Construction of fused cyclooctanoid ring systems via seven-membered ring carbonyl ylides

Article abstract of DOI:10.1246/bcsj.75.801

A series of α-diazo carbonyl compounds tethered to cyclopentanone/cyclohexanone/1-tetralone units have been synthesized using a diazomethane solution to construct various fused cyclooctane ring systems via rhodium-generated carbonyl ylides. The reaction of rhodium(II) acetate dimer with various α-diazo carbonyl compounds generated transient cyclic seven-membered ring carbonyl ylides, which underwent facile 1,3-dipolar cycloadditions with dipolarophiles, like N-phenylmaleimide, p-benzoquinone, and DMAD to furnish a variety of fused epoxy-bridged cyclooctane ring systems in a tandem manner. Interestingly, an oxepine ring system was generated via an intramolecular proton transfer of a seven-membered ring carbonyl ylide. A tri-oxa polycyclic compound was obtained in the case of p-benzoquinone as dipolarophile. A single-crystal X-ray analysis of a fused cyclootanoid derivative is reported to decisively establish the structure and stereochemistry of the fused epoxy-bridged cyclooctane ring systems; a further analysis revealed the existence of a unique intermolecular C-H ···π interaction motif in the solid-state architecture.

Full text of DOI:10.1246/bcsj.75.801

c. Jpn.
© 2002 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 75, 801–811 (2002)
801
e Chemical
ciety of Ja-
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e Chemical
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Construction of Fused Cyclooctanoid Ring Systems via Seven-Membered
Ring Carbonyl Ylides
Construction of Fused Cyclooctanoid Frameworks
S. Muthusamy et al.
Sengodagounder Muthusamy,* Srinivasarao Arulananda Babu, Chidambaram Gunanathan,
02
1
Eringathodi Suresh, and Parthasarathi Dastidar
1
Silicates and Catalysis Discipline, Central Salt and Marine Chemicals Research Institute, Bhavnagar 364 002, India
(Received August 29, 2001)
SJA8
09-2673
301
A series of α-diazo carbonyl compounds tethered to cyclopentanone/cyclohexanone/1-tetralone units have been
synthesized using a diazomethane solution to construct various fused cyclooctane ring systems via rhodium-generated
carbonyl ylides. The reaction of rhodium(Ⅱ) acetate dimer with various α-diazo carbonyl compounds generated transient
cyclic seven-membered ring carbonyl ylides, which underwent facile 1,3-dipolar cycloadditions with dipolarophiles, like
N-phenylmaleimide, p-benzoquinone, and DMAD to furnish a variety of fused epoxy-bridged cyclooctane ring systems
in a tandem manner. Interestingly, an oxepine ring system was generated via an intramolecular proton transfer of a sev-
en-membered ring carbonyl ylide. A tri-oxa polycyclic compound was obtained in the case of p-benzoquinone as dipo-
larophile. A single-crystal X-ray analysis of a fused cyclootanoid derivative is reported to decisively establish the struc-
ture and stereochemistry of the fused epoxy-bridged cyclooctane ring systems; a further analysis revealed the existence
of a unique intermolecular C–H≥π interaction motif in the solid-state architecture.
01
01
Although there are many synthetic processes which involve
both cyclization and cycloaddition approaches to five- and six-
membered ring systems, seven- and eight-membered ring sys-
tems have not attracted much attention. Cyclization strategies
to obtain medium-sized rings are often regarded as inappropri-
ate because of entropy factors that hamper ring closure.1 Some
very imaginative and elegant cycloaddition, annulation ap-
proaches, and metal-mediated synthesis towards medium-sized
rings have proven to be useful.2–6 Additionally, ring expansion
from more readily available carbocycles can provide efficient
access to seven- and eight-membered rings.6–10 Recently, a
protocol for eight- and nine-membered ring synthesis using an
annulation strategy has been reported11 by Molander et al. The
eight-membered ring is the latest entrant into the marked col-
lection of carbocyclic rings present in natural products, prima-
rily among terpenoids. In the past few years, the number of
carbocyclic skeletons in which a cyclooctane forms a part of
the condensed or bridged polycyclic system has proliferated
rapidly. The isolation and characterization of many complex
natural products containing cyclooctane rings and the attention
to synthesize them in a regio-, stereo-, and enantioselective
manner is an important intention in organic synthesis. Many
protocols involving diverse cycloadditions, cyclizations, radi-
cal-mediated ring expansions, fragmentation methods, rear-
rangement methods, and coupling reactions involving eight-
membered ring formations have been reported and reviewed.12
The cyclooctane structural units present in a wide range of nat-
ural products exist either as isolated rings, or form parts of bi-
cyclic or tricyclic frameworks, for example, tremulenediol A
(1),10 dumortenol (2),13 and roseadione (3)14 (Chart 1). A pos-
sible retro-synthetic analysis to fused cyclooctane skeletons
via α-diazo ketone involving a seven-membered carbonyl ylide
is shown in Scheme 1.
Chart 1.
Scheme 1.
Diazo compounds have found numerous applications in or-
ganic synthesis, and their use in either carbocyclic or heterocy-
clic ring formation is well precedented.15–17 The transition
metal-mediated carbon-carbon bond-forming reactions from
various α-diazo ketone precursors have been utilized in vari-
ous natural product syntheses, such as brevicomin,18 phorbol
derivatives,19,20 and zaragozic acid A.21

802 Bull. Chem. Soc. Jpn., 75, No. 4 (2002)
Construction of Fused Cyclooctanoid Frameworks
The chemistry of rhodium-generated five- and six-mem-
bered ring carbonyl ylides and their cycloaddition with a π-
bond has been extensively studied.22–24 Recently, we have re-
ported the formation of five- and six-membered ring carbonyl
ylides and their consequent cycloaddition reactions with vari-
ous dipolarophiles as an approach to epoxy-bridged polycyclic
systems.25–29 However, the chemistry of seven-membered ring
carbonyl ylides and their subsequent cycloadditions is still not
skillfully exploited. There appears to be only one report30
where seven-membered ring carbonyl ylide formation was ob-
served. The generation of carbonyl ylides, and followed by a
cycloaddition methodology represents a powerful tool to con-
struct polycyclic rings, because it creates multiple bonds in a
single operation with high regio- and stereocontrol of the re-
mote substituents. As a consequence of our continuing interest
in the development of tandem rhodium carbenoid reactions,25–29
we herein report on both the generation and reactions of vari-
ous seven-membered ring carbonyl ylides towards the synthe-
sis of fused cyclooctanoid ring systems.
Scheme 3.
Table 1. Keto Esters 9,10 Produced via the Enamine Method
Yielda)/%
Product
n
R1
R2
R3
9
10
—
33
—
—
—
a
b
c
d
e
1
1
2
2
3
H
CH3
H
H
H
CH3
H
CH3
H
CH3
79
49
84
76
83
CH2CH3
CH3
CH2CH3
CH2CH3
Results and Discussion
The generation of intermolecular carbonyl ylides and their
subsequent 1,3-dipolar cycloaddition reactions were report-
ed31,32 by Huisgen and co-workers. Generation followed by
cycloadditions of intramolecular carbonyl ylides have been
well exploited and applied to the synthesis of epoxy-bridged
cyclic systems. The epoxy-bridge serves as a latent hydroxy
substituent of defined stereochemistry. Most of the studies
found in the literature were carried out involving only a facile
formation of intramolecular five- and six-membered ring car-
bonyl ylides.15,22,23 The main feature in the generation of
intramolecualr carbonyl ylides relies on an attack of the neigh-
boring carbonyl oxygen at the rhodium carbenoid center to
form a carbonyl ylide dipole, which consequently undergoes
cycloaddition across a π-bond of a dipolarophile. An effective
overlap could occur if the distance between rhodium carbenoid
and lone pairs of carbonyl group is sufficiently close, and in
turn forms an intermediate carbonyl ylide. As shown in
Scheme 2, seven-membered ring carbonyl ylide intermediates
6b are proposed to be generated in the reaction of diazo carbo-
nyl compounds using rhodium(Ⅱ) acetate as a catalyst.
H
a) Yields (unoptimized) were based on cycloalkanones.
en-membered ring carbonyl ylides, the required diazo carbonyl
compounds 12 were assembled from commercially available
materials. The enamine,33 prepared from corresponding cy-
cloalkanone using pyrrolidine, was subjected to a Michael re-
action with acceptors, like ethyl acrylate or methyl methacry-
late, to afford the required alkylated cycloalkanone esters 9a–e,
10b (Scheme 3, Table 1). The reaction of enamine 8b with
ethyl acrylate afforded two products, 9b and 10b, due to the
existence of a mixture of unsymmetrical enamines that formed
from pyrrolidine and 2-methylcyclopentanone.
A careful hydrolysis of keto esters (prepared via Scheme 3)
using 8% aqueous KOH solution afforded the corresponding
acids 11a–f, respectively, in very good yield. The treatment of
acid 11a–f with ethyl chloroformate and triethylamine resulted
in a white suspension at room temperature, and the resulting
mixed anhydride was treated with freshly prepared ethereal di-
azomethane at 0–10 °C to furnish α-diazo ketones 12a–f, re-
spectively (Scheme 4). To a solution of diazo ketone 12a and
N-phenylmaleimide in dry dichloromethane was added 0.5
mol% rhodium(Ⅱ) acetate catalyst; and the reaction mixture
was stirred under an argon atmosphere for 3 h at room temper-
ature followed by chromatographic purification, which fur-
nished exclusively product 14a in 61% yield (Scheme 4, Table
2).
To study the generation and cycloaddition behavior of sev-
The IR spectrum of product 14a showed characteristic
strong bands at 1780 and 1717 cm−1 due to the presence of
1
carbonyl groups. The H NMR of product 14a showed the
characteristic singlet at δ 4.81 due to the presence of a bridge-
head proton (H-9) and two doublets at δ 3.69 and 3.21 for H-
10/14, respectively, with a coupling constant of J = 8.2 Hz.
13C NMR and dept-135 spectra exhibited the presence of eight
CH, four CH2, one CH3, and five quaternary carbons, that evi-
dently confirmed the formation of product 14a. This reaction
reveals that the generation of a seven-membered ring carbonyl
Scheme 2.

S. Muthusamy et al.
Bull. Chem. Soc. Jpn., 75, No. 4 (2002) 803
Scheme 5.
one (16d) without forming the expected cycloaddition product.
This reaction indicated that seven-membered carbonyl ylide
13d did not undergo cycloaddition with the electron-rich ful-
vene (Scheme 4). It is interesting to note that we have very re-
cently demonstrated the cycloaddition reaction of five-mem-
bered ring carbonyl ylides with various electron-rich ful-
venes.29
Scheme 4.
Reagents: (i) a) ClCOOEt, NEt3, Ether, b)
CH2N2, Ether; (ii) Rh2(OAc)4, DCM; (iii) N-phenylmale-
imide; (iv) DMAD; (v) cyclopenta-2,4-dienylidenecyclo-
hexane.
Consequently, we performed a rhodium-catalyzed reaction
of diazo ketone 12d in the presence of p-benzoquinone (17) as
a bifunctional dipolarophile (Scheme 5). This reaction was
carried out in the presence of 0.5 mol% of rhodium(II) acetate
in dry dichloromethane, and allowed to be stirred at room tem-
perature; the reaction was followed by TLC until disappear-
ance of diazo ketone 12d. The reaction mixture was purified
through neutral alumina column chromatography to afford
three products 18–20. All of these products were characterized
based on their interrelated spectral data. The reaction fur-
nished CwO (18), CwC (19), and CwO/water (20) addition
products in a similar manner to five- and six-membered ring
carbonyl ylide reactions28 with p-benzoquinone as a dipolaro-
phile. The formation of product 20 may be due to the addition
of a water molecule on 18, followed by a Michael-type cy-
clization reaction under the performed experimental condition.
It may be noted that product 20 was produced in a single step
from diazo carbonyl compound 12d by forming four new C–O
bonds and one C–C bond, in turn producing five chiral centers
in the molecule.
The reaction of diazo ketone 12d was performed in the ab-
sence of any dipolarophiles under similar reaction conditions,
followed by column purification of the reaction mixture, which
furnished product 16d in 69% yield (Scheme 4). The forma-
tion of product 16d may be attributed to an intramolecular pro-
ton transfer to produce 4,5,6,7,8,9-hexahydrobenzo[b]oxepin-
3-one. A general mechanism for a fast proton transfer is
shown in Scheme 6.34
After studying various ring systems, we were interested in
further illustrating the scope and synthetic utility of the tandem
cyclization-cycloaddition sequence using seven-membered
ring carbonyl ylides. To this end, we opted to study the rhodi-
um-catalyzed behavior of diazo carbonyl compound 22
(Scheme 7, Table 3). We synthesized the required diazo car-
Table 2. Fused Cyclooctanes 14,15 Produced via Scheme 4
Entry
n
R1
R2
R3
Time
Yielda)/%
h
14
61
58
49
57
58
64
—
—
—
15
—
—
—
—
—
—
54
61
45
a
b
c
d
e
f
g
h
i
1
1
1
2
2
3
1
1
1
H
CH3
H
H
H
CH3
H
CH3
H
H
2.5
3.0
3.0
2.0
2.5
3.0
1.5
2.5
3.0
H
H
H
H
H
H
CH3
H
H
CH3
H
H
H
CH3
CH3
H
H
a) Yields (unoptimized) refer to isolated and chromato-
graphically pure compounds of 14 and 15.
ylide as a transient species in the presence of rhodium(Ⅱ) ace-
tate is followed by trapping with N-phenylmaleimide to fur-
nish the cycloadduct 14a containing a cyclooctane ring system.
In order to generalize, we carried out a rhodium-catalyzed re-
action with other diazo carbonyl compounds 12b–f to afford
respective fused cyclooctane ring systems 14b–f. Similarly,
the reaction of diazo ketones 12a–c in the presence of DMAD
also afforded the corresponding fused cyclooctane ring sys-
tems 15g–i. All of these products were clearly characterized
based on their interrelated spectral data. The reaction of diazo
ketone 12d with cyclopenta-2,4-dienylidenecyclohexane in dry
dichloromethane was performed in the presence of rhodium(Ⅱ)
acetate, followed by chromatographic purification of the reac-
tion mixture, which afforded a rearranged product 16d, which
was characterized as 4,5,6,7,8,9-hexahydrobenzo[b]oxepin-3-

804 Bull. Chem. Soc. Jpn., 75, No. 4 (2002)
Construction of Fused Cyclooctanoid Frameworks
Scheme 6.
Fig. 1. ORTEP view of tetralone derived cyclooctanoid ring
system 24.
treated with ethyl chloroformate in the presence of triethy-
lamine to afford a mixed anhydride, which upon a treatment
with diazomethane furnished diazo compound 22. A rhodi-
um(Ⅱ)-catalyzed reaction of diazo ketone 22 was performed
with various dipolarophiles, like naphthoquinones and N-phen-
ylmaleimide. In the presence of N-phenylmaleimide, the reac-
tion afforded cycloadduct 24 and proton-transfer product
4,5,6,7-tetrahydronaphtho[1,2-b]-[1]oxepin-3(2H)-one (25),
which were well characterized based on interrelated spectral
data.
The IR spectrum of product 24 showed characteristic peaks
at 1782 and 1716 cm−1 due to the presence of carbonyl groups.
1
The H NMR spectrum revealed the characteristic singlet at δ
Scheme 7. Reagents: (i) 5% KOH, r.t., 5 h, 96%; (ii) a) ethyl
chloroformate/triethylamine, r.t., 45 min., b) CH2N2, dry
ether, 0 °C, 12 h then 10 °C, 2 h, 60%; (iii) N-phenylmale-
imide, 3.5 h; (iv) 1,4-naphthoquinone, 3.5 h; (v) 2,3-
dichloro-1,4-naphthoquinone, 3 h.
4.98 for the presence of a bridgehead proton, two doublets at δ
4.04 and 3.47 for H-15/19 protons with coupling constants of J
= 8.4 Hz, respectively. The 13C NMR and dept-135 spectra
exhibited the presence of eleven CH, four CH2, and seven qua-
ternary carbons. All of these spectral analyses evidently con-
firmed the formation of a novel cyclooctane derivative. To de-
termine the stereochemical aspects, product 24 was further
characterized by a single-crystal X-ray analysis (Fig. 1), which
clearly revealed the formation of an exo cycloadduct. The ob-
served angle of the epoxy-bridge was 110.2° (C14–O20–C1).
The cell parameters and intensity of the compound were mea-
sured in the range θ = 2-22.5° at room temperature. Twenty-
five reflections with θ = 7–10° were used to obtain accurate
cell dimensions. Three standard reflections, monitored every 1
h, showed no significant crystal decay for the entire period of
data collection. The crystal orientation, cell refinement, and
intensity measurements were carried out using the program
CAD-4PC. The raw intensity data were corrected for Lorentz
polarization effects. The Lorentz polarization correction and
data reduction were carried out using the NRCVAX program.35
Because the number of reflections to the parameter ratio was
Table 3. Yields of Product 24,25 Produced via Scheme 7
Yielda)/%
Reactant
24
40
—
—
—
25
13
42
44
60
N-Phenylmaleimide
1,4-Naphthoquinone
2,3-Dichloro-1,4-naphthoquinone
Rh2(OAc)4
a) Yields (unoptimized) were based on 22.
bonyl compound 22, starting from α-tetralone. The enamine33
prepared from (α-tetralone and pyrrolidine was subjected to a
Michael addition reaction with ethyl acrylate in dry 1,4-diox-
ane to furnish 3-(1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)pro-
pionic acid ethyl ester (21). Upon the hydrolysis of 21, the
corresponding acid was obtained, which was subsequently

S. Muthusamy et al.
Bull. Chem. Soc. Jpn., 75, No. 4 (2002) 805
low, the phenyl rings in the molecule were kept isotropic in the
final refinement cycles using the program SHELXL-97 until
convergence was reached. All of these the H-atoms were fixed
stereochemically by a riding model using the program
SHELXL-97.36 The final cycles of a least-squares refinement
in the locked fashion described earlier yielded R-value of R1 =
9.012% (wR2 = 22.40%) for compound 24.
Furthermore, we were eager to view the packing interac-
tions in molecule 24. The packing arrangement molecule 24 in
its solid-state architecture revealed two novel C–H≥π interac-
tions and viewed down a-axis, as shown in Fig. 2. It is inter-
esting to note that molecules are held together in the crystal
lattice via C–H≥π interactions.37 The molecules are associat-
ed as dimers with the N-phenyl rings of the dimeric units hav-
ing come closer to the aromatic part of tetralone from either
end to make effective C–H≥π interactions. The C–H≥π pa-
rameters for this dimeric interaction are H3≥C2G = 3.119 Å,
C3≥C2G = 3.850 Å, and < C3–H3≥C2G = 136.78°, where
C2G is the centroid of C24–C29.
The dimers run parallel to the b-axis (Fig. 2). The H15 atom
(endo proton) of the associated dimeric molecules are further
involved in C–H≥π bonding with the aromatic part tetralone
(C2–C7) of adjacent dimeric layers from both the side extend-
ing the layers into a sheet-like supramolecular architecture.
The parameters for this C–H≥π interaction are H15–C1G =
2.728 Å, C15≥C1G = 3.657 Å, and < C15–H15≥C1G =
158.26°, where C1G is the centroid of the fused phenyl ring,
C2–C7. A close-up ORTEP view of both of these C–H≥π in-
teractions is shown in Fig. 3.
Finally, the reaction of diazo ketone 22 in the presence of
0.5 mol% rhodium(Ⅱ) acetate dimer was carried out with 1,4-
naphthoquionone as well as 2,3-dichloro-1,4-naphthoquinone
as dipolarophiles. In these cases, we isolated only the intramo-
lecular proton-transfer product 25 (Scheme 7) instead of the
respective cycloadduct 26. The reason may be due to a favor-
able fast transfer of a proton34 (Scheme 6) instead of a cycload-
dition process and the strain involved in the product formation.
Similarly, the reaction was carried out in the absence of any di-
polarophile with rhodium(Ⅱ) acetate catalyst; purification of
the reaction mixture afforded the proton-transfer product in
61% yield.
In summary, we have described the generation of various
seven-membered ring carbonyl ylides from various α-diazo
carbonyl compounds and their subsequent 1,3-dipolar cycload-
dition with dipolarophiles to afford fused cyclooctane ring sys-
tems. Interestingly, the reaction of a seven-membered carbon-
yl ylide with p-benzoquinone provided three epoxy-bridged
polycyclic systems in a single step. A proton-transfer rear-
rangement was observed in the case of carbonyl ylides 13d, 23
instead of undergoing cycloaddition with a dipolarophile, such
as cyclopenta-2,4-dienylidenecyclohexane or 1,4-naphtho-
quinones, respectively. A single-crystal X-ray analysis of mol-
ecule 24 and its interactions in a solid-state architecture were
carried out to evidently assign the stereochemical aspects.
Fig. 2. Packing diagram of compound 24 viewed down a-
axis showing the dimeric association. Only H3 and H15
hydrogen atoms, which are involved in C–H≥π interac-
tions included in the figure.
Experimental
The melting points are uncorrected. The IR spectra were re-
Fig. 3. ORTEP diagram of 24 showing the C–H≥π interactions (thin lines) present in Fig. 2 that stabilizing the molecule in the
crystal lattice. C1G and C2G are the centroid of the aromatic part of tetralone C2–C7 and N-phenyl ring C24 to C29, respectively.

806 Bull. Chem. Soc. Jpn., 75, No. 4 (2002)
Construction of Fused Cyclooctanoid Frameworks
corded on a Perkin–Elmer Spectrum GX FT-IR spectrophotome-
ter. 1H NMR and 13C NMR spectra were recorded on a Bruker
Avance DPX 200 (200 MHz and 50.3 MHz, respectively) spec-
trometer and referenced to TMS. Carbon types were determined
from DEPT 13C NMR experiments. The chemical-shift (δ) values
are reported as parts per million (ppm). The multiplicity of the 1H
NMR signal is designated by one of the following abbreviations: s
= singlet, d = doublet, q = quartet, br = broad, and m = multip-
let. Coupling constants (J) are reported in Hz. Mass analyses
were performed on a Jeol D-300 (with an ionizing voltage of 70
eV) or a Jeol M Station 700 (FD+ method in absolute dichlo-
romethane) mass spectrometer. Elemental analyses were per-
formed on a Perkin–Elmer Model 2400 analyzer. An X-ray crys-
tallographic analysis was carried out in an Enraf Nonius CAD-4
diffractometer with Mo Kα radiation. All of the reactions were
carried out under an argon atmosphere and solutions dried with
anhydrous magnesium sulfate. Diethyl ether was distilled from
sodium benzophenone ketyl immediately before use. Toluene/
Benzene were dried and stored over sodium prior to use. Dry
dichloromethane was dried using P2O5. Thin-layer chromatogra-
phy was performed on silica/alumina plates and components were
visualized by observation under iodine or by sulfuric acid char-
ring. Column chromatography was performed on silica gel/neu-
tral alumina. Care was taken to avoid light during the course of
the reaction in the synthesis of diazo compounds and their further
conversion.
General Procedure for Alkylation of Enamines of Cyclic Al-
kanones to Prepare Cycloalkanone Esters (9, 10b, and 21) via
Stork-Enamine Alkylation Method.33 A benzene solution (100
cm3) of appropriate cyclic alkanone (50 mmol) and pyrrolidine
(100 mmol) was refluxed under a water separator in the presence
of a catalytic amount of p-toluenesulfonic acid for 12–15 h until
no water separation. The solvent, excess of pyrrolidine was re-
moved under reduced pressure and the crude enamine was taken
in dry 1,4-dioxane (100 cm3) under an argon atmosphere. To the
reaction mixture, ethyl acrylate or methyl methacrylate (65 mmol)
was added at room temperature with stirring and refluxed for 12–
15 h. After an appropriate period, 15 cm3 of water was added and
the reaction mixture further refluxed for 2 h. The reaction mixture
was concentrated, the crude reaction mixture was extracted using
ethyl acetate (3×75 cm3), and the organic layer was separated and
washed twice with dilute hydrochloric acid (50 cm3), brine solu-
tion, dried over anhydrous MgSO4, and concentrated in a vacuum.
The crude residue was purified over silica-gel column chromato-
graphy to afford the respective alkylated products 9a–e,10b.
benzene solution (50 cm3) of 2-methylcylcopentanone (5 g, 51
mmol) and pyrrolidine (8.5 cm3, 102 mmol) was refluxed under a
water separator to obtain the pyrrolidine enamine of 2-methyl-
cyclopentanone; to the crude enamine reaction mixture in dry 1,4-
dioxane (50 cm3) was added ethyl acrylate (7.1 cm3, 66.3 mmol)
at room temperature with stirring, and refluxed for 13 h; and the
reaction mixture was worked-up according to the general method
to obtain 9b (4.9 g, 49%) and 10b (3.3 g, 33%). 9b: Colorless oil;
1
IR (neat) 2935, 1734, 1313, 1232, 1170, 1140 cm−1; H NMR
(CDCl3, 200 MHz) δ 4.11 (2H, q, J = 7.2 Hz, OCH2), 2.45–1.40
(10H, m), 1.25 (3H, t, J = 7.2 Hz, CH2CH3), 1.09 (3H, d, J = 6.8
Hz, CH3); 13C NMR (CDCl3, 50.3 MHz) δ 221.2 (CwO), 172.8
(COO), 60.0 (OCH2), 47.7 (CH), 43.9 (CH), 31.8 (CH2), 29.6
(CH2), 27.3 (CH2), 25.3 (CH2), 14.2 (CH2), 14.0 (CH3).
Ethyl-3-(1-methyl-2-oxocyclopentyl)propionate
(10b).
Colorless oil; IR (neat) 2936, 2861, 1735, 1230 1201 cm−1; H
NMR (CDCl3, 200 MHz) δ 4.10 (2H, q, J = 7.2 Hz, OCH2), 2.40–
1.65 (8H, m), 1.60–1.20 (2H, m), 1.25 (3H, t, J = 7.2 Hz,
CH2CH3), 1.02 (3H, s, CH3); 13C NMR (CDCl3, 50.3 MHz) δ
221.8 (CwO), 172.9 (COO), 60.0 (OCH2), 47.0 (quat-C), 37.1
(CH2), 35.7 (CH2), 31.1 (CH2), 29.2 (CH2), 21.1 (CH3), 18.3
(CH2), 14.0 (CH3). Found: C, 66.69; H, 9.16%. Calcd for
C11H18O3: C, 66.64; H, 9.15%.
1
Methyl-2-methyl-3-(2-oxocyclohexyl)propionate (9c).
A
benzene solution (50 cm3) of cyclohexanone (5 g, 51 mmol) and
pyrrolidine (8.5 cm3, 102 mmol) was refluxed under a water sepa-
rator to obtain the pyrrolidine enamine of cyclohexanone; to the
crude enamine reaction mixture in dry 1,4-dioxane (50 cm3) was
added methyl methacrylate (7.1 cm3, 66.3 mmol) at room temper-
ature with stirring, and refluxed for 15 h; and the reaction mixture
was worked-up according to the general method to obtain 9c (8.5
g, 84%). Colorless oil; IR (neat) 2937, 2862, 1734, 1711, 1453,
1376, 1313, 1231, 1200, 1171, 1141 cm−1; 1H NMR (CDCl3, 200
MHz) δ 3.60 (3H, s, OCH3), 2.35–1.20 (12H, m), 1.15 (3H, d, J =
6.8 Hz, CH3); 13C NMR (CDCl3, 50.3 MHz) δ 212.4 (CwO), 177.4
(COO), 51.2 (OCH3), 48.1 (CH), 41.7 (CH2), 36.6 (CH), 33.9
(CH2), 33.2 (CH2), 27.8 (CH2), 24.8 (CH2), 17.4 (CH3).
Ethyl-3-(2-oxocyclohexyl)propionate (9d). A benzene solu-
tion (50 cm3) of cyclohexanone (5 g, 51 mmol) and pyrrolidine
(8.5 cm3, 102 mmol) was refluxed under a water separator to ob-
tain the pyrrolidine enamine of cyclohexanone; to the crude enam-
ine reaction mixture in dry 1,4-dioxane (50 cm3) was added ethyl
acrylate (7.2 cm3, 66.3 mmol) at room temperature with stirring,
and refluxed for 12 h; and the reaction mixture was worked-up ac-
cording to the general method to obtain 9d (7.6 g, 76%). Color-
1
Methyl-2-methyl-3-(2-oxocyclopentyl)propionate (9a).
A
less oil; H NMR (CDCl3, 200 MHz) δ 4.11 (2H, q, J = 7.2 Hz,
benzene solution (50 cm3) of cyclcopentanone (3 g, 35.7 mmol)
and pyrrolidine (6.1 cm3, 71.4 mmol) was refluxed under a water
separator to obtain the pyrrolidine enamine of cyclcopentanone; to
the crude enamine reaction mixture in dry 1,4-dioxane (30 cm3)
was added methyl methacrylate (5 cm3, 46.4 mmol) at room tem-
perature with stirring, and refluxed for 12 h; and the reaction mix-
ture was worked-up according to the general method to obtain 9a
(5.1 g, 79%). Colorless oil; IR (neat) 2959, 2879, 1737, 1736,
1458, 1269, 1156, 1095 cm−1; 1H NMR (CDCl3, 200 MHz) δ 3.67
(3H, s, OCH3), 2.70–2.55 (1H, m), 2.33–2.00 (6H, m), 1.85–1.49
(3H, m), 1.17 (3H, d, J = 6.8 Hz, CH3); 13C NMR (CDCl3, 50.3
MHz) δ 220.4 (CwO), 176.3 (COO), 51.6 (OCH3), 47.4 (CH),
38.0 (CH), 37.6 (CH2), 33.8 (CH2), 29.9 (CH2), 20.7 (CH2), 17.2
(CH3).
OCH2), 2.48–2.23 (5H, m,), 2.20–1.35 (8H, m), 1.25 (3H, t, J =
7.2 Hz, CH2CH3); 13C NMR (CDCl3, 50.3 MHz) δ 212.5 (CwO),
173.6 (COO), 60.2 (OCH2), 49.8 (CH), 42.2 (CH2), 34.2 (CH2),
31.9 (CH2), 28.1 (CH2), 25.1 (CH2), 24.9 (CH2), 14.2 (CH3).
Ethyl-3-(2-oxocycloheptyl)propionate (9e). A benzene so-
lution (50 cm3) of cycloheptanone (5 g, 44.6 mmol) and pyrroli-
dine (7.5 cm3, 89.3 mmol) was refluxed under a water separator to
obtain the pyrrolidine enamine of cycloheptanone; to the crude
enamine reaction mixture in dry 1,4-dioxane (30 cm3) was added
ethyl acrylate (6.3 cm3, 58 mmol) at room temperature with stir-
ring, and refluxed for 15 h; and the reaction mixture was worked-
up according to the general method to obtain 9e (7.9 g, 83%).
Colorless oil; IR (neat) 2980, 2931, 2858, 1735, 1702, 1452, 1376,
1246, 1176, 1034 cm−1; 1H NMR (CDCl3, 200 MHz) δ 4.13 (2H,
q, J = 7.2 Hz, OCH2), 2.55–2.20 (5H, m), 2.18–1.50 (7H, m),
Ethyl-3-(3-methyl-2-oxocyclopentyl)propionate (9b).
A

S. Muthusamy et al.
Bull. Chem. Soc. Jpn., 75, No. 4 (2002) 807
1.41–1.21 (3H, m), 1.25 (3H, t, J = 7.2 Hz, CH2CH3); 13C NMR
(CDCl3, 50.3 MHz) δ 215.2 (CwO), 173.3 (COO), 60.2 (OCH2),
51.1 (CH), 42.8 (CH2), 31.9 (CH2), 31.5 (CH2), 29.3 (CH2), 28.5
(CH2), 27.2 (CH2), 24.2 (CH2), 14.2 (CH3).
m), 2.28–1.99 (6H, m), 1.86–1.20 (3H, m), 1.18 (3H, d, J = 6.8
Hz, CH3). Found: C, 61.80; H, 7.29; N, 14.46%. Calcd for
C10H14N2O2: C, 61.84; H, 7.27; N, 14.42%.
2-(4-Diazo-3-oxobutyl)-5-methylcyclopentanone (12b). The
hydrolysis of the ester 9b (2 g, 10.1 mmol) with an 8% aqueous
potassium hydroxide solution for 6 h afforded 3-(3-methyl-2-oxo-
cyclopentyl)propionic acid (11b, 1.5 g, in 88%). A solution con-
taining 1.4 g (8.2 mmol) of crude acid in dry ether was treated
with 1 cm3 (10 mmol) of ethyl chloroformate and 1.8 cm3 (12.4
mmol) of triethylamine to afford a mixed anhydride, and a treat-
ment with 16.4 mmol of a diazomethane solution gave the diazo
ketone 12b (0.8 g, 49%). 11b: Colorless thick oil; IR (neat) 3349,
1736, 1457, 1418, 1211, 1151, 1121 cm−1; 1H NMR (CDCl3, 200
MHz) δ 4.89 (1H, br s, COOH), 2.60–1.75 (7H, m), 1.70–1.39
(3H, m), 1.11 (3H, d, J = 6.8 Hz, CH3). 12b: Bright yellow oil;
IR (neat) 3095, 2961, 2105, 1736, 1642, 1450, 1376, 1340, 1067
cm−1; 1H NMR (CDCl3, 200 MHz) δ 5.39 (1H, br s, CHN2), 2.60–
1.59 (6H, m), 1.55–1.30 (4H, m), 1.10 (3H, d, J = 6.8 Hz, CH3);
13C NMR (CDCl3, 50.3 MHz) δ 222.2 (CwO), 194.8 (CwO), 54.8
(CHN2), 48.1 (CH), 44.5 (CH), 41.1 (CH2), 31.6 (CH2), 27.3
(CH2), 26.0 (CH2), 14.7 (CH3). Found: C, 61.69; H, 7.26; N,
14.45%. Calcd for C10H14N2O2: C, 61.84; H, 7.27; N, 14.42%.
2-(4-Diazo-3-oxobutyl)-2-methylcyclopentanone (12c). The
hydrolysis of the ester 10b (2 g, 10.1 mmol) with an 8% aqueous
potassium hydroxide solution for 4.5 h afforded 3-(1-methyl-2-
oxocyclopentyl)propionic acid (11c, 6 g, in 90%). A solution con-
taining 1.4 g (8.2 mmol) of crude acid in dry ether was treated
with 1 cm3 (10.1 mmol) of ethyl chloroformate and 1.8 cm3 (12.4
mmol) of triethylamine to afford a mixed anhydride, and a treat-
ment with 16.4 mmol of a diazomethane solution gave the diazo
ketone 12c (0.8 g, 48%). 11c: Colorless thick oil; IR (neat) 3309,
1732, 1453, 1411, 1219, 1165, 1120, 986 cm−1; 1H NMR (CDCl3,
200 MHz) δ 6.71 (1H, br s, COOH), 2.65–1.80 (7H, m), 1.75–
1.45 (3H, m), 1.00 (3H, s, CH3). 12c: Bright yellow oil; IR (neat)
Ethyl-3-(1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)propio-
nate (21). A benzene solution (50 cm3) of 1-tetralone (5 g, 34.2
mmol) and pyrrolidine (5.7 cm3, 68.4 mmol) was refluxed under a
water separator to obtain the pyrrolidine enamine of 1-tetralone; to
the crude enamine reaction mixture in dry 1,4-dioxane (50 cm3)
was added ethyl acrylate (4.9 cm3, 45 mmol) at room temperature
with stirring, and refluxed for 15 h; and the reaction mixture was
worked-up according to the general method to obtain 21 (6.1 g,
73%). Pale orange oil; IR (neat) 2980, 2935, 2867, 1732, 1683,
1601, 1452, 1373, 1290, 1225, 1032 cm−1; 1H NMR (CDCl3, 200
MHz) δ 8.02–7.95 (1H, m, arom-H), 7.46–7.14 (3H, m, arom-H),
4.12 (2H, q, J = 7.1 Hz, OCH2), 3.01–2.95 (2H, m), 2.58–2.15
(5H, m), 1.95–1.77 (3H, m), 1.24 (3H, t, J = 7.1 Hz, CH2CH3);
13C NMR (CDCl3, 50.3 MHz) δ 199.4 (CwO), 173.4 (COO), 143.8
(arom quat-C), 133.2 (wCH), 132.4 (arom quat-C), 128.7 (wCH),
127.3 (wCH), 126.5 (wCH), 60.2 (OCH2), 46.7 (CH), 31.9 (CH2),
28.7 (CH2), 28.6 (CH2), 25.1 (CH2), 14.2 (CH3).
General Procedure for the Synthesis of Diazo Ketones (12a–
f and 22), from Keto Esters. Keto ester 9a–e/10b (12 mmol)
was carefully hydrolyzed using 8% aqueous potassium hydroxide
solution (20 cm3) with stirring at room temperature. The reaction
was monitored by TLC and continued until disappearance of the
starting material. The reaction mixture was extracted with ether
(3×10 cm3), acidified the aqueous layer (pH = 5), and extracted
with ether (3×15 cm3). The organic phase was concentrated un-
der reduced pressure at room temperature to obtain the corre-
sponding keto acids 11a–f. To a solution containing 1 equivalent
of appropriate keto acid 11a–f (10 mmol) in 100 cm3 of freshly
distilled dry ether was added 1.2 equivalent of freshly distilled
ethyl chloroformate followed by the slow addition of 1.5 equiva-
lent of dry triethylamine. The resulting mixture was stirred at
room temperature for 45 min. and the solid that formed was fil-
tered under an inert atmosphere. After the filtrate was added to 20
mmol of freshly prepared ethereal diazomethane solution, the
mixture stirred under an argon atmosphere for 12 h at 0 °C; it was
then allowed to warm to 10 °C for a period of 2 h under an argon
atmosphere. At the end of this time, the solvent was removed un-
der reduced pressure and chromatographic purification of this res-
idue through a neutral alumina column (pre-washed by ethyl ace-
tate) led to the corresponding diazo ketones 12a–f with 15% ethyl
acetate–hexane elution. The same sequences of reactions were
carried out to prepare the diazo ketone 22 from the keto ester 21.
1
3096, 2961, 2105, 1734, 1642, 1455, 1378, 1345, 1160 cm−1; H
NMR (CDCl3, 200 MHz) δ 5.40 (1H, br s, CHN2), 2.60–2.40 (4H,
m), 2.35–1.40 (6H, m), 1.01 (3H, s, CH3); 13C NMR (CDCl3, 50.3
MHz) δ 222.9 (CwO), 194.8 (CwO), 54.7 (CHN2), 47.8 (quat-C),
37.8 (CH2), 36.5 (CH2), 30.1 (CH2), 28.0 (CH2), 21.7 (CH3), 18.8
(CH2). Found: C, 61.76; H, 7.23; N, 14.39%. Calcd for
C10H14N2O2: C, 61.84; H, 7.27; N, 14.42%.
2-(4-Diazo-3-oxobutyl)cyclohexanone (12d).30 The hydrol-
ysis of the ester 9d (3 g, 15.1 mmol) with an 8% aqueous potassi-
um hydroxide solution for 4 h afforded 3-(2-oxocyclohexyl)propi-
onic acid (2.3 g in 90%). A solution containing 2 g (11.8 mmol)
of crude acid in dry ether was treated with 1.3 cm3 (14.1 mmol) of
ethyl chloroformate and 2.5 cm3 (17.6 mmol) of triethylamine to
afford a mixed anhydride, and a treatment with 23.5 mmol of a di-
azomethane solution gave the diazo ketone 12d (1.2 g, 53%).
12d: Thick yellow oil; IR (neat) 2934, 2861, 2075, 1712, 1709,
1648, 1448, 1291, 1265, 1219, 1167 cm−1; 1H NMR (CDCl3, 200
MHz) δ 5.31 (1H, br s, CHN2), 2.44–2.29 (5H, m), 2.17–1.35 (8H,
m); 13C NMR (CDCl3, 50.3 MHz) δ 212.8 (CwO), 194.9 (CwO),
54.4 (CH), 49.8 (CH2), 42.2 (CH2), 38.4 (CH2), 34.3 (CH2), 28.1
(CH2), 25.0 (CH2), 24.7 (CH2).
2-(4-Diazo-2-methyl-3-oxobutyl)cyclohexanone (12e). The
hydrolysis of the ester 9c (1 g, 5.1 mmol) with an 8% aqueous po-
tassium hydroxide solution for 5 h afforded 2-methyl-3-(2-oxocy-
clohexyl)propionic acid (11e, 0.7 g, in 81%). A solution contain-
ing 0.6 g (3.3 mmol) of crude acid in dry ether was treated with
0.37 cm3 (3.9 mmol) of ethyl chloroformate and 0.69 cm3 (4.9
2-(4-Diazo-2-methyl-3-oxobutyl)cyclopentanone
(12a).
The hydrolysis of the ester 9a (1 g, 5.4 mmol) with an 8% aqueous
potassium hydroxide solution for 6 h afforded 2-methyl-3-(2-oxo-
cyclopentyl)propionic acid (11a, 0.8 g, in 88%). A solution con-
taining 0.7 g (4.1 mmol) of crude acid in dry ether was treated
with 0.47 cm3 (4.9 mmol) of ethyl chloroformate and 0.87 cm3
(6.2 mmol) of triethylamine to afford a mixed anhydride, and a
treatment with 8.2 mmol of a diazomethane solution gave the dia-
zo ketone 12a (0.5 g, 62%). 11a: Colorless thick oil; IR (neat)
3234, 2972, 2881, 1735, 1730, 1460, 1405, 1158, 1120, 1038, 737
1
cm−1; H NMR (CD3CN, 200 MHz) δ 4.70 (1H, br s, COOH),
2.67–2.56 (1H, m), 2.29–1.96 (6H, m), 1.83–1.28 (3H, m), 1.16
(3H, d, J = 6.8 Hz, CH3). 12a: Thick yellow oil; IR (neat) 2967,
1
2878, 2104, 1811, 1736, 1639, 1458, 1325, 1155, 1023 cm−1; H
NMR (CDCl3, 200 MHz) δ 5.37 (1H, br s, CHN2), 2.84–2.74 (1H,

808 Bull. Chem. Soc. Jpn., 75, No. 4 (2002)
Construction of Fused Cyclooctanoid Frameworks
mmol) of triethylamine to afford a mixed anhydride, and a treat-
ment with 6.6 mmol of a diazomethane solution gave the diazo ke-
tone 12e (0.4 g, 54%). 11e: Colorless thick oil; IR (neat) 3180,
um(Ⅱ) acetate dimer, which was allowed to stir for 3 h under an ar-
gon atmosphere at room temperature, followed by TLC until dis-
appearance of the starting material. The solvent was removed un-
der reduced pressure and the residue was purified by a neutral alu-
mina column to furnish the respective cycloadducts.
1
2937, 2864, 1706, 1653, 1456, 1339, 1235, 1124 cm−1; H NMR
(CDCl3, 200 MHz) δ 7.71 (1H, br s, COOH), 2.60–1.27 (12H, m),
1.19 (3H, d, J = 6.8 Hz, CH3). 12e: Thick yellow oil; IR (neat)
α
Reaction of -Diazo Ketone 12a with N-Phenylmaleimide.
2932, 2862, 2096, 1733, 1708, 1629, 1453, 1736, 1259, 1200 cm−1
;
A mixture of N-phenylmaleimide (285 mg, 1.6 mmol) and diazo
ketone 12a (160 mg, 0.8 mmol) in dry dichloromethane (8 cm3)
was allowed to react with (1.8 mg) rhodium(Ⅱ) acetate dimer at
room temperature under an argon atmosphere for 2.5 h according
to the general method to afford 14a in (165 mg, 61%). Colorless
solid (from chloroform/hexane); mp 205–207 °C; IR (KBr) 2968,
1H NMR (CDCl3, 200 MHz) δ 5.33 (1H, br s, CHN2), 2.34–1.25
(12H, m), 1.17 (3H, d, J = 6.8 Hz, CH3). Found: C, 63.39; H,
7.79; N, 13.39%. Calcd for C11H16N2O2: C, 63.44; H, 7.74; N,
13.45%.
2-(4-Diazo-3-oxobutyl)cycloheptanone (12f). The hydroly-
sis of the ester 9e (1.5 g, 7.1 mmol) with an 8% aqueous potassi-
um hydroxide solution for 5 h afforded 3-(2-oxocycloheptyl)pro-
pionic acid (1.2 g in 93%). A solution containing 1 g (5.4 mmol)
of crude acid in dry ether was treated with 0.62 cm3 (6.5 mmol) of
ethyl chloroformate and 1.2 cm3 (8.2 mmol) of triethylamine to af-
ford a mixed anhydride, and a treatment with 10.8 mmol of a diaz-
omethane solution gave the diazo ketone 12f (0.6 g, 53%). 11f:
Colorless thick oil; IR (neat) 3247, 3091, 2928, 2854, 1738, 1729,
1
2938, 1780, 1717, 1598, 1498, 1458, 1385, 1191, 1089 cm−1; H
NMR (CDCl3, 200 MHz) δ 7.52–7.39 (3H, m, arom-H), 7.29–7.25
(2H, m, arom-H), 4.81 (1H, s, OCH), 3.69 (1H, d, J = 8.2 Hz),
3.45–3.36 (1H, m), 3.21 (1H, d, J = 8.2 Hz), 2.41–1.58 (9H, m),
1.07 (3H, d, J = 6.8 Hz, CH3); 13C NMR (CDCl3, 50.3 MHz) δ
214.6 (CwO), 175.6 (NCwO), 175.1 (NCwO), 132.2 (quat-C),
129.3 (wCH), 128.9 (wCH), 126.4 (wCH), 95.8 (quat-C), 84.7
(OCH), 52.6 (CH), 49.1 (CH), 48.6 (CH), 38.0 (CH), 35.1 (CH2),
31.5 (CH2), 27.6 (CH2), 20.6 (CH2), 15.7 (CH3); MS m/z (rel in-
tensity) 339 (M+; 100), 321 (10), 311 (46), 283 (21), 269 (16),
241 (47), 175 (61), 174 (40), 137 (69), 136 (18), 135 (19), 94 (80).
Found: C, 70.71; H, 6.23; N, 4.12%. Calcd for C20H21NO4: C,
70.78; H, 6.24; N, 4.13%.
1
1456, 1400, 1158, 1120, 1038, 980 cm−1; H NMR (CDCl3, 200
MHz) δ 5.71 (1H, br s, COOH), 2.59–2.19 (5H, m), 2.17–1.45
(7H, m), 1.40–1.20 (3H, m). 12f: Thick yellow oil; IR (neat)
3091, 2929, 2857, 2103, 1734, 1698, 1641, 1451, 1376, 1148 cm−1
;
1H NMR (CDCl3, 200 MHz) δ 5.30 (1H, br s, CHN2), 2.60–2.20
(5H, m), 2.15–1.58 (7H, m), 1.44–1.19 (3H, m); 13C NMR
(CDCl3, 50.3 MHz) δ 215.3 (CwO), 194.8 (CwO), 54.5 (CHN2),
50.7 (CH), 42.8 (CH2), 38.4 (CH2), 31.9 (CH2), 29.3 (CH2), 28.5
(CH2), 27.2 (CH2), 24.2 (CH2). Found: C, 63.49; H, 7.76; N,
13.41%. Calcd for C11H16N2O2: C, 63.44; H, 7.74; N, 13.45%.
2-(4-Diazo-3-oxobutyl)-3,4-dihydronaphthalen-1(2H)-one
(22). The hydrolysis of the ester 21 (2 g, 8.1 mmol) with an 8%
aqueous potassium hydroxide solution for 5 h afforded the 3-(1-
oxo-1,2,3,4-tetrahydronaphthalen-2-yl)propionic acid (1.7 g in
96%). A solution containing 1.5 g (6.9 mmol) of crude acid in dry
ether was treated with 0.8 cm3 (8.3 mmol) of ethyl chloroformate
and 1.5 cm3 (10.3 mmol) of triethylamine to afford a mixed anhy-
dride, and a treatment with 15.8 mmol of a diazomethane solution
gave the diazo ketone 22 (1 g, 60%). 3-(1-Oxo-1,2,3,4-tetrahy-
dronaphthalen-2-yl)propionic acid: Pale orange thick oil; IR (neat)
α
Reaction of -Diazo Ketone 12b with N-Phenylmaleimide.
A mixture of N-phenylmaleimide (240 mg, 1.4 mmol) and diazo
ketone 12b (135 mg, 0.7 mmol) in dry dichloromethane (8 cm3)
was allowed to react with (1.5 mg) rhodium(Ⅱ) acetate dimer at
room temperature under an argon atmosphere for 3 h according to
the general method to afford 14b (138 mg, 58%). Colorless solid
(from ethyl acetate/hexane); mp 185–187 °C; IR (KBr) 2961,
2873, 1777, 1715, 1494, 1459, 1390, 1196, 1090, 973, 738 cm−1
;
1H NMR (CDCl3, 200 MHz) δ 7.48–7.39 (3H, m, arom-H), 7.30–
7.25 (2H, m, arom-H), 4.90 (1H, s, OCH), 3.53 (1H, d, J = 8.4
Hz), 33.21 (1H, d, J = 8.4 Hz), 2.80–2.00 (4H, m), 1.90–1.17
(6H, m), 1.13 (3H, d, J = 6.8 Hz, CH3); 13C NMR (CDCl3, 50.3
MHz) δ 213.8 (CwO), 175.5 (NCO), 175.4 (NCO), 132.2 (quat-
C), 129.7 (wCH), 129.3 (wCH), 126.7 (wCH), 97.6 (quat-C), 85.3
(OCH), 53.5 (CH), 48.8 (CH), 48.1 (CH), 42.4 (CH2), 38.4 (CH2),
28.2 (CH2), 25.9 (CH2), 23.3 (CH2), 19.1 (CH3); MS m/z (rel in-
tensity) 339 (M+; 86), 321 (26), 282 (55), 267 (34), 188 (16), 175
(100), 174 (56), 166 (48), 136 (30), 135 (41). Found: C, 70.69;
H, 6.21; N, 4.09%. Calcd for C20H21NO4: C, 70.78; H, 6.24; N,
4.13%.
1
3478, 2934, 1716, 1684, 1602, 1454, 1288, 1226, 745 cm−1; H
NMR (CDCl3, 200 MHz) δ 7.93–7.89 (1H, m, arom-H), 7.60–7.51
(1H, m, arom-H), 7.49–7.24 (2H, m, arom-H), 4.75 (1H, br s,
COOH), 3.09–2.94 (2H, m), 2.58–2.33 (3H, m), 2.27–2.08 (2H,
m), 1.97–1.65 (2H, m). 22: Dark yellow thick oil; IR (neat) 3022,
2935, 2843, 2104, 1765, 1693, 1603, 1488, 1217, 1138, 1084, 987,
α
Reaction of -Diazo Ketone 12c with N-Phenylmaleimide.
754 cm−1
;
1H NMR (CDCl3, 200 MHz) δ 8.02–7.97 (1H, m,
A mixture of N-phenylmaleimide (240 mg, 1.4 mmol) and diazo
ketone 12c (135 mg, 0.7 mmol) in dry dichloromethane (8 cm3)
was allowed to react with (1.5 mg) rhodium(Ⅱ) acetate dimer at
room temperature under an argon atmosphere for 3 h according to
the general method to afford 14c (116 mg, 49%). Colorless solid
(from ethyl acetate/hexane); mp 177–179 °C; IR (KBr) 2956,
2876, 1718, 1496, 1456, 1387, 1198 cm−1; 1H NMR (CDCl3, 200
MHz) δ 7.47–7.39 (3H, m, arom-H), 7.29–7.25 (2H, m, arom-H),
4.83 (1H, s, OCH), 3.55 (1H, d, J = 8.4 Hz), 3.29 (1H, d, J = 8.4
arom-H), 7.49–7.42 (1H, m, arom-H), 7.32–7.21 (2H, m, arom-
H), 5.34 (1H, br s, CHN2), 3.04–2.98 (2H, m), 2.55–2.48 (3H, m),
2.28–2.13 (2H, m), 2.08–1.81 (2H, m); 13C NMR (CDCl3, 50.3
MHz) δ 200.3 (CwO), 195.2 (CwO), 144.3 (arom quat-C), 133.7
(wCH), 132.8 (arom quat-C), 129.2 (wCH), 127.7 (wCH), 126.9
(wCH), 54.9 (CHN2), 47.1 (CH), 38.7 (CH2), 29.4 (CH2), 28.9
(CH2), 25.7 (CH2). Found: C, 69.47; H, 5.89, N, 11.50%. Calcd
for C14H14N2O2: C, 69.41; H, 5.83, N, 11.56%.
General Procedure for the Rhodium(ꢀ)-Catalyzed Cycload-
Hz), 2.95–1.99 (5H, m), 1.95–1.17 (5H, m), 1.19 (3H, s, CH3); 13
C
dition of Diazo Ketones (12, 22) with Dipolarophiles.
An
NMR (CDCl3, 50.3 MHz) δ 212.4 (CwO), 175.8 (NCO), 173.7
(NCO), 132.2 (quat-C), 129.6 (wCH), 129.2 (wCH), 126.6 (wCH),
97.5 (quat-C), 86.3 (OCH), 52.0 (CH), 51.1 (quat-C), 48.1 (CH),
42.3 (CH2), 32.0 (CH2), 27.4 (CH2), 26.1 (CH2), 17.4 (CH2), 14.9
(CH3); MS m/z (rel intensity) 339 (M+; 61), 321 (24), 311 (17),
oven-dried flask containing 2 equivalents of dipolarophile and ap-
propriate diazo ketone in (8 cm3) dry dichloromethane (dried over
diphosphorus pentaoxide) was degasified under an argon atmo-
sphere. To this reaction mixture was added (0.5 mol%) rhodi-

S. Muthusamy et al.
Bull. Chem. Soc. Jpn., 75, No. 4 (2002) 809
283 (20), 282 (19), 255 (12), 175 (65), 174 (35), 167 (21), 138
(20), 137 (34), 136 (27), 135 (24). Found: C, 70.81; H, 6.29; N,
4.06%. Calcd for C20H21NO4: C, 70.78; H, 6.24; N, 4.13%.
mmol) in dry dichloromethane (5 cm3) was allowed to react with
(0.6 mg) rhodium(Ⅱ) acetate dimer at room temperature under an
argon atmosphere for 1.5 h according to the general method to
Reaction of -Diazo Ketone 12d with N-Phenylmaleimide.
afford
7-methyl-8-oxo-12-oxatricyclo[7.2.1.01,5]dodec-10-ene-
α
A mixture of N-phenylmaleimide (350 mg, 2 mmol) and diazo ke-
tone 12d (200 mg, 1 mmol) in dry dichloromethane (10 cm3) was
allowed to react with (2.2 mg) rhodium(Ⅱ) acetate dimer at room
temperature under an argon atmosphere for 2 h according to the
general method to afford 14d (193 mg, 57%). Colorless solid
(from chloroform/hexane) mp 206–208 °C; IR (KBr) 2933, 2864,
10,11-dicarboxylic acid dimethyl ester (15g, 42 mg, 54%). Color-
less thick oil; IR (neat) 2960, 2941, 1731, 1719, 1590, 1502, 1450,
1360, 1201, 1090, 980 cm−1; 1H NMR (CDCl3, 200 MHz) δ 5.10
(1H, s, OCH), 3.86 (3H, s, OCH3), 3.78 (3H, s, OCH3), 3.41–3.30
(1H, m), 2.38–1.59 (9H, m), 1.10 (3H, d, J = 6.8 Hz, CH3); MS
m/z 308 (M+). Found: C, 62.27; H, 6.57%. Calcd for C16H20O6:
C, 62.33; H, 6.54%.
1777, 1712, 1493, 1458, 1393, 1202, 1090 cm−1 1H NMR
;
α
(CDCl3, 200 MHz) δ 7.47–7.39 (3H, m, arom-H), 7.29–7.24 (2H,
m, arom-H), 4.85 (1H, s, OCH), 3.57 (1H, d, J = 8.4 Hz), 3.35
(1H, d, J = 8.4 Hz), 3.20–3.05 (1H, m), 2.35–2.23 (1H, m), 2.02–
1.26 (11H, m); 13C NMR (CDCl3, 50.3 MHz) δ 214.2 (CwO),
175.3 (NCwO), 174.9 (NCwO), 131.6 (quat-C), 129.3 (wCH),
128.9 (wCH), 126.3 (wCH), 90.0 (quat-C), 85.1 (OCH), 53.0
(CH), 52.7 (CH), 45.0 (CH), 37.4 (CH2), 36.2 (CH2), 28.0 (CH2),
25.7 (CH2), 25.4 (CH2), 22.6 (CH2); MS m/z (rel intensity) 339
(M+; 69), 321 (35), 312 (17), 282 (12), 175 (100), 174 (48), 166
(15), 148 (17), 138 (32), 137 (88). Found: C, 70.84, H, 6.26; N,
4.19%. Calcd for C20H21NO4: C, 70.78; H, 6.24; N, 4.13%.
Reaction of -Diazo Ketone 12b with DMAD.
A
mixture
of DMAD (150 mg, 1 mmol) and diazo ketone 12b (100 mg, 0.5
mmol) in dry dichloromethane (5 cm3) was allowed to react with
(1.1 mg) of rhodium(Ⅱ) acetate dimer at room temperature under
an argon atmosphere for 2.5 h according to the general method
to afford 2-methyl-8-oxo-12-oxatricyclo[7.2.1.01,5]dodec-10-ene-
10,11-dicarboxylic acid dimethyl ester (15h, 94 mg, 61%). Color-
less thick oil; IR (neat) 2957, 1726, 1650, 1281, 909 cm−1; H
1
NMR (CDCl3, 200 MHz) δ 5.13 (1H, s, OCH), 3.82 (3H, s,
OCH3), 3.80 (3H, s, OCH3), 3.20–2.25 (5H, m), 2.05–1.04 (5H,
m), 1.02 (3H, d, J = 6.8 Hz, CH3); 13C NMR (CDCl3, 50.3 MHz)
δ 210.6 (CwO), 165.1 (COO), 161.9 (COO), 144.8 (quat-C), 134.7
(quat-C), 104.1 (quat-C), 88.2 (OCH), 53.0 (OCH3), 52.9 (OCH3),
49.5 (CH), 45.5 (CH), 39.0 (CH2), 32.6 (CH2), 29.7 (CH2), 24.8
(CH2), 16.4 (CH3); MS m/z 308 (M+). Found: C, 62.21, H,
6.47%. Calcd for C16H20O6: C, 62.33; H, 6.54%.
α
Reaction of -Diazo Ketone 12e with N-Phenylmaleimide.
A mixture of N-phenylmaleimide (140 mg, 0.8 mmol) and diazo
ketone 12e (75 mg, 0.4 mmol) in dry dichloromethane (5 cm3) was
allowed to react with (0.7 mg) rhodium(Ⅱ) acetate dimer at room
temperature under an argon atmosphere for 2.5 h according to the
general method to afford 14e (81 mg, 58%). Colorless solid (from
chloroform/hexane) mp 211–213 °C; IR (KBr) 2863, 1776, 1711,
1455, 1392, 1089 cm−1; 1H NMR (CDCl3, 200 MHz) δ 7.52–7.39
(3H, m, arom-H), 7.29–7.25 (2H, m, arom-H), 4.81 (1H, s, OCH),
3.40 (1H, d, J = 8.4 Hz), 3.10 (1H, d, J = 8.4 Hz), 3.22–3.04 (1H,
m), 2.35–2.22 (1H, m), 2.12–1.26 (10H, m), 1.08 (3H, d, J = 6.8
Hz, CH3); 13C NMR (CDCl3, 50.3 MHz) δ 214.3 (CwO), 175.4
(NCwO), 174.8 (NCwO), 131.5 (quat-C), 129.3 (wCH), 128.9
(wCH), 126.3 (wCH), 90.1 (quat-C), 85.2 (OCH), 53.1 (CH), 52.6
(CH), 45.0 (CH), 37.8 (CH), 35.9 (CH2), 28.1 (CH2), 25.6 (CH2),
25.4 (CH2), 22.7 (CH2), 14.9 (CH3); MS m/z 353 (M+). Found: C,
71.41, H, 6.58; N, 3.93%. Calcd for C21H23NO4: C, 71.37; H,
6.56; N, 3.96%.
α
Reaction of -Diazo Ketone 12c with DMAD.
A
mixture
of DMAD (150 mg, 1 mmol) and diazo ketone 12c (100 mg, 0.5
mmol) in dry dichloromethane (5 cm3) was allowed to react with
(1.1 mg) rhodium(Ⅱ) acetate dimer at room temperature under an
argon atmosphere for 3 h according to the general method to
afford
5-methyl-8-oxo-12-oxatricyclo[7.2.1.01,5]dodec-10-ene-
10,11-dicarboxylic acid dimethyl ester (15i, 71 mg, 45%). Color-
less thick oil; IR (neat) 3024, 2956, 2882, 1728, 1656, 1438, 1326,
1271, 1233, 1055, 757 cm−1; 1H NMR (CDCl3, 200 MHz) δ 5.02
(1H, s, OCH), 3.88 (3H, s, OCH3), 3.77 (3H, s, OCH3), 3.00–2.50
(3H, m), 2.45–1.25 (7H, m), 1.21 (3H, s, CH3); 13C NMR (CDCl3,
50.3 MHz) δ 207.4 (CwO), 164.2 (COO), 161.5 (COO), 151.1
(quat-C), 130.4 (quat-C), 103.5 (quat-C), 88.4 (OCH), 53.3
(OCH3), 52.9 (OCH3), 51.1 (quat-C), 41.0 (CH2), 34.5 (CH2), 32.3
(CH2), 31.0 (CH2), 21.4 (CH2), 18.8 (CH3); MS m/z (rel intensity)
308 (M+; 5), 276 (30), 249 (27), 248 (32), 234 (21), 220 (18), 210
(27), 202 (31), 198 (27), 189 (58), 179 (55), 178 (32), 153 (25),
133 (21), 55 (100). Found: C, 62.39; H, 6.49%. Calcd for
C16H20O6: C, 62.33; H, 6.54%.
α
Reaction of -Diazo Ketone 12f with N-Phenylmaleimide.
A mixture of N-phenylmaleimide (350 mg, 2 mmol) and diazo ke-
tone 12f (210 mg, 1 mmol) in dry dichloromethane (10 cm3) was
allowed to react with (2.2 mg) rhodium(Ⅱ) acetate dimer at room
temperature under an argon atmosphere for 3 h according to the
general method to afford 14f (226 mg, 64%). Colorless solid
(from chloroform/hexane) mp 217–219 °C; IR (KBr) 2928, 2859,
α
Reaction of -Diazo Ketone 12d with Rhodium(ꢀ) Acetate
1777, 1709, 1493, 1396, 1195, 1094, 1027 cm−1
;
1H NMR
Dimer. A solution of diazo ketone 12d (100 mg, 0.5 mmol) in
dry dichloromethane (5 cm3) was allowed to react with (1.1 mg)
rhodium(Ⅱ) acetate dimer at room temperature under an argon at-
mosphere for 3.5 h according to the general method to afford
4,5,6,7,8,9-hexahydrobenzo[b]oxepin-3-one (16d, 58 mg, 69%).
Colorless thick oil; IR (neat) 2930, 1716, 1449, 1371, 1140, 1025
(CDCl3, 200 MHz) δ 7.52–7.36 (3H, m, arom-H), 7.30–7.26 (2H,
m, arom-H), 4.81 (1H, s, OCH), 3.62 (1H, d, J = 8.4 Hz), 3.36
(1H, d, J = 8.4 Hz), 3.16–3.03 (1H, m), 2.36–1.26 (14H, m); 13
C
NMR (CDCl3, 50.3 MHz) δ 214.2 (CwO), 175.3 (NCwO), 174.9
(NCwO), 131.7 (quat-C), 129.3 (wCH), 128.9 (wCH), 126.3
(wCH), 94.2 (quat-C), 84.1 (OCH), 54.2 (CH), 53.6 (CH), 49.9
(CH), 38.6 (CH2), 37.4 (CH2), 29.3 (CH2), 29.4 (CH2), 28.5 (CH2),
27.9 (CH2), 21.9 (CH2); MS m/z (rel intensity) 353 (M+; 40), 335
(13), 325 (14), 175 (56), 174 (56), 152 (31), 151 (71), 150 (35),
135 (23), 132 (10), 91 (72), 55 (100). Found: C, 71.41, H, 6.58;
N, 3.96%. Calcd for C21H23NO4: C, 71.37; H, 6.56; N, 3.96%.
cm−1; H NMR (CDCl3, 200 MHz) δ 4.26 (2H, s, OCH2), 2.92–
1
2.85 (2H, m), 2.18–1.23 (10H, m); 13C NMR (CDCl3, 50.3 MHz)
δ 213.4 (CwO), 152.5 (quat-C), 114.1 (quat-C), 78.4 (OCH2), 40.1
(CH2), 30.5 (CH2), 29.4 (CH2), 29.2 (CH2), 23.4 (CH2), 22.9
(CH2); MS m/z (rel intensity) 166 (M+; 45), 165 (20), 164 (17),
153 (44), 152 (19), 151 (27), 145 (13), 141 (20), 139 (25), 55
(100). Found: C, 72.21; H, 8.45%. Calcd for C10H14O2: C, 72.26;
H, 8.49%.
α
Reaction of -Diazo Ketone 12a with DMAD.
A
mixture
of DMAD (75 mg, 0.5 mmol) and diazo ketone 12a (50 mg, 0.25

810 Bull. Chem. Soc. Jpn., 75, No. 4 (2002)
Construction of Fused Cyclooctanoid Frameworks
α
Reaction of -Diazo Ketone 12d with p-Benzoquinone (17):
4,5,6,7-Tetrahydronaphtho[1,2-b][1]oxepin-3(2H)-one (25):
A mixture of p-benzoquinone (215 mg, 2 mmol) and diazo ketone
12d (195 mg, 1 mmol) was allowed to react with rhodium(Ⅱ) ace-
tate dimer (2.2 mg) in dichloromethane solution (10 cm3) at room
temperature under an argon atmosphere for 2.5 h according to the
general method to afford three products 18, 19, and 20 in 40%
overall yield. 18: (49 mg, 18%), mixture of diastereomers in the
ratio of 1:0.7, colorless solid (from chloroform/hexane) mp 156–
158 °C; IR (KBr) 2935, 2861, 1715, 1675, 1635, 1449, 1228,
Colorless thick oil; IR (neat) 3066, 2929, 2835, 1725, 1680, 1657,
1602, 1486, 1432, 1374, 1324, 1135, 1094 cm−1 1H NMR
;
(CDCl3, 200 MHz) δ 7.46–7.42 (1H, m, arom-H), 7.24–7.12 (3H,
m, arom-H), 4.45 (2H, s, OCH2), 3.09–3.02 (2H, m), 2.82–2.74
(2H, m), 2.52–2.45 (2H, m), 2.29–2.22 (2H, m); 13C NMR
(CDCl3, 50.3 MHz) δ 212.5 (CwO), 149.6 (quat-C), 135.4 (quat-
C), 132.3 (quat-C), 127.4 (wCH), 127.0 (wCH), 126.5 (wCH),
121.1 (wCH), 118.5 (quat-C), 78.9 (OCH2), 39.4 (CH2),
29.5(CH2), 28.8 (CH2), 27.7 (CH2); MS m/z 214 (M+). Found: C,
78.41; H, 6.57%. Calcd for C14H14O2: C, 78.48; H, 6.59%.
X-ray Crystal Structure Analysis of Compound 24. Crys-
tal data for the 1-tetralone derived cyclooctane derivative 24:
C24H21NO4, Mr = 387.42, 0.10×0.06×0.04 mm, Monoclinic,
P21/a, a = 11.275(5) Å, b = 12.927(3) Å, c = 13.791(5) Å, β =
113.30(3)°, V = 1846.1(11) Å3, T = 293(2) K, R1 = 0.0912, wR2
= 0.2240 on observed data, Z = 4, Dcalc. = 1.394 Mg m−3, F(000)
= 816, Absorption coefficient = 0.095 mm−1, λ = 7107 Å, 2402
reflections were collected on a CAD-4 diffractometer, 989 ob-
served reflections (I ꢀ 2σ (I)). The largest difference peak and
hole = 0.353 and −0.305e Å−3, respectively. The structure was
solved by direct methods and refined by full-matrix least squares
on F2 using SHELX-97.33 Crystallographic data have been depos-
ited at the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK and
copies can be obtained on request, free of charge, by quoting the
publication citation and deposition numbers CCDC 174919. The
data are also deposited as Document No. 75014 at the Office of
the Editor of Bull. Chem. Soc. Jpn.
1207, 1149, 1089, 1053 cm−1; H NMR (CDCl3, 200 MHz) δ
1
7.25–7.15 (1H, m), 6.99–6.91 (1H, m), 6.52–6.16 (2H, m), 4.33
(1H, s, OCH), 3.10–2.89 (1H, m), 2.47–1.22 (12H, m); 13C NMR
(CDCl3, 50.3 MHz) δ 211.7 (CwO), 184.6 (CwO), 147.1 (wCH),
142.5 (wCH), 131.3 (wCH), 127.5 (wCH), 116.1 (quat-C), 86.6
(OCH), 78.6 (quat-C), 47.0 (CH), 41.6 (CH2), 38.8 (CH2), 30.9
(CH2), 25.1 (CH2), 24.9 (CH2), 23.8 (CH2); MS m/z 274 (M+).
Found: C, 69.88; H, 6.70%. Calcd for C16H18O4: C, 70.06; H,
6.61%. 19: (16 mg, 6%), thick oil; IR (neat) 2932, 2911, 1732,
1675, 1610, 1460, 1271, 1252, 1036, 913 cm−1; 1H NMR (CDCl3,
200 MHz) δ 6.91 (1H, d, J = 10.4 Hz), 6.84 (1H, d, J = 10.4 Hz),
4.69 (1H, s, OCH), 3.27 (1H, d, J = 8.4 Hz), 3.20 (1H, d, J = 8.4
Hz), 2.80–1.24 (13 H, m); 13C NMR (CDCl3, 50.3 MHz) δ 202.6
(CwO), 193.0 (CwO), 192.9 (CwO), 143.1 (wCH), 142.6 (wCH),
92.8 (quat-C), 86.2 (OCH), 52.3 (CH), 51.4 (CH), 43.5 (CH), 41.6
(CH2), 38.7 (CH2), 30.8 (CH2), 25.1 (CH2), 24.9 (CH2), 23.9
(CH2); MS m/z 274 (M+). Found: C, 70.19; H, 6.54%. Calcd for
C16H18O4: C, 70.06; H, 6.61%. 20: (44 mg, 16%), colorless solid
(from ethyl acetate/hexane) mp 172–174 °C; IR (KBr) 3433,
3075, 2934, 1170, 1663, 1173, 823 cm−1 1H NMR (CDCl3/
;
DMSO-d6, 200 MHz) δ 6.95 (1H, d, J = 10.2 Hz), 6.08 (1 H, d, J
= 10.2 Hz), 4.78 (1 H, s, OCH), 2.95–2.85 (2H, m), 2.60 (1H, s,
OH), 1.90–1.12 (14H, m); 13C NMR (CDCl3/DMSO-d6, 50.3
MHz) δ 196.9 (CwO), 148.2 (wCH), 129.6 (wCH), 115.3 (quat-C),
110.9 (quat-C), 91.0 (OCH), 89.5 (quat-C), 80.3 (OCH), 46.2
(CH2), 43.7 (CH), 38.9 (CH2), 36.8 (CH2), 31.4 (CH2), 26.5 (CH2),
24.9 (CH2), 24.2 (CH2); MS m/z (rel intensity) 292 (M+; 15), 261
(31), 247 (39), 246 (36), 186 (29), 153 (91), 152 (39), 151 (27), 54
(100). Found: C, 64.74; H, 6.52%. Calcd for C16H20O5: C, 65.74;
H, 6.89%.
This research was supported by Young Scientist Scheme,
CSIR, New Delhi. We are grateful to Prof. W. Sander, Ruhr
University, Germany and RSIC, Lucknow, India for perform-
ing mass spectral analysis. Authors thank Dr. P. K. Ghosh, Di-
rector and Dr. R. V. Jasra for their encouragement of this work.
S. A. B. and C. G. would like to thank CSIR, New Delhi for a
fellowship.
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α
Reaction of -Diazo Ketone 22 with N-Phenylmaleimide.
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5.46; N, 3.62%.
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