereomers
A and diastereomers B, and the proportion of the mixture as
(38%–50%)A:(50%–62%)B, (40%–70%)A:(30%–60%)B and
(71%–97%)A:(3%–29%)B for compounds bearing five-, six-
and seven-membered cyclanone rings, respectively, was calcu-
lated from the area of proton signals. This stereochemistry was
based on the close proximities between H-3ꢀꢀ and H-3ꢀ and of
H-2ꢀꢀ with H-6ꢀꢀꢀ and some of the aliphatic signals of the
cyclanone ring for diastereomers B and between H-3ꢀ and
H-2ꢀꢀ for diastereomers A (Fig. 1a). In the HMBC spec-
tra of α,β:γ,δ-diepoxides 4a–i, the correlations between the
carbonyl carbon resonances (δC 192.4–200.9) and the sig-
nals of an epoxide ring appearing as a doublet at δH 3.24–
3.70 allowed assignment of these proton resonances to H-3ꢀ.
From the 2D-COSY experiments, all the proton resonances
of the α,β:γ,δ-diepoxide system were assigned, H-3ꢀ
Conclusions
Epoxidation of (E,E)-2-cinnamylidene-1-indanones, (E,E)-
2-cinnamylidene-1-tetralones, and (E,E)-2-cinnamylidene-1-
benzosuberones has been achieved. Dimethyldioxirane in
acetone proved to be a convenient oxidant for this purpose,
and under these reaction conditions, the major products were a
diastereomeric mixture of α,β:γ,δ-diepoxides in each case. The
oxidation reaction was more efficient on compounds bear-
ing neutral or electron-rich substituents on the cinnamyli-
dene aromatic ring. The presence of an ortho-nitro substituent
slowed down the reaction rate and as a consequence the
α,β-monoepoxides were also isolated.

Oxidation of (E,E)-Cinnamylideneketones
85
Experimental
147.9 (C-2ꢀꢀ), 148.8 (C-3a), 193.5 (C-1). m/z 291 (M+•, 2), 274
(100), 244 (44), 115 (89). νmax/cm−1 1695, 1623, 1518, 1468,
1341, 1250, 1162, 1106, 973, 938, 790, 733. (Found: C 74.31,
H 4.42. C18H13NO3 requires C 74.22, H 4.49%).
Melting points were determined on a Kofler hot-stage apparatus
and are uncorrected. H and 13C NMR spectra were recorded
1
on Bruker Avance 300 spectrometer (at 300.13 and 75.47 MHz,
respectively); chemical shifts are reported in ppm (δ) usingTMS
as internal reference and coupling constants (J) are given in
Hz. The 1H assignments were made using two-dimensional gra-
dient selected correlation spectroscopy (gCOSY) and NOESY
(800 ms mixing time) experiments, whereas in the case of
13C assignments, we used two-dimensional gradient selected
heteronuclear single quantum coherence (gHSQC) and two-
dimensional gradient selected heteronuclear multiple bond
coherence (gHMBC) (delays for one-bond and long-range J C/H
couplings were optimized for 145 and 7 Hz, respectively) exper-
iments. The IR spectra were obtained with a Perkin–Elmer 16
PC instrument. Mass spectra were recorded on aVG trio-2 appa-
ratus. Elemental analyses (C, H) were measured in-house with a
Carlo Erba 1106 instrument. Dimethyldioxirane (as an acetone
solution) was prepared as described[13] and its peroxide content
was determined iodometrically.
(E,E)-2-[3-(2-Nitrophenyl)allylidene]-1-tetralone 3f
(2.20 g, 72%), mp 192–193◦C. δH (CDCl3) 3.03 (4H, s, H-3 and
H-4), 7.13 (1H, dd, J 15.0 and 11.7, H-2ꢀ), 7.28 (1H, d, J 7.4,
H-5), 7.36 (1H, t, J 7.4, H-7), 7.46 (1H, ddd, J 7.7, 7.4, and
1.0, H-4ꢀꢀ), 7.50 (1H, t, J 7.4, H-6), 7.51 (1H, d, J 15.0, H-3ꢀ),
7.56 (1H, d, J 11.7, H-1ꢀ), 7.63 (1H, ddd, J 7.6, 7.4, and 0.8,
H-5ꢀꢀ), 7.76 (1H, dd, J 7.6 and 1.0, H-6ꢀꢀ), 7.98 (1H, dd, J 7.7
and 0.8, H-3ꢀꢀ), 8.12 (1H, dd, J 7.4 and 1.2, H-8). δC (CDCl3)
26.2 (C-3), 28.7 (C-4), 124.9 (C-3ꢀꢀ), 127.1 (C-7), 128.1 (C-2ꢀ),
128.19 and 128.22 (C-5 and C-8), 128.4 (C-6ꢀꢀ), 128.9 (C-4ꢀꢀ),
132.2 (C-1ꢀꢀ), 133.1 (C-5ꢀꢀ), 133.3 (C-6), 133.5 (C-8a), 134.6
(C-1ꢀ), 134.8 (C-3ꢀ), 136.7 (C-2), 143.3 (C-4a), 147.9 (C-2ꢀꢀ),
187.1 (C-1). m/z 305 (M+•, 2), 288 (100), 170 (48), 115 (86).
νmax/cm−1 1662, 1606, 1581, 1517, 1340, 1240, 1161, 1131,
1026, 973, 925, 865, 790, 736, 708, 640. (Found: C 74.66, H
4.87. C19H15NO3 requires C 74.74, H 4.95%).
General Method for the Preparation of Exocyclic
α,β,γ,δ-Unsaturated Ketones 3a–i
A mixture of the cyclic ketone (1a–c, 10.0 mmol), the appro-
priate trans-cinnamaldehyde (2a–c, 12.0 mmol), 10% aqueous
solution of KOH (10 mL), and ethanol (50 mL) was stirred at
room temperature for 4 h, then poured into H2O (100 mL).
The precipitate was separated by filtration, washed with water,
and recrystallized from methanol to give exocyclic α,β,γ,δ-
unsaturated ketones 3a–i. Compounds 3a,d,e,g are known
substances,[11] whereas the physical and spectroscopic data of
the new compounds 3b,c,f,h,i are given below.
(E,E)-2-[3-(2-Methoxyphenyl)allylidene]-
1-benzosuberone 3h
(2.25 g, 74%), mp 108–109◦C. δH (CDCl3) 1.98 (2H, quint, J
6.8, H-4), 2.56 (2H, t, J 6.8, H-3), 2.81 (2H, t, J 6.8, H-5), 3.90
(3H, s, 2ꢀꢀ-OCH3), 6.92 (1H, d, J 8.1, H-3ꢀꢀ), 6.98 (1H, ddd, J
7.7, 7.6, and 0.6, H-5ꢀꢀ), 7.16 (1H, dd, J 15.5 and 11.6, H-2ꢀ),
7.18 (1H, dd, J 7.4 and 1.0, H-6), 7.30 (1H, ddd, J 8.1, 7.7,
and 1.7, H-4ꢀꢀ), 7.35 (1H, dt, J 7.3 and 1.0, H-8), 7.43 (1H, d, J
15.5, H-3ꢀ), 7.45 (1H, ddd, J 7.4, 7.3, and 1.5, H-7), 7.53 (1H,
d, J 11.6, H-1ꢀ), 7.58 (1H, dd, J 7.7 and 1.7, H-6ꢀꢀ), 7.74 (1H,
dd, J 7.3 and 1.5, H-9). δC (CDCl3) 24.5 (C-3), 26.6 (C-4), 31.2
(C-5), 55.5(2ꢀꢀ-OCH3), 111.0(C-3ꢀꢀ), 120.7(C-5ꢀꢀ), 124.0(C-2ꢀ),
125.6 (C-1ꢀꢀ), 126.9 (C-8), 127.2 (C-6ꢀꢀ), 128.8 (C-6), 128.9
(C-9), 130.0 (C-4ꢀꢀ), 132.1 (C-7), 136.3 (C-3ꢀ), 137.0 (C-2),
137.8 (C-1ꢀ), 139.2 (C-9a), 139.5 (C-5a), 157.3 (C-2ꢀꢀ), 198.0
(C-1). m/z 304 (M+•, 100), 273 (11), 197 (19), 115 (31).
νmax/cm−1 1649, 1604, 1583, 1483, 1452, 1301, 1246, 1162,
1101, 1024, 969, 746, 712. (Found: C 82.77, H 6.69. C21H20O2
requires C 82.86, H 6.62%).
(E,E)-2-[3-(2-Methoxyphenyl)allylidene]-1-indanone 3b
(2.38 g, 86%), mp 160–161◦C. δH (CDCl3) 3.85 (2H, br s, H-3),
3.91 (3H, s, 2ꢀꢀ-OCH3), 6.92 (1H, d, J 8.1, H-3ꢀꢀ), 6.98 (1H, dd, J
7.7 and 7.5, H-5ꢀꢀ), 7.10 (1H, dd, J 15.5 and 11.9, H-2ꢀ), 7.31 (1H,
ddd, J 8.1, 7.7, and 1.6, H-4ꢀꢀ), 7.41 (1H, dd, J 7.6 and 7.4, H-6),
7.42 (1H, d, J 15.5, H-3ꢀ), 7.47 (1H, dt, J 11.9 and 2.0, H-1ꢀ), 7.53
(1H, d, J 7.4, H-4), 7.59 (1H, d, J 7.5, H-6ꢀꢀ), 7.60 (1H, dt, J 7.4
and 1.1, H-5), 7.88 (1H, d, J 7.6, H-7). δC (CDCl3) 30.4 (C-3),
55.5 (2ꢀ-OCH3), 111.1 (C-3ꢀꢀ), 120.7 (C-5ꢀꢀ), 124.1 (C-7), 124.9
(C-2ꢀ), 125.3 (C-1ꢀꢀ), 126.2 (C-4), 127.40 (C-6), 127.44 (C-6ꢀꢀ),
130.4 (C-4ꢀꢀ), 134.2 (C-5), 134.4 (C-1ꢀ), 135.4 (C-2), 137.3 (C-
3ꢀ), 139.4 (C-7a), 148.9 (C-3a), 157.5 (C-2ꢀꢀ), 193.7 (C-1). m/z
276 (M+•, 100), 261 (27), 169 (38), 115 (39). νmax/cm−1 1685,
1611, 1484, 1465, 1326, 1292, 1244, 1176, 1152, 1099, 1028,
981, 934, 748. (Found: C 82.70, H 5.91. C19H16O2 requires
C 82.58, H 5.84%).
(E,E)-2-[3-(2-Nitrophenyl)allylidene]-1-benzosuberone 3i
(2.58 g, 81%), mp 179–180◦C. δH (CDCl3) 1.99 (2H, quint, J
6.8, H-4), 2.57 (2H, t, J 6.8, H-3), 2.82 (2H, t, J 6.8, H-5), 7.08
(1H, dd, J 15.3 and 11.4, H-2ꢀ), 7.19 (1H, d, J 7.6, H-6), 7.35
(1H, ddd, J 7.6, 7.5, and 1.1, H-8), 7.466 (1H, t, J 7.6, H-7),
7.468 (1H, ddd, J 8.2, 7.8, and 1.3, H-4ꢀꢀ), 7.48 (1H, d, J 11.4,
H-1ꢀ), 7.52 (1H, d, J 15.3, H-3ꢀ), 7.63 (1H, ddd, J 7.8, 7.7, and
1.0, H-5ꢀꢀ), 7.74 (1H, dd, J 7.7 and 1.3, H-6ꢀꢀ), 7.75 (1H, dd, J
7.5 and 1.5, H-9), 7.99 (1H, dd, J 8.2 and 1.0, H-3ꢀꢀ). δC (CDCl3)
24.6 (C-3), 26.5 (C-4), 31.1 (C-5), 124.9 (C-3ꢀꢀ), 127.0 (C-8),
128.1 (C-2ꢀ), 128.4 (C-6ꢀꢀ), 128.9, 129.0, and 129.1 (C-6, C-7,
and C-9), 132.2 (C-1ꢀꢀ), 132.4 (C-4ꢀꢀ), 133.1 (C-5ꢀꢀ), 135.0
(C-3ꢀ), 135.1 (C-1ꢀ), 138.6 (C-9a), 139.4 (C-5a), 140.0 (C-2),
147.9 (C-2ꢀꢀ), 197.6 (C-1). m/z 319 (M+•, 1), 302 (94), 184
(80), 115 (100). νmax/cm−1 1652, 1605, 1581, 1521, 1451, 1346,
1303, 1247, 1167, 1106, 1040, 969, 869, 779, 742, 675. (Found:
C 72.31, H 5.42. C20H17NO3 requires C 72.22, H 5.36%).
(E,E)-2-[3-(2-Nitrophenyl)allylidene]-1-indanone 3c
(2.21 g, 76%), mp 220–221◦C. δH (CDCl3) 3.88 (2H, s, H-3),
7.01 (1H, dd, J 14.8 and 11.0, H-2ꢀ), 7.43 (1H, dd, J 7.9 and
7.7, H-6), 7.44 (1H, d, J 11.0, H-1ꢀ), 7.48 (1H, dd, J 7.7 and
7.4, H-4ꢀꢀ), 7.53 (1H, d, J 14.8, H-3ꢀ), 7.54 (1H, d, J 8.2, H-4),
7.62 (1H, dd, J 8.2 and 7.9, H-5), 7.65 (1H, dd, J 7.4 and 7.3,
H-5ꢀꢀ), 7.76 (1H, d, J 7.3, H-6ꢀꢀ), 7.88 (1H, d, J 7.7, H-7), 8.00
(1H, dd, J 7.7 and 1.0, H-3ꢀꢀ). δC (CDCl3) 30.3 (C-3), 124.3
(C-7), 125.0 (C-3ꢀꢀ), 126.3 (C-4), 127.6 (C-6), 128.4 (C-6ꢀꢀ),
129.0 (C-2ꢀ), 129.2 (C-4ꢀꢀ), 131.9 (C-1ꢀꢀ), 132.1 (C-1ꢀ), 133.2
(C-5ꢀꢀ), 134.7 (C-5), 135.9 (C-3ꢀ), 138.2 (C-2), 138.9 (C-7a),

86
A. Lévai et al.
General Procedure for the Dimethyldioxirane Oxidation
of Exocyclic α,β,γ,δ-Unsaturated Ketones 3a–i
6.90 (1H, d, J 8.0, H-3ꢀꢀꢀ), 6.96 (1H, t, J 7.9, H-5ꢀꢀꢀ), 7.18 (1H,
d, J 7.9, H-6ꢀꢀꢀ), 7.27–7.30 (1H, m, H-4ꢀꢀꢀ), 7.46 (1H, t, J 7.5,
H-6), 7.53 (1H, d, J 7.5, H-4), 7.70 (1H, t, J 7.5, H-5), 7.85∗
(1H, d, J 7.5, H-7). δC (CDCl3) 29.5 (C-3), 51.7 (C-3ꢀꢀ), 55.3
(2ꢀꢀꢀ-OCH3), 59.2 (C-2ꢀꢀ), 60.1 (C-3ꢀ), 63.7 (C-2), 110.2 (C-3ꢀꢀꢀ),
120.7 (C-5ꢀꢀꢀ), 124.12 (C-7), 124.4 (C-1ꢀꢀꢀ), 125.2 (C-6ꢀꢀꢀ), 126.7
(C-4), 128.0 (C-6), 129.2 (C-4ꢀꢀꢀ), 135.57 (C-7a), 135.8 (C-5),
151.4 (C-3a), 157.8 (C-2ꢀꢀꢀ), 199.7 (C-1).
The required amount of isolated DMDO in acetone (0.07–
0.10 M) was added to the anhydrous CH2Cl2 solution (20 mL)
of the appropriate exocyclic α,β,γ,δ-unsaturated ketone (3a–i,
5.0 mmol) at room temperature. The mixture was left to stand
at room temperature and the progress of the reaction was mon-
itored by TLC. Another equivalent of DMDO was added every
day until the complete conversion of the starting material. The
complete conversion of compounds 3a,b,d,e,g,h into the cor-
responding α,β:γ,δ-diepoxides 4a,b,d,e,g,h was performed by
using 5 equivalents of dimethyldioxirane within 120 h, whereas
the nitrosubstituted compounds 3c,f,i could be converted to their
α,β:γ,δ-diepoxides 4c,f,i with 18 equivalents of DMDO in 432 h.
After the complete consumption of the starting material, the sol-
vent was evaporated under reduced pressure and the residue was
crystallized from methanol to afford the diastereomeric mix-
ture of α,β:γ,δ-diepoxides 4a,b,d,e,g,h (4a, 1.10 g, 79%; 4b,
1.12 g, 73%; 4d, 1.04 g, 71%; 4e, 1.18 g, 73%; 4g, 1.09 g, 71%;
4h, 1.24 g, 74%). In the case of nitro-derivatives, the resulting
residue was purified by preparative TLC, using a 9:1 mixture
of CH2Cl2:light petroleum as eluent. After several elutions, the
fraction with the higher Rf value was identified as the α,β-
monoepoxides 5a–c (5a, 230 mg, 15%; 5b, 225 mg, 14%; 5c,
201 mg, 12%) and that with the lower Rf value identified as the
α,β:γ,δ-diepoxides 4c,f,i (4c, 1.13 g, 70%; 4f, 1.16 g, 69%; 4i,
1.23 g, 70%).
Diastereomer B: rel-(2R,3ꢀS,2ꢀꢀR,3ꢀꢀS)-Spiro[indan-1-one-2,
2ꢀ-[2-(2-methoxyphenyl)-1,2-epoxypropyl]oxirane] δH (CDCl3)
3.00 (1H, dd, J 5.6 and 1.8, H-2ꢀꢀ), 3.33 and 3.66 (2 × 1H, 2d, J
18.2, H-3), 3.58 (1H, d, J 5.6, H-3ꢀ), 4.37 (1H, d, J 1.8, H-3ꢀꢀ),
6.90 (1H, d, J 8.0, H-3ꢀꢀꢀ), 6.96 (1H, t, J 7.9, H-5ꢀꢀꢀ), 7.18 (1H, d,
J 7.9, H-6ꢀꢀꢀ), 7.27–7.30 (1H, m, H-4ꢀꢀꢀ), 7.46 (1H, dd, J 7.7 and
7.5, H-6), 7.53 (1H, d, J 7.5, H-4), 7.70 (1H, t, J 7.5, H-5), 7.86∗
(1H, d, J 7.7, H-7). δC (CDCl3) 29.2 (C-3), 53.0 (C-3ꢀꢀ), 55.4
(2ꢀꢀꢀ-OCH3), 58.3 (C-2ꢀꢀ), 59.9 (C-3ꢀ), 63.4 (C-2), 110.1 (C-3ꢀꢀꢀ),
120.6 (C-5ꢀꢀꢀ), 124.15 (C-7), 124.2 (C-1ꢀꢀꢀ), 125.0 (C-6ꢀꢀꢀ), 126.7
(C-4), 128.1 (C-6), 129.3 (C-4ꢀꢀꢀ), 135.63 (C-7a), 135.8 (C-5),
151.0 (C-3a), 158.0 (C-2ꢀꢀꢀ), 199.4 (C-1). ∗Can be interchanged.
mp 162–163◦C. m/z 308 (M+•, 3), 219 (45), 121 (62), 91
(100). νmax/cm−1 1720, 1605, 1497, 1467, 1248, 1107, 1027,
986, 930, 887, 846, 744, 596. (Found:C73.92, H5.18. C19H16O4
requires C 74.01, H 5.23%).
Diastereomeric Mixture (50A:50B) of Spiro[indan-1-one-
2,2ꢀ-[2-(2-nitrophenyl)-1,2-epoxypropyl]oxirane] 4c
Diastereomer A: rel-(2R,3ꢀS,2ꢀꢀS,3ꢀꢀR)-Spiro[indan-1-one-2,2ꢀ-
[2-(2-nitrophenyl)-1,2-epoxypropyl]oxirane] δH (CDCl3) 3.03
(1H, dd, J 4.9 and 2.1, H-2ꢀꢀ), 3.40 and 3.61 (2 × 1H, 2d, J 18.2,
H-3), 3.70 (1H, d, J 4.9, H-3ꢀ), 4.69 (1H, d, J 1.9, H-3ꢀꢀ), 7.47
(1H, t, J 7.4, H-6), 7.51–7.56 (2H, m, H-4 and H-4ꢀꢀꢀ), 7.66
(1H, dd, J 7.5 and 1.4, H-6ꢀꢀꢀ), 7.67–7.73 (2H, m, H-5 and
H-5ꢀꢀꢀ), 7.85–7.88 (1H, m, H-7), 8.22 (1H, dd, J 8.1 and 1.3,
H-3ꢀꢀꢀ). δC (CDCl3) 29.5 (C-3), 54.1 (C-3ꢀꢀ), 58.8 (C-2ꢀꢀ), 60.0
(C-3ꢀ), 63.4 (C-2), 124.2 (C-7), 124.9 (C-3ꢀꢀꢀ), 126.7 (C-4), 126.9
(C-6ꢀꢀꢀ), 128.2 (C-6), 129.13∗ (C-4ꢀꢀꢀ), 132.6 (C-1ꢀꢀꢀ), 134.4∗
(C-5ꢀꢀꢀ), 135.4 (C-7a), 136.0 (C-5), 147.6 (C-2ꢀꢀꢀ), 150.9 (C-3a),
199.4 (C-1).
Diastereomeric Mixture (38A:62B) of Spiro[indan-1-one-
2,2ꢀ-(2-phenyl-1,2-epoxypropyl)oxirane] 4a
Diastereomer A: rel-(2R,3ꢀS,2ꢀꢀS,3ꢀꢀR)-Spiro[indan-1-one-2,2ꢀ-
(2-phenyl-1,2-epoxypropyl)oxirane] δH (CDCl3) 3.20 (1H, dd, J
3.8 and 1.9, H-2ꢀꢀ), 3.36 and 3.59 (2 × 1H, 2d, J 18.6, H-3), 3.66
(1H, d, J 3.8, H-3ꢀ), 3.92 (1H, d, J 1.9, H-3ꢀꢀ), 7.27–7.42 (5H, m,
H-2ꢀꢀꢀ,3ꢀꢀꢀ,4ꢀꢀꢀ,5ꢀꢀꢀ,6ꢀꢀꢀ), 7.47 (1H, t, J 7.6, H-6), 7.53 (1H, dd, J 7.6
and 0.6, H-4), 7.70 (1H, t, J 7.6, H-5), 7.85 (1H, d, J 7.6, H-7).
δC (CDCl3) 29.7 (C-3), 55.6 (C-3ꢀꢀ), 58.8 (C-2ꢀꢀ), 59.6 (C-3ꢀ),
63.55 (C-2), 124.1 (C-7), 125.6 (C-2ꢀꢀꢀ,6ꢀꢀꢀ), 126.74 (C-4), 128.1
(C-6), 128.66 (C-3ꢀꢀꢀ,5ꢀꢀꢀ), 128.70 (C-4ꢀꢀꢀ), 135.5 (C-1ꢀꢀꢀ), 135.5
(C-7a), 135.9 (C-5), 151.4 (C-3a), 199.5 (C-1).
Diastereomer B: rel-(2R,3ꢀS,2ꢀꢀR,3ꢀꢀS)-Spiro[indan-1-one-
2,2ꢀ-[2-(2-nitrophenyl)-1,2-epoxypropyl]oxirane] δH (CDCl3)
2.97 (1H, dd, J 6.1 and 2.0, H-2ꢀꢀ), 3.30 and 3.56 (2 × 1H, 2d, J
18.2, H-3), 3.63 (1H, d, J 6.1, H-3ꢀ), 4.45 (1H, d, J 2.0, H-3ꢀꢀ),
7.47 (1H, t, J 7.4, H-6), 7.51–7.56 (2H, m, H-4 and H-4ꢀꢀꢀ), 7.60
(1H, dd, J 7.9 and 1.5, H-6ꢀꢀꢀ), 7.67–7.73 (2H, m, H-5 and
H-5ꢀꢀꢀ), 7.85–7.88 (1H, m, H-7), 8.19 (1H, dd, J 8.3 and 1.2,
H-3ꢀꢀꢀ). δC (CDCl3) 29.2 (C-3), 55.4 (C-3ꢀꢀ), 59.4 (C-2ꢀꢀ), 59.6
(C-3ꢀ), 63.2 (C-2), 124.2 (C-7), 124.8 (C-3ꢀꢀꢀ), 126.7 (C-4), 127.3
(C-6ꢀꢀꢀ), 128.1 (C-6), 129.05∗ (C-4ꢀꢀꢀ), 132.9 (C-1ꢀꢀꢀ), 134.6∗
(C-5ꢀꢀꢀ), 135.6 (C-7a), 135.9 (C-5), 147.2 (C-2ꢀꢀꢀ), 151.3 (C-3a),
199.1 (C-1). ∗Can be interchanged.
Diastereomer B: rel-(2R,3ꢀS,2ꢀꢀR,3ꢀꢀS)-Spiro[indan-1-one-2,
2ꢀ-(2-phenyl-1,2-epoxypropyl)oxirane] δH (CDCl3) 3.06 (1H,
dd, J 6.0 and 1.9, H-2ꢀꢀ), 3.34 and 3.62 (2 × 1H, 2d, J 18.0,
H-3), 3.52 (1H, d, J 6.0, H-3ꢀ), 4.03 (1H, d, J 1.9, H-3ꢀꢀ), 7.27–
7.42 (5H, m, H-2ꢀꢀꢀ,3ꢀꢀꢀ,4ꢀꢀꢀ,5ꢀꢀꢀ,6ꢀꢀꢀ), 7.47 (1H, t, J 7.6, H-6), 7.55
(1H, dd, J 7.1 and 1.0, H-4), 7.70 (1H, dd, J 7.6 and 7.1, H-5),
7.85 (1H, d, J 7.6, H-7). δC (CDCl3) 29.1 (C-3), 57.0 (C-3ꢀꢀ), 59.7
(C-2ꢀꢀ), 59.8 (C-3ꢀ), 63.60 (C-2), 124.2 (C-7), 125.6 (C-2ꢀꢀꢀ,6ꢀꢀꢀ),
126.71 (C-4), 128.2 (C-6), 128.66 (C-3ꢀꢀꢀ,5ꢀꢀꢀ), 128.70 (C-4ꢀꢀꢀ),
135.5 (C-1ꢀꢀꢀ), 135.8 (C-7a), 135.9 (C-5), 150.8 (C-3a), 199.1
(C-1).
mp 142–143◦C. m/z 323 (M+•, 1), 160 (69), 115 (42), 91
(100). νmax/cm−1 1720, 1607, 1520, 1468, 1342, 1303, 1252,
1201, 950, 855, 789, 733, 670. (Found: C 66.98, H 4.11.
C18H13O5 requires C 66.87, H 4.05%).
mp 119–120◦C. m/z 278 (M+•, 1), 219 (35), 115 (78), 91
(100). νmax/cm−1 1724, 1610, 1470, 1299, 1256, 1203, 986,
930, 737, 696, 597. (Found: C 77.76, H 5.01. C18H14O3 requires
C 77.68, H 5.07%).
Diastereomeric Mixture (47A:53B) of Spiro[indan-1-one-
2,2ꢀ-[2-(2-methoxyphenyl)-1,2-epoxypropyl]oxirane] 4b
Diastereomer A: rel-(2R,3ꢀS,2ꢀꢀS,3ꢀꢀR)-Spiro[indan-1-one-2,2ꢀ-
[2-(2-methoxyphenyl)-1,2-epoxypropyl]oxirane] δH (CDCl3)
3.06 (1H, dd, J 4.2 and 2.1, H-2ꢀꢀ), 3.34 and 3.63 (2 × 1H, 2d, J
18.5, H-3), 3.64 (1H, d, J 4.2, H-3ꢀ), 4.21 (1H, d, J 2.1, H-3ꢀꢀ),
Diastereomeric Mixture (40A:60B) of Spiro[(3,4-
dihydro-2H-naphthalen-1-one)-2,2ꢀ-(2-phenyl-1,2-
epoxypropyl)oxirane] 4d
Diastereomer A: rel-(2R,3ꢀS,2ꢀꢀS,3ꢀꢀR)-Spiro[(3,4-dihydro-2H-
naphthalen-1-one)-2,2ꢀ-(2-phenyl-1,2-epoxypropyl)oxirane] δH
(CDCl3) 2.38 (1H, dt, J 13.8 and 5.0, H-3), 2.49–2.58 (1H, m,

Oxidation of (E,E)-Cinnamylideneketones
87
H-3), 3.18 (1H, dd, J 4.4 and 1.8, H-2ꢀꢀ), 3.25–3.37 (2H, m,
H-4), 3.28 (1H, d, J 4.4, H-3ꢀ), 3.90 (1H, d, J 1.8, H-3ꢀꢀ), 7.26–
7.40 (7H, m, H-5, H-7, H-2ꢀꢀꢀ,3ꢀꢀ,4ꢀꢀ,5ꢀꢀ,6ꢀꢀꢀ), 7.55 (1H, t, J 7.5,
H-6), 8.06 (1H, d, J 7.8, H-8). δC (CDCl3) 26.47 (C-3), 28.0
(C-4), 55.2 (C-3ꢀꢀ), 58.5 (C-2ꢀꢀ), 61.2 (C-3ꢀ), 62.2 (C-2), 125.5
(C-2ꢀꢀꢀ,6ꢀꢀꢀ), 127.1 (C-7), 127.8 (C-8), 128.59 (C-3ꢀꢀꢀ,5ꢀꢀꢀ), 128.7
(C-4ꢀꢀꢀ), 128.8 (C-5), 132.42 (C-8a), 134.3 (C-6), 135.7 (C-1ꢀꢀꢀ),
143.51 (C-4a), 192.6 (C-1).
Diastereomeric Mixture (70A:30B) of Spiro[(3,4-
dihydro-2H-naphthalen-1-one)-2,2ꢀ-[2-(2-nitrophenyl)-
1,2-epoxypropyl]oxirane] 4f
Diastereomer A: rel-(2R,3ꢀS,2ꢀꢀS,3ꢀꢀR)-Spiro[(3,4-dihydro-2H-
naphthalen-1-one)-2,2ꢀ-[2-(2-nitrophenyl)-1,2-epoxypropyl]
oxirane] δH (CDCl3) 2.35 (1H, dt, J 14.7 and 4.7, H-3), 2.51
(1H, dt, J 14.7 and 4.5, H-3), 3.02 (1H, dd, J 6.0 and 1.8, H-2ꢀꢀ),
3.12 (1H, dt, J 16.4 and 4.7, H-4), 3.24–3.30 (1H, m, H-4), 3.48
(1H, d, J 6.0, H-3ꢀ), 4.49 (1H, d, J 1.8, H-3ꢀꢀ), 7.32 (1H, d, J 7.5,
H-5), 7.38 (1H, t, J 7.5, H-7), 7.52–7.55 (1H, m, H-4ꢀꢀꢀ), 7.59
(1H, t, J 7.5, H-6), 7.67 (1H, d, J 7.3, H-6ꢀꢀꢀ), 7.72 (1H, t, J 7.3,
H-5ꢀꢀꢀ), 8.09 (1H, d, J 7.5, H-8), 8.20 (1H, d, J 8.2, H-3ꢀꢀꢀ). δC
(CDCl3) 26.6 (C-3), 27.4 (C-4), 54.0 (C-3ꢀꢀ), 58.5 (C-2ꢀꢀ), 61.7
(C-2), 62.0 (C-3ꢀ), 124.8 (C-3ꢀꢀꢀ), 127.0 (C-6), 127.3 (C-6ꢀꢀꢀ),
127.9 (C-8), 128.8 (C-5), 129.06 (C-4ꢀꢀꢀ), 132.4 (C-8a), 133.0
(C-1ꢀꢀꢀ), 134.4 (C-7), 134.7 (C-5ꢀꢀꢀ), 143.7 (C-4a), 147.3 (C-2ꢀꢀꢀ),
192.4 (C-1).
Diastereomer B: rel-(2R,3ꢀS,2ꢀꢀR,3ꢀꢀS)-Spiro[(3,4-dihydro-
2H-naphthalen-1-one)-2,2ꢀ-(2-phenyl-1,2-epoxypropyl)oxirane]
δH (CDCl3) 2.31 (1H, dt, J 13.7 and 4.6, H-3), 2.60 (1H, ddd,
J 13.7, 11.6, and 4.8, H-3), 3.09 (1H, dd, J 6.3 and 1.6, H-2ꢀꢀ),
3.20 (1H, dt, J 11.6 and 4.6, H-4), 3.28 (1H, d, J 6.3, H-3ꢀ), 3.31–
3.38 (1H, m, H-4), 4.01 (1H, d, J 1.6, H-3ꢀꢀ), 7.29–7.40 (7H, m,
H-5, H-7, H-2ꢀꢀꢀ,3ꢀꢀ,4ꢀꢀ,5ꢀꢀ,6ꢀꢀꢀ), 7.56 (1H, t, J 7.2, H-6), 8.09 (1H,
d, J 7.8, H-8). δC (CDCl3) 26.53 (C-3), 28.0 (C-4), 57.7 (C-3ꢀꢀ),
58.4 (C-2ꢀꢀ), 61.6 (C-3ꢀ), 62.1 (C-2), 125.6 (C-2ꢀꢀꢀ,6ꢀꢀꢀ), 127.0
(C-7), 127.7 (C-8), 128.58 (C-3ꢀꢀꢀ,5ꢀꢀꢀ), 128.7 (C-4ꢀꢀꢀ), 128.8
(C-5), 132.44 (C-8a), 134.3 (C-6), 135.6 (C-1ꢀꢀꢀ), 143.47 (C-4a),
192.6 (C-1).
Diastereomer B: rel-(2R,3ꢀS,2ꢀꢀR,3ꢀꢀS)-Spiro[(3,4-dihydro-
2H-naphthalen-1-one)-2,2ꢀ-[2-(2-nitrophenyl)-1,2-epoxypropyl]
oxirane] δH (CDCl3) 2.32 (1H, dt, J 15.2 and 4.6, H-3), 2.63
(1H, dt, J 15.2 and 4.7, H-3), 3.00 (1H, dd, J 6.6 and 1.8, H-2ꢀꢀ),
3.20 (1H, dt, J 12.0 and 4.6, H-4), 3.27–3.37 (1H, m, H-4), 3.42
(1H, d, J 6.6, H-3ꢀ), 4.64 (1H, d, J 1.8, H-3ꢀꢀ), 7.33 (1H, d, J 7.5,
H-5), 7.38 (1H, t, J 7.7, H-7), 7.55–7.60 (2H, m, H-6, H-4ꢀꢀꢀ),
7.69 (1H, d, J 7.3, H-6ꢀꢀꢀ), 7.72 (1H, t, J 7.3, H-5ꢀꢀꢀ), 8.09 (1H, dd,
J 7.7, H-8), 8.21 (1H, d, J 8.3, H-3ꢀꢀꢀ). δH (CDCl3) 26.7 (C-3),
28.0 (C-4), 56.1 (C-3ꢀꢀ), 58.3 (C-2ꢀꢀ), 61.2 (C-3ꢀ), 62.0 (C-2),
124.8 (C-3ꢀꢀꢀ), 127.0 (C-6), 127.3 (C-6ꢀꢀꢀ), 127.8 (C-8), 128.8
(C-5), 129.12 (C-4ꢀꢀꢀ), 132.0 (C-8a), 132.7 (C-1ꢀꢀꢀ), 134.4 (C-7),
134.7 (C-5ꢀꢀꢀ), 143.6 (C-4a), 146.8 (C-2ꢀꢀꢀ), 192.4 (C-1).
mp 113–114◦C. m/z 337 (M+•, 1), 173 (90), 131 (32),
115 (100). νmax/cm−1 1688, 1599, 1522, 1456, 1346, 1312,
1227, 940, 860, 791, 738, 698, 665. (Found: C 67.53, H 4.54.
C19H15NO5 requires C 67.65, H 4.48%).
mp 153–154◦C. m/z 292 (M+•, 1), 233 (62), 115 (78), 91
(100). νmax/cm−1 1691, 1604, 1461, 1309, 1220, 1162, 946, 881,
845, 761, 699, 612, 547. (Found: C 78.16, H 5.47. C19H16O3
requires C 78.06, H 5.52%).
Diastereomeric Mixture (57A:43B) of Spiro[(3,4-
dihydro-2H-naphthalen-1-one)-2,2ꢀ-[2-(2-methoxyphenyl)-
1,2-epoxypropyl]oxirane] 4e
Diastereomer A: rel-(2R,3ꢀS,2ꢀꢀS,3ꢀꢀR)-Spiro[(3,4-dihydro-2H-
naphthalen-1-one)-2,2ꢀ-[2-(2-methoxyphenyl)-1,2-epoxypropyl]
oxirane] δH (CDCl3) 2.36 (1H, dt, J 16.0 and 4.9, H-3), 2.59
(1H, ddd, J 16.0, 11.8, and 4.7, H-3), 3.04 (1H, dd, J 5.0 and
2.0, H-2ꢀꢀ), 3.12–3.29 (2H, m, H-4), 3.37 (1H, d, J 5.0, H-3ꢀ),
3.86 (3H, s, OCH3), 4.21 (1H, d, J 2.0, H-3ꢀꢀ), 6.90 (1H, d, J
8.3, H-3ꢀꢀꢀ), 6.97 (1H, t, J 7.4, H-5ꢀꢀꢀ), 7.20 (1H, dd, J 7.4 and
1.6, H-6ꢀꢀꢀ), 7.26–7.33 (1H, m, H-4ꢀꢀꢀ), 7.34 (1H, d, J 7.8, H-5),
7.39 (1H, t, J 7.4, H-7), 7.57 (1H, ddd, J 7.8, 7.4, and 1.4, H-6),
8.10 (1H, dd, J 7.4 and 0.9, H-8). δC (CDCl3) 26.8 (C-3), 27.8
(C-4), 51.6 (C-3ꢀꢀ), 55.3 (2ꢀꢀꢀ-OCH3), 58.2 (C-2ꢀꢀ), 62.1 (C-3ꢀ),
62.3 (C-2), 110.1 (C-3ꢀꢀꢀ), 120.8 (C-5ꢀꢀꢀ), 124.4 (C-1ꢀꢀꢀ), 125.2
(C-6ꢀꢀꢀ), 127.0 (C-7), 127.9 (C-8), 128.7 (C-5), 129.2 (C-4ꢀꢀꢀ),
132.6 (C-8a), 134.3 (C-6), 143.7 (C-4a), 157.8 (C-2ꢀꢀꢀ), 192.7
(C-1).
Diastereomeric Mixture (71A:29B) of Spiro[(6,7,8,9-
tetrahydrobenzocyclohepten-5-one)-2,2ꢀ-(2-phenyl-
1,2-epoxypropyl)oxirane] 4g
Diastereomer A: rel-(2R,3ꢀS,2ꢀꢀS,3ꢀꢀR)-Spiro[(6,7,8,9-tetra-
hydrobenzocyclohepten-5-one)-2,2ꢀ-(2-phenyl-1,2-epoxypropyl)
oxirane] δH (CDCl3) 1.91–1.99 (m, 2H, 4-H), 1.99–2.09 (1H, m,
H-3), 2.11–2.32 (1H, m, H-3), 2.98–3.04 (2H, m, H-5), 3.16 (1H,
dd, J 5.0 and 2.0, H-2ꢀꢀ), 3.38 (1H, d, J 5.0, H-3ꢀ), 3.95 (1H, d, J
2.0, H-3ꢀꢀ), 7.25 (1H, d, J 7.3, H-6), 7.29–7.32 (2H, m, H-2ꢀꢀꢀ,6ꢀꢀꢀ),
7.35–7.40 (4H, m, H-8 and H-3ꢀꢀꢀ,4ꢀꢀꢀ,5ꢀꢀꢀ), 7.53 (1H, dt, J 7.3 and
1.4, H-7), 7.79 (1H, dd, J 7.7 and 1.4, H-9). δC (CDCl3) 22.9
(C-4), 24.7 (C-3), 32.2 (C-5), 55.3 (C-3ꢀꢀ), 59.1 (C-2ꢀꢀ), 61.3
(C-3ꢀ), 63.3 (C-2), 125.4 (C-2ꢀꢀꢀ,6ꢀꢀꢀ), 127.2 (C-8), 128.63
(C-4ꢀꢀꢀ), 128.7 (C-3ꢀꢀꢀ,5ꢀꢀꢀ), 129.1 (C-9), 129.6 (C-6), 133.5 (C-7),
135.7 (C-1ꢀꢀꢀ), 136.7 (C-9a), 140.0 (C-5a), 200.6 (C-1).
Diastereomer B: rel-(2R,3ꢀS,2ꢀꢀR,3ꢀꢀS)-Spiro[(3,4-dihydro-
2H-naphthalen-1-one)-2,2ꢀ-[2-(2-methoxyphenyl)-1,2-epoxy
propyl]oxirane] δH (CDCl3) 2.37 (1H, dt, J 16.0 and 4.9,
H-3), 2.59 (1H, ddd, J 16.0, 11.8, and 4.7, H-3), 3.02 (1H, dd, J
6.1 and 1.8, H-2ꢀꢀ), 3.17–3.33 (2H, m, H-4), 3.31 (1H, d, J 6.1,
H-3ꢀ), 3.88 (3H, s, OCH3), 4.35 (1H, d, J 1.8, H-3ꢀꢀ), 6.90 (1H,
d, J 8.3, H-3ꢀꢀꢀ), 6.95 (1H, t, J 7.6, H-5ꢀꢀꢀ), 7.17 (1H, dd, J 7.6 and
1.6, H-6ꢀꢀꢀ), 7.26–7.33 (1H, m, H-4ꢀꢀꢀ), 7.33 (1H, d, J 7.8, H-5),
7.37 (1H, t, J 7.6, H-7), 7.56 (1H, ddd, J 7.8, 7.6, and 1.4, H-6),
8.09 (1H, dd, J 7.6 and 1.0, H-8). δC (CDCl3) 26.5 (C-3), 28.1
(C-4), 53.9 (C-3ꢀꢀ), 55.4 (2ꢀꢀꢀ-OCH3), 57.9 (C-2ꢀꢀ), 61.7 (C-3ꢀ),
62.3 (C-2), 110.2 (C-3ꢀꢀꢀ), 120.6 (C-5ꢀꢀꢀ), 124.3 (C-1ꢀꢀꢀ), 125.1
(C-6ꢀꢀꢀ), 127.1 (C-7), 127.8 (C-8), 128.8 (C-5), 129.3 (C-4ꢀꢀꢀ),
132.6 (C-8a), 134.3 (C-6), 143.6 (C-4a), 158.1 (C-2ꢀꢀꢀ), 192.8
(C-1).
Diastereomer B: rel-(2R,3ꢀS,2ꢀꢀR,3ꢀꢀS)-Spiro[(6,7,8,9-tetra-
hydrobenzocyclohepten-5-one)-2,2ꢀ-(2-phenyl-1,2-epoxypropyl)
oxirane] δH (CDCl3) 1.91–1.99 (2H, m, H-4), 1.99–2.09 (1H, m,
H-3), 2.11–2.32 (1H, m, H-3), 2.98–3.04 (2H, m, H-5), 3.02 (1H,
dd, J 7.2 and 1.7, H-2ꢀꢀ), 3.24 (1H, d, J 7.2, H-3ꢀ), 4.03 (1H, d, J
1.7, H-3ꢀꢀ), 7.27 (1H, d, J 7.0, H-6), 7.31–7.33 (2H, m, H-2ꢀꢀꢀ,6ꢀꢀꢀ),
7.35–7.40 (4H, m, H-8 and H-3ꢀꢀꢀ,4ꢀꢀꢀ,5ꢀꢀꢀ), 7.53 (1H, dt, J 7.0 and
1.5, H-7), 7.78 (1H, dd, J 7.7 and 1.4, H-9). δC (CDCl3) 22.7
(C-4), 24.6 (C-3), 32.2 (C-5), 58.1 (C-3ꢀꢀ), 58.9 (C-2ꢀꢀ), 61.6
(C-3ꢀ), 63.2 (C-2), 125.5 (C-2ꢀꢀꢀ,6ꢀꢀꢀ), 127.1 (C-8), 128.63
(C-4ꢀꢀꢀ), 128.66 (C-3ꢀꢀꢀ,5ꢀꢀꢀ), 129.0 (C-9), 129.7 (C-6), 133.5
(C-7), 135.6 (C-1ꢀꢀꢀ), 136.8 (C-9a), 140.3 (C-5a), 200.6 (C-1).
mp 107–108◦C. m/z 322 (M+•, 3), 233 (73), 121 (55), 91
(100). νmax/cm−1 1686, 1602, 1497, 1466, 1303, 1250, 1222,
1107, 1027, 943, 889, 744, 708. (Found: C 74.61, H 5.57.
C20H18O4 requires C 74.52, H 5.63%).

88
A. Lévai et al.
mp 156–157◦C. m/z 306 (M+•, 1), 247 (13), 118 (54), 91
133.5 (C-7), 134.6 (C-5ꢀꢀꢀ), 137.0 (C-9a), 140.1 (C-5a), 147.4
(C-2ꢀꢀꢀ), 200.9 (C-1).
(100). νmax/cm−1 1693, 1597, 1457, 1297, 1269, 1207, 1100,
967, 943, 898, 826, 758, 615, 550. (Found: C 78.51, H 5.86.
C20H18O3 requires C 78.41, H 5.92%).
Diastereomer B: rel-(2R,3ꢀS,2ꢀꢀR,3ꢀꢀS)-Spiro[(6,7,8,9-tetra-
hydrobenzocyclohepten-5-one)-2,2ꢀ-[2-(2-nitrophenyl)-1,2-epoxy-
propyl]oxirane] δH (CDCl3) 1.84–1.93 (2H, m, H-4), 2.00 (1H,
ddd, J 14.6, 6.7, and 3.3, H-3), 2.25 (1H, ddd, J 14.6, 9.5, and
7.8, H-3), 3.00 (1H, dd, J 7.0 and 1.8, H-2ꢀꢀ), 2.98–3.04 (1H, m,
H-5), 3.14 (1H, ddd, J 14.3, 10.1, and 7.3, H-5), 3.38 (1H, d, J
7.0, H-3ꢀ), 4.69 (1H, d, J 1.8, H-3ꢀꢀ), 7.23 (1H, d, J 7.6, H-6), 7.36
(1H, dt, J 7.7 and 1.2, H-8), 7.49–7.57 (2H, m, H-7 and H-4ꢀꢀꢀ),
7.62 (1H, dd, J 7.6 and 1.6, H-6ꢀꢀꢀ), 7.72 (1H, ddd, J 7.9, 7.6,
and 1.1, H-5ꢀꢀꢀ), 7.78 (1H, dd, J 7.7 and 1.4, H-9), 8.22 (1H, dd,
J 8.0 and 1.1, H-3ꢀꢀꢀ). δC (CDCl3) 22.7 (C-4), 24.6 (C-3), 32.2
(C-5), 56.5 (C-3ꢀꢀ), 58.7 (C-2ꢀꢀ), 61.2 (C-3ꢀ), 63.0 (C-2), 124.94
(C-3ꢀꢀꢀ), 126.9 and 127.1 (C-8 and C-6ꢀꢀꢀ), 129.0 (C-9), 129.1
(C-4ꢀꢀꢀ), 129.6 (C-6), 132.6 (C-1ꢀꢀꢀ), 133.5 (C-7), 134.3 (C-5ꢀꢀꢀ),
136.9 (C-9a), 140.2 (C-5a), 147.4 (C-2ꢀꢀꢀ), 200.9 (C-1).
mp 197–198◦C. m/z 351 (M+•, 1), 187 (63), 118 (64), 91
(100). νmax/cm−1 1693, 1598, 1531, 1458, 1348, 1296, 1206,
906, 799, 765, 704. (Found: C 68.46, H 4.82. C20H17NO5
requires C 68.36, H 4.88%).
Diastereomeric Mixture (80A:20B) of
Spiro[(6,7,8,9-tetrahydrobenzocyclohepten-5-one)-2,2ꢀ-
[2-(2-methoxyphenyl)-1,2-epoxypropyl]oxirane] 4h
Diastereomer A: rel-(2R,3ꢀS,2ꢀꢀS,3ꢀꢀR)-Spiro[(6,7,8,9-tetra-
hydrobenzocyclohepten-5-one)-2,2ꢀ-[2-(2-methoxyphenyl)-1,2-
epoxypropyl]oxirane] δH (CDCl3) 1.85–2.00 (2H, m, H-4),
1.95–2.04 (1H, m, H-3), 2.24–2.34 (1H, m, H-3), 2.99 (1H, dd, J
6.0 and 2.1, H-2ꢀꢀ), 2.95–2.98 (1H, m, H-5), 3.08 (1H, dd, J 12.2
and 5.8, H-5), 3.32 (1H, d, J 6.0, H-3ꢀ), 3.90 (3H, s, 2ꢀꢀꢀ-OCH3),
4.29 (1H, d, J 2.1, H-3ꢀꢀ), 6.92 (1H, d, J 8.1, H-3ꢀꢀꢀ), 6.99 (1H, d,
J 7.4, H-5ꢀꢀꢀ), 7.21 (1H, dd, J 7.4 and 1.7, H-6ꢀꢀꢀ), 7.25 (1H, d, J
7.5, H-6), 7.31 (1H, ddd, J 8.1, 7.4, and 1.7, H-4ꢀꢀꢀ), 7.37 (1H, dt,
J 7.5 and 1.1, H-8), 7.53 (1H, dt, J 7.5 and 1.4, H-7), 7.80 (1H,
dd, J 7.5 and 1.4, H-9). δC (CDCl3) 22.9 (C-4), 25.0 (C-3), 32.2
(C-5), 51.5 (C-3ꢀꢀ), 55.29 (2ꢀꢀꢀ-OCH3), 58.9 (C-2ꢀꢀ), 62.2 (C-3ꢀ),
63.0 (C-2), 110.0 (C-3ꢀꢀꢀ), 120.8 (C-5ꢀꢀꢀ), 124.3 (C-1ꢀꢀꢀ), 124.9
(C-6ꢀꢀꢀ), 127.2 (C-8), 129.1 (C-9), 129.2 (C-4ꢀꢀꢀ), 129.5 (C-6),
133.5 (C-7), 136.78 (C-9a), 140.1 (C-5a), 157.8 (C-2ꢀꢀꢀ), 200.9
(C-1).
rel-(2R,3ꢀS)-Spiro[indan-1-one-2,2ꢀ-[2-(2-
nitrophenyl)ethenyl]oxirane] 5a
Diastereomer B: rel-(2R,3ꢀS,2ꢀꢀR,3ꢀꢀS)-Spiro[(6,7,8,9-tetra-
hydrobenzocyclohepten-5-one)-2,2ꢀ-[2-(2-methoxyphenyl)-1,2-
epoxypropyl]oxirane] δH (CDCl3) 1.85–2.00 (2H, m, H-4),
1.95–2.04 (1H, m, H-3), 2.24–2.34 (1H, m, H-3), 2.90–2.93 (1H,
m, H-5), 2.95–2.98 (1H, m, H-2ꢀꢀ), 3.13 (1H, dd, J 14.0 and 5.7,
H-5), 3.31 (1H, d, J 6.8, H-3ꢀ), 3.88 (3H, s, 2ꢀꢀꢀ-OCH3), 4.37
(1H, d, J 1.8, H-3ꢀꢀ), 6.90 (1H, d, J 8.1, H-3ꢀꢀꢀ), 6.99 (1H, t, J 7.4,
H-5ꢀꢀꢀ), 7.18 (1H, dd, J 7.4 and 1.7, H-6ꢀꢀꢀ), 7.27 (1H, d, J 7.5,
H-6), 7.29 (1H, ddd, J 8.1, 7.4, and 1.7, H-4ꢀꢀꢀ), 7.36 (1H, dt, J
7.5 and 1.1, H-8), 7.53 (1H, dt, J 7.5 and 1.4, H-7), 7.79 (1H,
dd, J 7.5 and 1.4, H-9). δC (CDCl3) 22.7 (C-4), 24.5 (C-3), 32.2
(C-5), 54.2 (C-3ꢀꢀ), 55.32 (2ꢀꢀꢀ-OCH3), 58.4 (C-2ꢀꢀ), 61.6 (C-3ꢀ),
63.3 (C-2), 110.1 (C-3ꢀꢀꢀ), 120.5 (C-5ꢀꢀꢀ), 124.3 (C-1ꢀꢀꢀ), 124.9
(C-6ꢀꢀꢀ), 127.1 (C-8), 129.0 (C-9), 129.3 (C-4ꢀꢀꢀ), 129.6 (C-6),
133.5 (C-7), 136.82 (C-9a), 140.3 (C-5a), 158.0 (C-2ꢀꢀꢀ), 200.9
(C-1).
δH (CDCl3) 3.34 and 3.44 (2H, AB, J 18.2, H-3), 4.12 (1H, dd, J
6.9 and 0.5, H-3ꢀ), 6.07 (1H, dd, J 15.9 and 6.9, H-1ꢀꢀ), 7.35 (1H,
d, J 15.9, H-2ꢀꢀ), 7.43–7.51 (2H, m, H-4ꢀꢀ and H-6), 7.52 (1H, d,
J 7.4, H-4), 7.62–7.63 (2H, m, H-5ꢀꢀꢀ and H-6ꢀꢀꢀ), 7.68 (1H, dd,
J 7.4 and 1.2, H-5), 7.85 (1H, d, J 7.8, H-7), 8.01 (1H, d, J 8.1,
H-3ꢀꢀꢀ). δC (CDCl3) 29.0 (C-3), 61.6 (C-3ꢀ), 66.6 (C-2), 124.1
(C-7), 124.8 (C-3ꢀꢀꢀ), 126.7 (C-4), 128.1 (C-6), 128.2 (C-1ꢀꢀ),
128.9 (C-4ꢀꢀꢀ), 129.0 (C-6ꢀꢀꢀ), 131.7 (C-1ꢀꢀꢀ), 131.8 (C-2ꢀꢀ), 135.4
(C-5ꢀꢀꢀ), 135.7 (C-7a), 135.8 (C-8), 147.5 (C-2ꢀꢀꢀ), 150.9 (C-3a),
199.5 (C-1). m/z (Electrospray ionization (ESI)-MS): 308.0919.
C18H14NO4 requires [M + H]+ 308.0923.
rel-(2R,3ꢀS)-Spiro[(3,4-dihydro-2H-naphthalen-1-one)-
2,2ꢀ-[2-(2-nitrophenyl)ethenyl]oxirane] 5b
δH (CDCl3) 2.27 (1H, dt, J 13.7 and 4.4, H-3), 2.60 (1H, ddd,
J 13.7, 9.4, and 7.3, H-3), 3.09–3.13 (2H, m, H-4), 3.92 (1H,
d, J 6.5, H-3ꢀ), 6.18 (1H, dd, J 15.8 and 6.5, H-1ꢀꢀ), 7.30 (1H,
d, J 7.5, H-5), 7.32 (1H, d, J 15.8, H-2ꢀꢀ), 7.37 (1H, dd, J 7.9
and 7.5, H-7), 7.47 (1H, ddd, J 8.4, 5.7, and 2.9, H-4ꢀꢀꢀ), 7.55
(1H, dt, J 7.5 and 1.4, H-6), 7.60–7.64 (2H, m, H-5ꢀꢀꢀ and H-
6ꢀꢀꢀ), 8.00 (1H, dd, J 8.4 and 1.1, H-3ꢀꢀꢀ), 8.09 (1H, dd, J 7.9
and 1.4, H-8). δC (CDCl3) 26.2 (C-3), 27.8 (C-4), 62.8 (C-3ꢀ),
64.7 (C-2), 124.7 (C-3ꢀꢀꢀ), 127.03 and 127.05 (C-7 and C-1ꢀꢀ),
127.7 (C-8), 128.8 (C-5), 128.90 and 128.94 (C-4ꢀꢀꢀ and C-6ꢀꢀꢀ),
131.8 (C-1ꢀꢀꢀ), 132.2 (C-2ꢀꢀ), 132.6 (C-8a), 132.6 (C-5ꢀꢀꢀ), 134.3
(C-6), 143.4 (C-4a), 147.5 (C-2ꢀꢀꢀ), 193.1 (C-1). m/z (ESI-MS):
322.1074. C19H16NO4 requires [M + H]+ 322.1079.
mp 145–146◦C. m/z 336 (M+•, 2), 247 (27), 121 (76), 91
(100). νmax/cm−1 1694, 1599, 1496, 1457, 1289, 1253, 1165,
1027, 944, 895, 764, 647. (Found: C 74.89, H 5.91. C21H20O4
requires C 74.98, H 5.99%).
Diastereomeric Mixture (97A:3B) of Spiro[(6,7,8,9-
tetrahydrobenzocyclohepten-5-one)-2,2ꢀ-
[2-(2-nitrophenyl)-1,2-epoxypropyl]oxirane] 4i
Diastereomer A: rel-(2R,3ꢀS,2ꢀꢀS,3ꢀꢀR)-Spiro[(6,7,8,9-tetra-
hydrobenzocyclohepten-5-one)-2,2ꢀ-[2-(2-nitrophenyl)-1,2-epoxy-
propyl]oxirane] δH (CDCl3) 1.84–1.93 (2H, m, H-4), 2.00 (1H,
ddd, J 14.6, 6.7, and 3.3, H-3), 2.25 (1H, ddd, J 14.6, 9.5, and
7.8, H-3), 3.00 (1H, dd, J 6.3 and 2.1, H-2ꢀꢀ), 2.96–3.02 (1H, m,
H-5), 3.14 (1H, ddd, J 14.3, 10.1, and 7.3, H-5), 3.46 (1H, d, J
6.3, H-3ꢀ), 4.60 (1H, d, J 2.1, H-3ꢀꢀ), 7.23 (1H, d, J 7.6, H-6), 7.36
(1H, dt, J 7.6 and 1.2, H-8), 7.52 (1H, dt, J 7.6 and 1.4, H-7),
7.54 (1H, ddd, J 8.0, 7.5, and 1.7, H-4ꢀꢀꢀ), 7.66 (1H, dd, J 7.9 and
1.7, H-6ꢀꢀꢀ), 7.72 (1H, ddd, J 7.9, 7.5, and 1.1, H-5ꢀꢀꢀ), 7.75 (1H,
dd, J 7.6 and 1.4, H-9), 8.21 (1H, dd, J 8.0 and 1.1, H-3ꢀꢀꢀ). δC
(CDCl3) 23.0 (C-4), 24.9 (C-3), 31.9 (C-5), 53.9 (C-3ꢀꢀ), 59.0
(C-2ꢀꢀ), 61.7 (C-3ꢀ), 63.0 (C-2), 124.89 (C-3ꢀꢀꢀ), 127.1 (C-8 and
C-6ꢀꢀꢀ), 129.0 (C-9), 129.1 (C-4ꢀꢀꢀ), 129.5 (C-6), 132.9 (C-1ꢀꢀꢀ),
rel-(2R,3ꢀS)-Spiro[(6,7,8,9-tetrahydrobenzocyclohepten-
5-one)-2,2ꢀ-[2-(2-nitrophenyl)ethenyl]oxirane] 5c
δH (CDCl3) 1.86–1.94 (1H, m, H-4), 1.96–2.06 (2H, m, H-3 and
H-4), 2.23–2.36 (1H, m, H-3), 2.88–3.05 (2H, m, H-5), 4.00 (1H,
d, J 7.1, H-3ꢀ), 6.16 (1H, dd, J 15.5 and 7.1, H-1ꢀꢀ), 7.21 (1H, d,
J 7.6, H-6), 7.37 (1H, dt, J 7.6 and 0.9, H-8), 7.39 (1H, d, J 15.5,
H-2ꢀꢀ), 7.45–7.51 (1H, m, H-4ꢀꢀꢀ), 7.51 (1H, dt, J 7.6 and 1.4,
H-7), 7.60–7.64 (2H, m, H-5ꢀꢀꢀ and H-6ꢀꢀꢀ), 7.79 (1H, dd, J 7.6
and 1.4, H-9), 8.02 (1H, d, J 7.8, H-3ꢀꢀꢀ). δC (CDCl3) 22.7 (C-4),
24.5 (C-3), 32.1 (C-5), 62.8 (C-3ꢀ), 65.7 (C-2), 124.8 (C-3ꢀꢀꢀ),

Oxidation of (E,E)-Cinnamylideneketones
89
127.1 (C-8), 127.2 (C-1ꢀꢀ), 128.90 and 128.94 (C-4ꢀꢀꢀ and C-6ꢀꢀꢀ),
129.1(C-9), 129.6(C-6), 131.8(C-2ꢀꢀ), 131.9(C-1ꢀꢀꢀ), 133.42and
133.44 (C-8 and C-5ꢀꢀꢀ), 136.9 (C-9a), 140.2 (C-5a), 147.6 (C-
2ꢀꢀꢀ), 201.1 (C-1). m/z (ESI-MS): 352.1185. C20H18NO4 requires
[M + H]+ 335.1158.
(f) A. M. S. Silva, D. C. G. A. Pinto, H. R. Tavares, J. A. S. Cavaleiro,
M. L. Jimeno, J. Elguero, Eur. J. Org. Chem. 1998, 2031.
doi:10.1002/(SICI)1099-0690(199809)1998:9<2031::AID-EJOC20
31>3.0.CO;2-#
[7] A. M. S. Silva, J. A. S. Cavaleiro, J. Elguero, Liebigs Ann./Recueil
1997, 2065.
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V. L. M. Silva, Eur. J. Org. Chem. 2001, 3213. doi:10.1002/1099-
0690(200109)2001:17<3213::AID-EJOC3213>3.0.CO;2-K
[9] C. M. M. Santos,A. M. S. Silva, J.A. S. Cavaleiro,A. Lévai,T. Patonay,
Eur. J. Org. Chem. 2007, 2877. doi:10.1002/EJOC.200700123
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S. R. Thornton, C. J. Todd, J. Chem. Soc., Perkin Trans. 1 1996, 343.
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Acknowledgements
Thanks are due to the Hungarian Scientific Research Fund (Grant no.
T049468) and also to the University of Aveiro, ‘Fundação para a Ciência
e a Tecnologia’ and FEDER for funding the Organic Chemistry Research
Unit. The technical assistance of Mrs M. Nagy and Mr L. Szabó is highly
appreciated.
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