Cascade reactions of β-amino-substituted α,β-unsaturated fischer carbene complexes with 1,5-dien-3-ynes as a convenient access to ring-annelated benzene derivatives

Article abstract of DOI:10.1002/ejoc.200500130

Upon heating pentacarbonyl(3-dimethylamino-1-ethoxypropenylidene)chromium complexes 1 with 1,5-dien-3-ynes 2 in pyridine at 80°C, benzene-annelated cyclopentenones 8 and their regioisomers 9, resulting from a sequence of cocyclization, 6π-electrocyclization and hydrolysis, were isolated in 12-75% yield (13 examples). The more flexible the alkenyl substituents were in the dienynes 2, the longer were the reaction times needed to achieve good chemical yields. This new cascade reaction of Fischer carbene complexes provides a direct route to trindanone analogues under milder conditions than traditional methods, and is compatible with more functionalities. Compounds 14 and 15 with steroid-like skeletons were thus prepared in 54-77% yields (4 examples) from complex 1-iPr and the bicyclic alkyne 2. Hexacycles 17 and 18 were accessible with high diastereoselectivity in the triquinane moiety by the same method in 45 % yield,

Full text of DOI:10.1002/ejoc.200500130

FULL PAPER
Cascade Reactions of β-Amino-Substituted α,β-Unsaturated Fischer Carbene
Complexes with 1,5-Dien-3-ynes as a Convenient Access to Ring-Annelated
Benzene Derivatives
Yao-Ting Wu,[a] Mathias Noltemeyer,[b] and Armin de Meijere*[a]
Keywords: Cascade reaction / Template synthesis / 6π-Electrocyclization / Fischer carbenes
Upon heating pentacarbonyl(3-dimethylamino-1-ethoxypro-
penylidene)chromium complexes 1 with 1,5-dien-3-ynes 2 in
pyridine at 80 °C, benzene-annelated cyclopentenones 8 and
a direct route to trindanone analogues under milder condi-
tions than traditional methods, and is compatible with more
functionalities. Compounds 14 and 15 with steroid-like skel-
their regioisomers 9, resulting from a sequence of cocycliza- etons were thus prepared in 54–77% yields (4 examples)
tion, 6π-electrocyclization and hydrolysis, were isolated in
12–75% yield (13 examples). The more flexible the alkenyl
substituents were in the dienynes 2, the longer were the re-
action times needed to achieve good chemical yields. This
new cascade reaction of Fischer carbene complexes provides
from complex 1-iPr and the bicyclic alkyne 2. Hexacycles 17
and 18 were accessible with high diastereoselectivity in the
triquinane moiety by the same method in 45% yield,
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
derivatives were obtained from cyclohexene derivatives with
two vicinal leaving groups, in good to excellent yields.[3]
Introduction
Constructions of six-membered carbocycles by 6π-elec- With this experience in mind, we conceived the possibility
trocyclizations of (E,Z,E)-1,3,5-hexatrienes, assembled to access ethoxycyclopentene-annelated cyclohexadienes 4
either by a twofold Heck coupling of a 1,2-dihalocycloalk- by 6π-electrocyclization of 1,2-dialkenyl-substituted [(di-
ene with two identical alkenes[1] or by a Stille–Heck coup- methylamino)ethoxy]cyclopentadienes 3, which ought to be
ling sequence with an alkenylstannane and an alkene, easily assembled by [3+2] cocyclization of β-dimethyl-
respectively, on 2-bromocyclohex-1-enyl triflates,[2] have amino-substituted α,β-unsaturated Fischer carbene-
been developed and promoted by us[3] and other groups[4] in chromium complexes 1 and 1,5-dien-3-ynes 2 in pyridine,
recent years. By this methodology, various 2,3-disubstituted according to our previously published general protocol
2,3,5,6,7,8-hexahydro- and 5,6,7,8-tetrahydronaphthalene (Scheme 1).[5] Therefore, we set out to prepare various 1,5-
Scheme 1. Conceived synthesis of 1,2-dialkenyl-5-dimethylamino-3-ethoxycyclopentadienes 3 and their 6π-electrocyclization to six-ring
annelated protected cyclopentenones 4.
dien-3-ynes and examined the possibility to construct oligo-
substituted dihydroindene derivatives of type 4.
[a] Institut für Organische und Biomolekulare Chemie, Georg-
August-Universität Göttingen,
Tammannstrasse 2, 37077 Göttingen, Germany
Fax: + 49-551399475
E-mail: Armin.deMeijere@chemie.uni-goettingen.de
[b] Institut für Anorganische Chemie, Georg-August-Universität
Göttingen,
Results and Discussion
Various 1,5-dien-3-ynes of type 2 were easily prepared by
Sonogashira coupling of an alkenyl halide or an enol triflate
5 with a terminal alkyne 6 (Scheme 2).[6] Unfortunately,
Tammannstrasse 4, 37077 Göttingen, Germany
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
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DOI: 10.1002/ejoc.200500130
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Cascade Reaction for Access to Ring-Annelated Benzene Derivatives
FULL PAPER
substituted styrene derivatives 7 were observed as bypro-
ducts and at least in one case even isolated (Entry 2 in
Table 1). They were obviously formed by a palladium-cata-
lyzed formal [4+2] cycloaddition of one enyne to another
one as has been systematically studied by Yamamoto et
al.[7] The formation of 7h from 2-methylbut-1-en-3-yne (6h)
could be suppressed by lowering the reaction temperature
and shortening the time. However, the low chemical yield of
2fi was probably due to the formation of the corresponding
styrene derivative 7i as the major product from 1-buten-3-
yne (6i), however, in the applied workup procedure 7i was
not isolated and therefore not quantified.
Scheme 3. Synthesis of indanone derivatives 8-R and 9-R. For de-
tails see Table 2.
Scheme 2. Synthesis of various 1,5-dien-3-ynes 2. For details see
Table 1.
Upon heating complexes 1 with conjugated dienynes 2 in
According to the previously reported systematic study,[5b]
pyridine at 80 °C for 3 d, only the indenone derivatives 8- the regioselectivity in the cocyclization to yield cyclopenta-
R/9-R, apparently arising from sequential cocyclization, 6π- dienes 3 depends upon the steric demand and the electronic
electrocyclization, elimination of dimethylamine and hy- properties of the substituents on the alkyne, and the former
drolysis, were obtained, instead of the expected dihydroin- plays a more important role than the latter. This is again
denes 4 (Scheme 3).
confirmed by the current results. With two different substit-
Table 1. Preparation of 1,5-dien-3-ynes 2 by Sonogashira coupling of alkenyl halides or enol triflates 5 with terminal alkynes 6 (see
Scheme 2).
[a] In addition, 13% of 4-methyl-(1Ј-propenyl)benzene was obtained.
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Y.-T. Wu, M. Noltemeyer, A. de Meijere
FULL PAPER
Table 2. One-pot access to indanone derivatives 8-R and 9-R (see Scheme 3).
Entry
Complex
1-R
Alkyne
R1
R2
R3
R4
Product
Ratio
8:9
Yield
(%)
2
1
2
3
1-cPr
1-iPr
1-cPr
2hh
2hh
2ah
H
H
Me
Me
–(CH2)3–
–(CH2)3–
–(CH2)3–
Me
Me
Me
H
H
H
8hh-cPr
8hh-iPr
8ah-cPr +
9ah-cPr
8ah-iPr +
9ah-iPr
8ah-tBu +
9ah-tBu
8aa-cPr
8aa-Me
8aa-iPr
8bh-iPr +
9bh-iPr
8bh-tBu +
9bh-tBu
8bb-iPr
8bb-tBu
8cb-iPr +
9cb-iPr
–
–
22
70
16
1:1.1
4
5
1-iPr
2ah
2ah
Me
Me
H
H
1.1:1
1:1.1
51
37
1-tBu
6
7
8
9
1-cPr
1-Me
1-iPr
1-iPr
2aa
2aa
2aa
2bh
–(CH2)3–
–(CH2)3–
–(CH2)3–
–(CH2)4–
–(CH2)3–
–(CH2)3–
–(CH2)3–
–
–
–
19
12
75
46
Me
Me
H
H
1.1:1
10
1-tBu
2bh
–(CH2)4–
1.1:1
21
11
12
13
1-iPr
1-tBu
1-iPr
2bb
2bb
2cb
–(CH2)4–
–(CH2)4–
–(CH2)4–
–(CH2)4–
–(CH2)4–
–
–
68[a]
19[a]
67[a]
–O(CH2)3–
1.1:1
14
1-iPr
2dh
–(CH2)6–
Me
H
8dh-iPr +
9dh-iPr
–
0
[a] Reaction time 4 d.
uents of similar size on the dienynes 2, two isomers 8-R moiety 13. However, upon chromatography 13 obviously
and 9-R were formed with virtually no regioselectivity. The undergoes rapid hydrolysis so that the ketone 8bb-iPr was
unsymmetrical dienyne 2bc with one dihydropyrane and the only isolated product. In a control experiment, the com-
one cyclohexene moiety on the triple bond also gave both plex 1-iPr was heated with the alkyne 2bb in pyridine for
regioisomers 8bc-iPr and 9bc-iPr upon cocyclization with 1- only 40 h. After removal of [Cr(CO)5Py] and the starting
iPr in a ratio of 1:1.1. Unfortunately, good chemical yields material 2bb by chromatography, an inseparable mixture
apparently can only be achieved with the isopropyl-substi- was obtained, in which the initial cocyclization product 11
tuted complex 1-iPr and to a lesser extent, the tert-butyl and the final indanone 8bb-iPr were identified as major
analogue 1-tBu. The more flexible the alkenyl substituents components.
were in the dienynes 2, the longer were the reaction times
needed to complete the conversion. With a cyclooctenyl
substituent as in 2dh employed with 1-iPr, none of the cas-
cade reaction products 8dh-iPr/9dh-iPr and not even the
corresponding cyclopentadiene of type 3 was observed.
When complex 1-tBu was employed, besides the in-
danone derivatives 8/9, alkenylaminocarbene complexes of
type 10 were formed in these reactions (Scheme 3).[8] This
isomerization apparently competes with the formal [3+2]
cycloaddition, and this is the major reason for lower chemi-
cal yields of the corresponding cocyclization products in
certain cases (Entries 5, 10 and 12, Table 2).
It is quite remarkable that the 6π-electrocyclization of
the dialkenylcyclopentadienes of type 11, which are initially
formed in the formal [3+2] cycloaddition of e. g. complex
1-iPr to the dienyne 2bb (Scheme 4), apparently proceeds
with a comparable rate as the formation of 11 at 80 °C.
The thus formed trisannelated cyclohexadiene 12, by two
consecutive 1,5-hydrogen shifts and elimination of dime-
thylamine followed by another two consecutive 1,5-hydro-
gen shifts eventually yields the more stable aromatic com-
pound 13.[9,10] The basic conditions certainly promote this
Scheme 4. Mechanistic rationalization of the formation of in-
danone derivatives of type 8bb-iPr. A: formal [3+2] cycloaddition.
1
elimination. The H- and 13C-NMR spectra of the crude
product clearly show the ethoxy group of the vinyl ether B: 6π-electrocyclization.
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Cascade Reaction for Access to Ring-Annelated Benzene Derivatives
FULL PAPER
Trisannelated benzene derivatives, such as trindane and initially formed five-membered ring enol ethers had to be
dodecahydrotriphenylene, were first reported by Wallach enforced by addition of hydrochloric acid to the reaction
and by Mannich as minor products of acid-catalyzed cycliz- mixture after removal of the solvent pyridine. Products 14
ing aldol condensations of cyclopentanone and cyclohexa- and 15 were thus obtained with almost no regioselectivity.
none, respectively.[11] The chemical and physical properties With a tert-butyl substituent on the dienyne as in 2fj and
of these compounds and their analogues have been studied 2gj, the cocyclization products were not formed.
extensively to examine the bond length alternation.[12]
While a significant perturbation of aromaticity attributable
to the so-called Mills–Nixon effect[13a] has not been ob-
served,[13b,13c] trisannelated arenes of this type have offered
opportunities for the synthesis of complex natural prod-
ucts.[14] However, very few procedures are available for tar-
get-oriented preparations of such trisannelated benzene de-
rivatives, and most of them are carried out under harsh con-
ditions, e. g. in strongly acidic solution or at high tempera-
ture.[15] Trindanone is accessible by further oxidation of
trindane, and it has been regarded as a potential key inter-
mediate in a rational synthesis of fullerene.[16] Cocycliza-
tions of Fischer carbene complexes of type 1 with appropri-
ately substituted dienynes as developed here provide ac-
cesses to trisannelated benzene derivatives with additional
functionalities under much milder conditions than the
traditional methods.
By the same methodology, tetracyclic steroid-like struc-
Scheme 5. Synthesis of tetracyclic compounds 14/15 with steroid-
tures 14/15 are accessible from complex 1-iPr and annelated
like skeletons via complex 1-iPr and 1,5-dien-3-ynes 2. For details
dienynes 2 (Scheme 5).[17] In these cases, hydrolysis of the see Table 3.
Table 3. One-pot access to steroid-like tetracyclic skeletons 14/15 (see Scheme 5).
[a] Diastereomer ratio (1.2:1) in each regioisomer.
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Y.-T. Wu, M. Noltemeyer, A. de Meijere
FULL PAPER
Scheme 6. Access to hexacycles 17/18 in a one-pot operation from complex 16 and dienyne 2eh. The mechanistic details are shown for
one of the two regioisomers only.
Starting from the carbene complex 16 with a protected ably predominantly 21 with cis,anti,cis-configuration.[18]
carbonyl group in a cyclopentyl substituent and the dihy- Dehydration of the alcohols 21 and/or 23 then would afford
dronaphthalene-annelated dienyne 2eh, a 1:1 mixture of the the alkenes 22 and/or 24, subsequent addition of hydrogen
hexacycles 17/18 also was obtained in a one-pot operation. chloride to the double bond in 22 and/or 24 would eventu-
The triquinane portions of the molecules 17/18 were formed ally yield the final products 17 and 18.
with high diastereoselectivity (Scheme 6). The initially ex-
pected aldol products 21 and 23 were not observed.[18] Since
the relative configurations of the hexacycles with their four
Conclusions
stereogenic centers could not be assigned unambiguously
1
based on the H-, 13C-, and even NOESY-2D-NMR spec-
tra, crystals were grown by slow diffusion crystallization
from diethyl ether/pentane. The X-ray crystal structure
analysis (Figure 1)[19] then rigorously established the mole-
cule as the hexacyclic chloride 17 with cis,syn,cis-configura-
tion in the triquinane moiety.
Reaction of β-amino-substituted α,β-unsaturated Fischer
carbene complexes of type 1 with 1,5-dien-3-ynes affords
indanone derivatives 8-R/9-R, even steroid-like skeletons
14/15. Further elaboration of molecular complexity can be
brought about by employing complexes like 16 which, after
cocyclization with dienynes such as 2eh, lead to hexacyclic
skeletons such as 17/18. However, improved regioselectivity
would be desirable.
Experimental Section
1
General: H and 13C NMR: Bruker AM 250 (250 and 62.9 MHz)
or Bruker AMX 300 (300 and 75 MHz). IR: Bruker IFS 66 (FT-
IR). Low-resolution EI-MS: Varian MAT CH 7, MAT 731, ioniz-
ing voltage 70 eV. High-resolution EI-MS (HR EIMS): Varian
MAT 311 A. X-ray crystal structure determination: The data were
collected with a Stoe–Siemens-AED diffractometer. Melting points
were determined with a Büchi melting point apparatus and are un-
corrected. Elemental analysis: Mikroanalytisches Laboratorium des
Instituts für Organische und Biomolekulare Chemie der Georg-Au-
gust-Universität Göttingen. Chromatography: Merck silica gel 60
(230–400 mesh) or ICN neutral alumina (Super I, activity II). Sol-
vents for chromatography were technical grade and freshly distilled
before use. Tetrahydrofuran was distilled from sodium benzophe-
none ketyl, and pyridine was distilled from calcium hydride. Penta-
Figure 1. Structure of the hexacycle 17 in the crystal.[19]
Apparently, the initial cocyclization product 19 from the
complex 16 and the dienyne 2eh is hydrolyzed under the
acidic conditions to yield the diketone 20, which undergoes
an intramolecular aldol reaction to furnish the dia-
stereomeric triquinane derivatives 21 and/or 23, most prob- carbonyl[(2E)-3-cyclopropyl-3-dimethylamino-1-ethoxy-2-propen-
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Cascade Reaction for Access to Ring-Annelated Benzene Derivatives
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1-ylidene]chromium (1-cPr),[5b] pentacarbonyl[(2E)-3-dimeth-
ylamino-1-ethoxy-2-buten-1-ylidene]chromium (1-Me),[5b] penta-
4,6,8-H), 6.92 (d, 3J = 8.2 Hz, 1 H, 5-H) ppm. 13C NMR
(62.9 MHz, CDCl3, plus DEPT): δ = 29.5, 33.3 (–, C-1,2), 55.1 (+,
carbonyl[(2E)-3-dimethylamino-1-ethoxy-4-methyl-2-penten-1-ylid- OCH3), 111.0, 113.7, 126.5, 128.7 (+, C-4,5,6,8), 120.8, 126.9,
ene]chromium (1-iPr),[5b] pentacarbonyl[(2Z)-3-dimethylamino-1- 134.5, 158.8 (Cquat, C-3,7,9,10) ppm. MS (70 eV): m/z (%) = 240/
ethoxy-4,4-dimethyl-2-penten-1-ylidene]chromium (1-tBu),[5b] 1-
bromo-1-cyclopentene (5a),[20] 1-bromo-1-cyclohexene (5b),[20] 5-
239/238/237 (98/17/100/12) [M+], 159 (52) [M+ – Br], 144 (74) [M+ –
Br – CH3], 128/127 (23/23), 116/115 (52/100), 63 (14). C11H11BrO
bromo-3,4-dihydro-2H-pyran (5c),[20] 3-bromo-1,2-dihydronaph- (239.1): calcd. C 55.25, H 4.64; found C 55.05, H 4.49.
thalene (5e),[21] 2-bromo-6-methoxy-3,4-dihydro-2H-naphthalen-1-
2,2-Dimethyl-3-methylenpent-4-yne (6j): A 500 mL flask equipped
one,[22] 2-bromo-6-methoxy-1,2,3,4-tetrahydronaphthalen-1-ol,[21]
with a magnetic stirring bar was charged with 3-hydroxy-2,2,3-tri-
(–)-4a-methyl-4,4a,5,6,7,8-hexahydro-3H-naphthalen-2-one,[23] 1-
methyl-4-pentyne (20.0 g, 158 mmol) and p-toluenesulfonic acid
ethynyl-1-cyclopentene (6a),[24] 2-methyl-1-buten-3-yne (6h),[24] 1-
monohydrate (1.00 g). The reaction mixture was heated at 120 °C
ethynyl-1-cyclohexene (6b),[24] 1-buten-3-yne (6i),[24] 2,5-dimethyl-
(oil bath temperature) and the product directly distilled from it.
1,5-hexadien-3-yne (2hh),[25] pentacarbonyl[(2E)-4-(1Ј,4Ј-dioxa-
The crude product was dried with MgSO4 and distilled again to
spiro[4.4]non-6Ј-yl)-3-dimethylamino-1-ethoxy-2-buten-1-ylidene]-
afford 10.1 g (59%) of 6j as a colorless oil, b. p. 98 °C.[26]
chromium (16)[18] were prepared according to published pro-
cedures.
4-(1Ј-Cyclopentenyl-2-methylbut-1-en-3-yne (2ah) and 4-Methyl-(2Ј-
propenyl)benzene (7h): Preparation according to GP1. To a solution
of 1-bromo-1-cyclopentene (5a) (5.84 g, 39.7 mmol) in diisopro-
pylamine (40 mL) was added PPh3 (100 mg), LiCl (100 mg), CuI
(75.0 mg), PdCl2(PPh3)2 (100 mg) and finally 2-methylbut-1-en-3-
yne (6h) (5.00 mL, 53.6 mmol), and the mixture was heated at 60 °C
for 16 h. The suspension was diluted with pentane (100 mL) and
washed with water (50 mL). The aqueous phase was extracted with
pentane (50 mL). The combined organic phases were washed with
water (30 mL) and hydrochloric acid (1 n, 3 × 30 mL). The solution
was dried with MgSO4. After filtration, the solvents were removed
under ambient pressure, and the residue was distilled under reduced
pressure to afford 3.76 g of a colorless oil [b. p. 75 °C (20 Torr)],
which contained 2ah (90 %) and 4-methyl-(2Ј-propenyl)benzene
(10 %). The amount of 2ah corresponded to 3.38 g (64 %). MS
(70 eV): m/z (%) = 132 (100) [M+], 117 (78) [M+ – CH3], 115 (58),
91 (64), 77 (14), 65 (16), 51 (10). 2ah: 1H NMR (250 MHz, CDCl3):
δ = 1.40–1.70 (m, 5 H, CH3, 4Ј-H), 1.90 (m, 4 H, 3Ј,5Ј-H), 5.20–
5.23 and 5.27–5.29 (m, 2 H, 4-H), 6.02 (m, 1 H, 2Ј-H) ppm. 13C
NMR (62.9 MHz, CDCl3, plus DEPT): δ = 23.3 (–, C-4Ј), 23.5 (+,
CH3), 33.3, 36.3 (–, C-3Ј,5Ј), 85.7, 91.6 (Cquat, C-1,2), 121.2 (–, C-
4), 124.4, 126.9 (Cquat, C-3,1Ј), 137.8 (+, C-2Ј) ppm. The NMR
spectroscopic data of 4-methyl-(2Ј-propenyl)benzene agreed with
the previously reported ones.[27]
General Procedure for the Preparation of Internal Alkynes 2 by the
Sonogashira Coupling (GP1): To an amine solution (50 mL) of the
respective terminal alkyne 6 (100 mmol) and alkenyl halide 5
(100 mmol) in a screw-capped Pyrex bottle is added 200 mg of
[dichlorobis(triphenylphosphane)palladium(ii) [PdCl2(PPh3)2],
500 mg of copper(i) iodide (CuI), and 150 mg of triphenylphos-
phane (PPh3) at ambient temperature. The mixture is heated at 40–
85 °C under argon for 4–18 h. After cooling to room temperature,
the suspension is filtered through a 3 cm thick layer of Celite, and
the Celite rinsed well with Et2O (150 mL). The solvents from the
filtrate are removed under reduced pressure, and the residue is sub-
jected to chromatography on silica gel (150 g). Elution with pen-
tane/Et2O affords the coupling product 2. Most of these 1,5-dien-3-
ynes are not stable enough to prepare pure samples for elementary
analyses, but they can be used for synthetic purposes without being
analytically pure.
General Procedure for Cocyclizations of Complexes 1 with Alkynes
2 (GP2): A thick-walled, screw-cap Pyrex bottle equipped with a
magnetic stirring bar is charged with a 0.05 m solution of the com-
plex 1 in anhydrous pyridine. Dry argon is bubbled through the
solution for 5 min, and 1.5 equiv. of the freshly prepared respective
alkyne 2 is immediately added. The sealed bottle is kept in an oil
bath at 80 °C for 3–6 d. The solvent is removed under reduced pres-
sure, the residue is diluted with Et2O, and the solution exposed to
air for 2 h. After filtration and removal of solvent, the residue is
purified by column chromatography on aluminum oxide (act. II).
Di(1Ј-cyclohexenyl)ethyne (2bb): (According to GP1). To a solution
of 1-iodo-1-cyclohexene (5b) (5.82 g, 28.0 mmol) in diisopro-
pylamine (30 mL) was added 1-ethynyl-1-cyclohexene (6b) (3.19 g,
30.0 mmol), PdCl2(PPh3)2 (70.0 mg), PPh3 (70.0 mg), CuI
(50.0 mg), and LiCl (60.0 mg), and the mixture was heated at 40 °C
for 5 h. After filtration of the mixture and evaporation of the sol-
vents under reduced pressure, the residue was subjected to
chromatography on silica gel (70 g). Elution with pentane gave
4.80 g (92%) of 2bb [Rf — 0.75 (pentane)] as a colorless oil. The
NMR spectroscopic data agreed with the previously reported
ones.[28]
3-Bromo-7-methoxy-1,2-dihydronaphthalene (5f): A solution of 2-
bromo-6-methoxy-1,2,3,4-tetrahydronaphthalen-1-ol (prepared
from 6-methoxy-1,2,3,4-tetrahydronaphthalen-1-one (25.0 g,
142 mmol) via 2-bromo-6-methoxy-1,2,3,4-tetrahydro-naphthalen-
1-one without any serious purifications) in benzene (250 mL) was
treated with a catalytic amount of p-toluenesulfonic acid monohy-
drate (540 mg), and the mixture was heated under reflux for 3 h
using a Dean–Stark apparatus. After cooling to ambient tempera-
ture, a satd. solution of potassium carbonate (50 mL) was added
to the mixture, and the aqueous phase was extracted with CH2Cl2
(3 × 100 mL). The combined organic extracts were dried with
MgSO4. After evaporation of the solvents under reduced pressure,
the residue was subjected to chromatography on silica gel (800 g).
Elution with pentane/Et2O/CH2Cl2 (18:1:1) gave 15.0 g (44 %,
based on the employed 6-methoxy-1,2,3,4-tetrahydronaphthalen-1-
one) of 5f [Rf — 0.70 (pentane/Et2O, 9:1)] as a colorless solid, m.p.
3-(3Ј-Methylbut-3Ј-en-1Ј-ynyl)-1,2-dihydronaphthalene (2eh): Prepa-
ration according to GP1. To a solution of 3-bromo-1,2-dihydrona-
phthalene (5e) (4.98 g, 23.8 mmol) in diisopropylamine (30 mL)
was added PPh3 (50 mg), CuI (50 mg), LiCl (50 mg), PdCl2-
(PPh3)2 (60 mg), and 5.00 mL (53.6 mmol) of 2-methylbut-1-en-3-
yne (6h), and the mixture was heated at 70 °C for 2 h. After fil-
tration and evaporation of the solvents under reduced pressure, the
residue was subjected to chromatography on silica gel (100 g). Elu-
tion with pentane gave 3.38 g (73%) of 2eh [Rf — 0.36 (pentane)]
41 °C. IR (KBr): ν = 3020 cm–1 (C–H), 2934, 2833, 1626 (C=C), as a colorless oil. IR (film): ν = 3094 cm–1 (C–H), 3065, 3015, 2942,
˜
˜
1
1601, 1496, 1322, 1293, 1274, 1246, 1157, 1030, 873, 849, 828. H
2889, 2835, 2190 (CϵC), 1615 (C=C), 1484, 1453, 1428, 1372,
NMR (250 MHz, CDCl3): δ = 2.76 (t, 3J = 8.2 Hz, 2 H, 2-H), 2.95 1305, 889, 748. 1H NMR (250 MHz, CDCl3): δ = 2.04 (s, 3 H,
3
3
3
(t, J = 8.2 Hz, 2 H, 1-H), 3.01 (s, 3 H, OCH3), 6.69–6.78 (m, 3 H, CH3), 2.53 (t, J = 7.5 Hz, 2 H, 2-H), 2.91 (t, J = 7.5 Hz, 2 H, 1-
Eur. J. Org. Chem. 2005, 2802–2810
www.eurjoc.org © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2807

Y.-T. Wu, M. Noltemeyer, A. de Meijere
H), 5.33–5.35 and 5.42–5.43 (m, 2 H, 4Ј-H), 6.86 (s, 1 H, 4-H), 3 d. Chromatography on aluminum oxide (act. II, 40 g) eluting with
FULL PAPER
7.08–7.23 (m, 4 H, 5,6,7,8-H) ppm. 13C NMR (62.9 MHz, CDCl3,
plus DEPT): δ = 23.5 (+, CH3), 27.5, 27.7 (–, C-1,2), 89.9, 92.6
(Cquat, CϵC), 121.0, 126.9, 133.7, 134.7 (Cquat, C-3,9,10,3Ј), 121.7
(–, C-4Ј), 126.3, 126.6, 127.4, 127.6, 133.1 (+, C-4,5,6,7,8) ppm.
pentane/Et2O (from 1:0 to 3:1) gave 231 mg (51%) of 8ah-iPr and
9ah-iPr [Rf = 0.64 (pentane/Et2O, 3:1); ratio 1.1:1] as a pale-yellow
oil. IR (film): ν = 2960 cm–1 (C–H), 1706 (C=O), 1609, 1465, 1399,
˜
1269, 736. 1H NMR (250 MHz, CDCl3): δ = 0.41, 0.46 (d, 3J =
3
MS (70 eV): m/z (%) = 194 (100) [M+], 178 (40), 165 (10), 152 (12), 6.8 Hz, 3 H, iPr-H), 1.03, 1.04 (d, J = 6.8 Hz, 3 H, iPr-H), 2.00–
128 (14), 115 (12). C15H14 (194.3): calcd. C 92.74, H 7.26; found
C 92.84, H 7.02.
2.57 (m, 5 H, 2,7-H and iPr-H), 2.33, 2.56 (s, 3 H, CH3), 2.78–2.92
(m, 3 H) and 3.12–3.18 (m, 1 H) [total 4 H, 6,8-H], 3.30–3.32, 3.39–
3.41 (m, 1 H, 3-H of 8ah-iPr and 1-H of 9ah-iPr), 6.95, 7.20 (s, 1 H,
5-H) ppm. 13C NMR (62.9 MHz, CDCl3, plus DEPT): δ = 14.8,
14.9, 18.1, 18.3 (+, iPr-C), 21.8, 22.1 (+, CH3), 25.2, 25.3 (–, C-7),
28.7, 29.1 (+, iPr-C), 30.5, 30.6, 31.5, 32.8 (–, C-6,8), 37.9, 38.0
(–, C-2), 42.8, 43.2 (+, C-3 of 8ah-iPr and C-1 of 9ah-iPr), 125.5,
131.6 (+, C-5), 132.7, 132.9, 133.1, 136.5, 138.1, 139.7, 144.5, 151.5,
154.3 × 2 (Cquat, Ar-C), 207.3, 207.8 (Cquat, CO) ppm. MS (70 eV):
m/z (%) = 228 (40) [M+], 186 (25), 185 (100) [M+ – C3H7]. C16H20O
(228.3): calcd. C 84.16, H 8.83; found C 83.96, H 8.68.
(4aR)-4a-Methyl-7-(3Ј-methylbut-3Ј-en-1Ј-ynyl)-1,2,3,4,4a,5,6,8a-oc-
tahydronaphthalene (2gh): Preparation according to GP1. To a solu-
tion of (4aR)-4a-methyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-
yl trifluoromethanesulfonate (5g) (4.47 g, 15.0 mmol) in DMF
(40 mL) was added PPh3 (50 mg), CuI (50 mg), LiCl (50 mg),
PdCl2(PPh3)2 (60 mg), NEt3 (1.52 g, 15.0 mmol) and 2-methylbut-
1-en-3-yne (6h) (4.00 mL, 42.9 mmol), and the mixture was heated
at 50 °C for 12 h. The reaction mixture was diluted with 50 mL of
pentane/Et2O (1:1) and washed with water (200 mL). The aqueous
phase was extracted with pentane/Et2O (1:1; 4 × 50 mL). The com-
bined organic phases were washed with water (30 mL) and hydro-
chloric acid (1 n, 30 mL). The solution was dried with MgSO4. Af-
ter filtration and evaporation of the solvents under reduced pres-
sure, the residue was subjected to chromatography on silica gel
(100 g). Elution with pentane gave 2.74 g (85%) of 2gh [Rf — 0.63
3-Isopropyl-2,3,4,5,6,7,8,9-octahydrotrinden-1-one (8aa-iPr): Prepa-
ration according to GP2. To a solution of complex 1-iPr (723 mg,
2.00 mmol) in pyridine (40 mL) was added di(1-cyclopentenyl)eth-
yne (2aa) (633 mg, 4.00 mmol), and the mixture was stirred at
80 °C for 3 d. Chromatography on aluminum oxide (act. II, 40 g)
eluting with pentane/Et2O (from 1:0 to 3:1) gave 382 mg (75%) of
8aa-iPr [Rf = 0.63 (pentane/Et2O, 3:1)] as a colorless solid, m.p.
(pentane)] as a colorless oil. IR (film): ν = 2922 cm–1 (C–H), 2855,
˜
2188 (CϵC), 1671 (C=C), 1608, 1446, 1373, 891. 1H NMR
121–122 °C. IR (KBr): ν = 2956 cm–1 (C–H), 1695 (C=O), 1588,
˜
1
3
(250 MHz, CDCl3): δ = 0.80 (s, 3 H, CH3), 1.02–1.57 (9 H) and 1448, 1281, 1126. H NMR (250 MHz, CDCl3): δ = 0.43 (d, J =
1.68–2.05 (4 H) (m, total 13 H, 1,2,3,4,5,6,8a-H), 1.89 (s, 3 H, 6.8 Hz, 3 H, iPr-H), 0.98 (d, 3J = 6.8 Hz, 3 H, iPr-H), 1.94–2.22
CH3), 5.16–5.18 and 5.22–5.24 (m, 2 H, 4Ј-H), 5.98–6.01 (m, 1 H, (m, 4 H, 5,8-H), 2.23–2.48 (m, 3 H, iPr-H, 2-H), 2.69 (t, 3J =
8-H) ppm. 13C NMR (62.9 MHz, CDCl3, plus DEPT): δ = 16.3 (+,
7.6 Hz, 2 H), 2.76 (t, J = 7.9 Hz, 2 H), 2.87 (t, J = 7.7 Hz, 2 H),
3
3
3
CH3), 22.1, 26.6, 28.4, 34.0, 40.9, 42.6 (–, C-1,2,3,4,5,6), 23.6 (+,
and 3.11 (t, J = 7.4 Hz, 2 H) [total 8 H, 4,6,7,9-H], 3.20–3.35 (m,
CH3), 31.5 (Cquat, C-4a), 39.9 (+, C-8a), 87.9, 89.9 (Cquat, CϵC), 1 H, 3-H) ppm. 13C NMR (62.9 MHz, CDCl3, plus DEPT): δ =
119.7, 127.0 (Cquat, C-7,3Ј), 120.8 (+, C-8), 133.7 (–, C-4Ј) ppm.
14.6, 21.6 (+, iPr-C), 25.0 × 2 (–, C-5,8), 28.5 (+, iPr-C), 30.0, 30.4,
MS (70 eV): m/z (%) = 214 (100) [M+], 199 (59) [M+ – CH3], 185 30.6, 31.2 (–, C-4,6,7,9), 37.4 (–, C-2), 43.2 (+, C-3), 131.4, 138.2,
(10), 171 (23), 157 (34), 143 (30), 131 (20), 118 (96), 95 (29), 91
(38), 81 (50), 77 (21), 67 (39), 55 (29), 53 (14), 41 (36). C16H22
(214.4): calcd. C 89.65, H 10.35; found C 89.99, H 10.97.
139.6, 140.6, 147.0, 151.7 (Cquat, Ar-C), 206.6 (Cquat, C-1) ppm. MS
(70 eV): m/z (%) = 254 (26) [M+], 211 (100) [M+ – C3H7]. C18H22O
(254.4): calcd. C 84.99, H 8.72; found C 84.74, H 8.50.
3-Isopropyl-4,7-dimethylindan-1-one (8hh-iPr): Preparation accord-
ing to GP2. To a solution of complex 1-iPr (723 mg, 2.00 mmol) in
pyridine (40 mL) was added 2,5-dimethylhexa-1,5-dien-3-yne (2hh)
(531 mg, 5.00 mmol), and the mixture was stirred at 80 °C for 3 d.
Chromatography on aluminum oxide (act. II, 40 g) eluting with
pentane/Et2O (from 1:0 to 3:1) gave 282 mg (70%) of 8hh-iPr [Rf
3-Isopropyl-2,3,4,5,6,7,8,9,10,11-decahydrocyclopenta[l]phenan-
thren-1-one (8bb-iPr): Preparation according to GP2. To a solution
of complex 1-iPr (723 mg, 2.00 mmol) in pyridine (40 mL) was
added di(1-cyclohexenyl)ethyne (2bb) (745 mg, 4.00 mmol), and the
mixture was stirred at 80 °C for 4 d. Chromatography on aluminum
oxide (act. II, 40 g) eluting with pentane/Et2O (from 1:0 to 3:1)
gave 382 mg (68%) of 8bb-iPr [Rf = 0.73 (pentane/Et2O, 3:1)] as a
= 0.65 (pentane/Et O, 3:1)] as a colorless oil. IR (film): ν =
˜
2
2984 cm–1 (C–H), 1705 (C=O), 1581, 1495, 1248, 821. 1H NMR colorless solid, m.p. 148–149 °C. IR (KBr): ν = 2931 cm–1 (C–H),
˜
3
(250 MHz, CDCl3): δ = 0.37 (d, J = 6.8 Hz, 3 H, iPr-H), 1.02 (d,
1692 (C=C), 1571, 1546, 1278, 1124. 1H NMR (250 MHz, CDCl3):
3J = 6.8 Hz, 3 H, iPr-H), 2.23–2.37 (m, 1 H, iPr-H), 2.31 (s, 3 H, δ = 0.41 (d, 3J = 6.8 Hz, 3 H, iPr-H), 1.04 (d, 3J = 6.8 Hz, 3 H,
3
CH3), 2.44–2.47 (m, 2 H, 2-H), 2.53 (s, 3 H, CH3), 3.35 (qui, J = iPr-H), 1.50–2.10 (m, 8 H, 5,6,9,10-H), 2.22–2.82 (m, 9 H, iPr-H,
3
3
3
7.9, J = 7.9, J = 7.9 Hz, 1 H, 3-H), 6.94 (d, J = 7.5 Hz, 1 H, 5- 4,7,8,11-H), 3.08–3.23 (m, 2 H, 2-H), 3.23–3.35 (m, 1 H, 3-H) ppm.
H), 7.16 (d, 3J = 7.5 Hz, 1 H, 6-H) ppm. 13C NMR (62.9 MHz, 13C NMR (62.9 MHz, CDCl3, plus DEPT): δ = 14.6, 22.0 (+, iPr-
CDCl3, plus DEPT): δ = 14.7 (+, iPr-C), 17.7, 17.8 (+, CH3), 21.6 C), 21.8, 22.1, 22.6, 22.8, 25.9, 26.3, 26.4, 27.2 (–, C-
(+, iPr-C), 29.0 (+, iPr-C), 38.2 (–, C-2), 42.5 (+, C-3,4), 129.2,
135.2 (+, C-5,6), 132.2, 134.3, 135.3, 156.6 (Cquat, C-3a,4,7,7a),
207.9 (Cquat, C-1,2,5,6) ppm. MS (70 eV): m/z (%) = 202 (48) [M+],
160 (41), 159 (100) [M+ – C3H7], 129 (10), 116 (12), 115 (16), 91
(10). C14H18O (202.3): calcd. C 83.12, H 8.97; found C 82.80,
H 8.69.
4,5,6,7,8,9,10,11), 28.5 (+, iPr-C), 38.4 (–, C-2), 42.0 (+, C-3),
131.4, 131.4, 134.1, 134.7, 142.3, 154.7 (Cquat, Ar-C), 207.8 (Cquat
C-1) ppm. MS (70 eV): m/z (%) = 282 (54) [M+], 239 (100) [M+
C3H7]. C20H26O (282.4): calcd. C 85.06, H 9.28; found C 84.84,
H 9.34.
,
–
17-Isopropyl-12-methyl-6,7,16,17-tetrahydrocyclopenta[a]phenan-
3-Isopropyl-4-methyl-3,6,7,8-tetrahydro-2H-as-indacen-1-one (8ah- thren-15-one (14eh-iPr) and 15-Isopropyl-12-methyl-6,7,15,16-tetra-
iPr) and 1-Isopropyl-4-methyl-1,6,7,8-tetrahydro-2H-as-indacen-3-
one (9ah-iPr): Preparation according to GP2. To a solution of com-
plex 1-iPr (723 mg, 2.00 mmol) in pyridine (40 mL) was added 4-
hydrocyclopenta[a]phenanthren-17-one (15eh-iPr). Variant A: Prepa-
ration according to GP2. To a solution of complex 1-iPr (723 mg,
2.00 mmol) in pyridine (40 mL) was added 3-(3Ј-methylbut-3Ј-en-
(1Ј-cyclopentenyl)-2-methylbut-1-en-3-yne (2ah) (651 mg; 1Ј-ynyl)-1,2-dihydronaphthalene (2eh) (583 mg 3.00 mmol) and the
4.43 mmol; 90% purity) and the mixture was stirred at 80 °C for mixture was stirred at 80 °C for 3 d. After dilution with Et2O,
2808
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 2802–2810

Cascade Reaction for Access to Ring-Annelated Benzene Derivatives
FULL PAPER
concd. hydrochloric acid was added to the reaction mixture (Ͻ pH
2). Chromatography on aluminum oxide (act. II, 40 g) eluting with
pentane/Et2O (from 1:0 to 3:1) gave 313 mg (54%) of 14eh-iPr and
15eh-iPr (ratio 1.1:1) as a semi-solid. 14eh-iPr could be isolated in
pure form by chromatography on silica gel (60 g) eluting with pen-
tane/Et2O (5:1).
= 1.20–1.49 (2 H), 1.71–2.13 (4 H), 2.17–2.30 (1 H) [m, total 7 H,
2
3
3
1,2,3,13-H], 2.39 (s, 3 H, CH3), 2.58 (dЈЈtЈЈ, J = 13.0, J = 8.5, J
= 8.5 Hz, 1 H, 13-H), 2.72–2.88 (m, 2 H, 6-H), 2.96–3.06 (m, 1 H,
13a-H), 3.23–3.44 (m, 1 H, 5-H), 3.49–3.56 (m, 1 H, 5-H), 3.67 (d,
3J = 8.8 Hz, 1 H, 3b-H), 4.01 (ЈЈqЈЈ, 3J = 8.8, 3J = 8.8, 3J = 8.8 Hz,
1 H, 12b-H), 7.24–7.35 (3 H), 7.69 (d, 3J = 7.4 Hz, 1 H, Ar-H), 7.73
(s, 1 H, 11-H) ppm. 13C NMR (62.9 MHz, CDCl3, plus DEPT): δ
= 18.3 (+, CH3), 21.9 (–, C-5), 23.6, 27.5, 37.8 (–, C-1,2,3), 28.1
(–, C-6), 37.2 (–, C-13), 43.2 (+, C-12b), 59.9 (+, C-13a), 64.0 (+,
C-3b), 82.4 (Cquat, C-3a), 123.6, 126.9, 127.7, 128.2, 131.3 (+, Ar-
C), 132.0, 132.8, 133.3, 134.8, 135.6, 137.4, 155.8 (Cquat, Ar-C),
205.7 (Cquat, CO) ppm. MS (70 eV): m/z (%) = 365/364/363/362/361
(8/34/28/100/9) [M+], 326 (36) [M+ – HCl], 245 (34), 229 (11), 215
(18), 79 (16). C24H23ClO (362.9): calcd. C 79.43, H 6.39; found
C 79.55, H 6.02.
Variant B: Preparation according to GP2. To a solution of complex
1-iPr (871 mg, 2.41 mmol) in pyridine (48 mL) was added 3-(3Ј-
methylbut-3Ј-en-1Ј-ynyl)-1,2-dihydronaphthalene (2eh) (702 mg,
3.61 mmol), and the mixture was stirred at 80 °C for 6 d. After
dilution with Et2O, concd. hydrochloric acid was added to the reac-
tion mixture (Ͻ pH 2). Chromatography on aluminum oxide (act.
II, 40 g) eluting with pentane/Et2O (from 1:0 to 3:1) gave 540 mg
(77%) of 14eh-iPr and 15eh-iPr (ratio 1.1:1) as a semi-solid.
14eh-iPr: Colorless solid, m.p. 105 °C. IR (KBr): ν = 2952 cm–1 (C–
˜
Mixture of 17 and 18: Colorless crystals. IR (KBr): ν = 2956 cm–1
˜
H), 2930, 1695 (C=O), 1563, 1485, 1445, 1318, 1234, 1091, 913,
759. 1H NMR (250 MHz, CDCl3, plus HH-, CH-COSY, HMBC
(C–H), 2871, 1691 (C=O), 1584, 1559, 1443, 1338, 1256, 1227,
1010, 770, 732. MS (70 eV): m/z (%) = 365/364/363/362/361 (5/16/
12/50/4) [M+], 326 (100) [M+ – HCl], 248 (43), 245 (20), 215 (10).
C24H23ClO (362.9): calcd. C 79.43, H 6.39; found C 79.77, H 6.17.
18: 1H NMR (250 MHz, CDCl3): δ = 1.21–1.39 (2 H), 1.70–2.03
3
3
and NOESY): δ = 0.51 (d, J = 6.8 Hz, 3 H, iPr-H), 1.11 (d, J =
6.8 Hz, 3 H, iPr-H), 2.34–2.50 (m, 1 H, iPr-H), 2.45 (s, 3 H, CH3),
2.58–2.61 (m, 2 H, 16-H), 2.78–2.86 (m, 2 H, 7-H), 3.26–3.61 (m,
3
3 H, 6,17-H), 7.23–7.34 (m, 3 H, Ar-H), 7.71 (d, J = 7.7 Hz, 1 H,
2
Ar-H), 7.76 (s, 1 H, Ar-H) ppm. 13C NMR (62.9 MHz, CDCl3,
plus DEPT): δ = 14.8, 22.0 (+, iPr-C), 18.2 (+, CH3), 21.8 (–, C-
6), 27.9 (–, C-7), 29.2 (+, iPr-C), 38.8 (–, C-16), 42.3 (+, C-17),
123.4, 126.7, 127.3, 127.9, 131.0 (+, Ar-C), 132.9, 133.2, 133.4,
134.0, 134.4, 137.1, 156.0 (Cquat, Ar-C), 208.2 (Cquat, CO) ppm.
MS (70 eV): m/z (%) = 290 (51) [M+], 247 (100) [M+ – C3H7], 229
(11), 203 (16). C21H22O (290.4): calcd. C 86.85, H 7.64; found
C 87.10, H 7.88.
(4 H), 2.15–2.37 (1 H) [m, total 7 H, 1,2,3,13-H], 2.56 (dЈЈtЈЈ, J =
3
3
14.3, J = 8.0, J = 8.0 Hz, 1 H, 13-H), 2.67 (s, 3 H, CH3), 2.70–
3
3.04 (m, 5 H, 11,12,13a-H), 3.67 (d, J = 8.8 Hz, 1 H, 3b-H), 4.08
3
3
3
(ЈЈqЈЈ, J = 8.8, J = 8.8, J = 8.8 Hz, 1 H, 12c-H), 7.26–7.38 (m,
3 H, Ar-H), 7.52 (s, 1 H, 6-H), 7.79 (dd, 3J = 8.3, 4J = 1.2 Hz, 1 H,
Ar-H) ppm. 13C NMR (62.9 MHz, CDCl3, plus DEPT): δ = 18.3
(+, CH3), 21.9 (–, C-5), 23.6, 27.5, 37.8 (–, C-1,2,3), 28.1 (–, C-6),
37.2 (–, C-13), 43.2 (+, C-12c), 59.9 (+, C-13a), 64.0 (+, C-3b), 82.4
(Cquat, C-3a), 124.6, 125.6, 127.1, 128.3, 128.7 (+, Ar-C), 131.0,
Mixture of 14eh-iPr and 15eh-iPr: A semi-solid. IR (film): ν =
˜
131.8, 133.4, 137.3, 137.7, 140.1, 155.9 (Cquat, Ar-C), 205.7 (Cquat
CO) ppm.
,
2960 cm–1 (C–H), 1697 (C=O), 1585, 1565, 1445, 1265, 738. MS
(70 eV): m/z (%) = 290 (64) [M+], 247 (100) [M+ – C3H7], 203 (22).
C21H22O (290.4): calcd. C 86.85, H 7.64; found C 86.58, H 7.38.
Supporting Information Available: Experimental procedures and
spectroscopic data of all compounds not presented here (see foot-
note on the first page of this article and http://www.acs.org).
1
3
15eh-iPr: H NMR (250 MHz, CDCl3): δ = 0.44 (d, J = 6.7 Hz,
3
3 H, iPr-H), 1.11 (d, J = 6.7 Hz, 3 H, iPr-H), 2.21–2.28 (m, 1 H,
iPr-H), 2.70 (s, 3 H, CH3), 2.56–2.97 (m, 6 H, 6,7,16-H), 3.41–3.50
(m, 1 H, 15-H), 7.23–7.34 (m, 3 H, Ar-H), 7.52 (s, 1 H, Ar-H), 7.78
(d, 3J = 7.8 Hz, 1 H, Ar-H) ppm. 13C NMR (62.9 MHz, CDCl3,
plus DEPT): δ = 14.7, 22.0 (+, iPr-C), 18.3 (+, CH3), 23.9, 28.5
(–, C-6,7), 29.9 (+, iPr-C), 38.5 (–, C-16), 42.2 (+, C-15), 124.5,
125.4, 126.9, 127.9, 128.2 (+, Ar-C), 131.4, 133.4, 133.6, 136.0,
137.7, 139.4, 156.1 (Cquat, Ar-C), 207.3 (Cquat, CO) ppm.
Acknowledgments
This work was supported by the State of Niedersachsen and the
Fonds der Chemischen Industrie. Generous gifts of chemicals by
BASF, Bayer, Degussa-Hüls AG and Chemetall GmbH are grate-
fully acknowledged. The authors are indebted to Dr. Burkhard
Knieriem, Göttingen, for his careful proofreading of the final ma-
nuscript.
( )-(3aα,3bα,12bα,13aα)-3a-Chloro-2,3,3a,3b,4,5,6,12b,13,13a-de-
cahydro-12-methyl-1H-cyclopenta[1Ј,2Ј:4,5]pentaleno[2,1-a]phenan-
threne-4-one (17) and ( )-(3aα,3bα, 12cα,13aα)-3a-Chloro-
2,3,3a,3b,4,11,12,12c,13,13a-decahydro-5-methyl-1H-cyclopenta-
[1Ј,2Ј:4,5]pentaleno[2,1-a]phenanthrene-4-one (18): Preparation ac-
cording to GP2. To a solution of complex 16 (1.33 g, 2.90 mmol)
in pyridine (58 mL) was added 3-(3Ј-methylbut-3Ј-en-1Ј-ynyl)-1,2-
dihydronaphthalene (2eh) (839 mg, 4.32 mmol), and the mixture
was stirred at 80 °C for 6 d. After oxidation, filtration and removal
of the solvents, the residue was diluted with 1,4-dioxane (100 mL).
To the solution was added concd. hydrochloric acid (Ͻ pH 1), and
this reaction mixture was stirred at ambient temperature for 2 d.
The solvents were removed under reduced pressure. Chromatog-
raphy on silica gel (70 g) eluting with pentane/Et2O (10:1) gave
471 mg (45%) of 17 and 18 (ratio 1:1) as a semi-solid. Compoune
17 could be isolated in pure form by careful chromatography on
silica gel (120 g) eluting with pentane/Et2O (10:1).
[1] a) O. Reiser, S. Reichow, A. de Meijere, Angew. Chem. 1987,
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Eur. J. Org. Chem. 2005, 2802–2810
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Received: February 22, 2005
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Eur. J. Org. Chem. 2005, 2802–2810