Catalytic one-pot synthesis of [5.5.5.6]fenestrane systems via a dicobalt octacarbonyl-catalyzed tandem cycloaddition of dienediynes

Article abstract of DOI:10.1039/b108034b

Catalytic one-pot synthesis of fenestrane derivatives from dienediynes was developed: fenestranes were synthesized in high yields by a dicobalt octacarbonyl-catalyzed tandem cycloaddition of dienediynes.

Full text of DOI:10.1039/b108034b

Catalytic one-pot synthesis of [5.5.5.6]fenestrane systems via a dicobalt
octacarbonyl-catalyzed tandem cycloaddition of dienediynes†
Do Han Kim,a Seung Uk Son,a Young Keun Chung*a and Sueg-Geun Leeb
a School of Chemistry and Center for Molecular Catalysis, Seoul National University, Seoul 151-747, Korea.
E-mail: ykchung@plaza.snu.ac.kr; Fax: (+82)2-889-0310; Tel: +82-2-880-6662
b Korea Research Institute of Chemical Technology, PO Box 107, Yusong, Taejeon 305-600, Korea
Received (in Cambridge, UK) 5th September 2001, Accepted 20th November 2001
First published as an Advance Article on the web
Catalytic one-pot synthesis of fenestrane derivatives from
dienediynes was developed: fenestranes were synthesized in
high yields by a dicobalt octacarbonyl-catalyzed tandem
cycloaddition of dienediynes.
atm of CO for 18 h yielded a fenestrane derivative 3a in 84%
yield [eqn. (1)].§
One of the challenging uses of organometallic chemistry is to
find reactions and strategies that allow for the facile conversion
of simple compounds into complex materials, medicines, or
molecules of theoretical interest.1 Recently we have demon-
strated2 that the dicobalt octacarbonyl-catalyzed carbonylative
cycloaddition of diene or triyne with/without diene or alkyne
can produce up to four new 5-membered rings in one step. This
success encouraged us to analyze the retrosynthesis of fenes-
tranes,3 which has been studied in relation to the question of
whether a tetrahedral carbon can be flattened.
Most of the previous syntheses of fenestranes are based on
the Pauson-Khand reaction,4 photocycloaddition,5 Pd-catalyzed
carbonylative cyclization,6 aldolization7 or cyclodehydration8
as the key step(s). They gave only small quantities of the desired
tetracycles and suffered from a low selectivity and tedious
separating problems. Now we report a catalytic synthesis of
fenestrane derivatives using dicobalt octacarbonyl-catalyzed
tandem cycloaddition of dienediynes under CO pressure.
Keese’s group reported a one-pot synthesis of [5.5.5.5]fenes-
tranes from enediyne via the Pauson-Khand reaction.4b How-
ever, the reported yields were low.
(1)
The structure of 3a was established by H and 13C NMR
1
spectroscopic investigations (COSY, long range COSY, DEPT,
HECTOR, long range HECTOR, phase sensitive NOESY, and
2D-INADEQUATE), and mass spectrometry.¶ The correlation
peaks obtained from the COSY spectrum allow us to identify
the consecutive connections of methyl-14 protons to methyine-
9 proton, 9 to 10, 10 to 11, 11 to 12 and 12 to 13. The other
connections were derived from the combinative information
observed from the DEPT, 2D C–H correlation, and 2D long
range C–H correlation spectra. No other products were
observed. The reaction involves the formation of five carbon–
carbon bonds.
Although this multibond formation reaction seems to be
complex, it may be simple: the dicobalt octacarbonyl-catalyzed
carbonylative [2 + 2 + 1] cycloaddition of diyne with carbon
monoxide followed by a subsequent intramolecular [4 + 2]
cycloaddition provides 3a. Another feasible reaction pathway is
that the diene unit reacts first with the closer triple bond and the
thus formed cyclohexa-1,4-diene undergoes a Pauson-Khand
reaction with the remote triple bond.12 The central triple bond
acts as a double functionality that could be used in both
cyclizations. In the same way as in the synthesis of 3a, the
dicobalt octacarbonyl-catalyzed tandem cyclization of dien-
Thus, at first we thought that enediyne (1) or triynes (2) might
be appropriate precursors for the construction of a fenestrane
structure through two sequential [2 + 2 + 1] cycloaddition
reactions. The inner triple bond of triynes might permit the
construction of a quaternary center from two sequential carbon–
carbon bond formation steps. Contrary to our expectation, a
fenestrane structure was not formed. Instead, in the case of
enediynes, polymeric materials were obtained and, in the case
of triynes, an unnatural tetracyclic structure was obtained as the
sole product.9
After many experimental trials, we chose dienediyne as a
precursor to fenestrane.
For the cyclization, dienediyne derivatives 1a, 1b, and 1c
(Scheme 1) were prepared from the a-hydroxy diynes 2a, 2b
and 2c. Compound 2b was prepared according to the procedures
in the literature.10 The same procedure as used for the synthesis
of 2b has been applied to the synthesis of 2a and 2c. The
reaction of a-hydroxy diynes with sodium hydride followed by
hexa-2,4-dienyl bromide led to the isolation of 1a, 1b, and 1c in
high yields which were fully characterized.11‡
Treatment of dienediyne 1a (0.68 mmol) with dicobalt
octacarbonyl (5 mol%) in dichloromethane at 130 °C under 30
† Electronic supplementary information (ESI) available: characterization of
synthesized compounds. See http://www.rsc.org/suppdata/cc/b1/b108034b/
Scheme 1
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CHEM. COMMUN., 2002, 56–57
This journal is © The Royal Society of Chemistry 2002

18.9 ppm; IR nCO 1693 cm21; exact mass calc. 396.2089, obsd.
396.2088.
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(b) F. Sato, H. Urabe and S. Okamoto, Chem. Rev., 2000, 100, 2835; (c)
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diynes 1b and 1c afforded 3b and 3c in 74% and 51% yields,
respectively.
In conclusion, we have developed a new catalytic route to
fenestrane derivatives via dicobalt octacarbonyl-catalyzed cy-
cloaddition of dienediynes. The following significant points are
noteworthy. All the reactions described here are catalytic with
high conversion rates and experimentally a simple reaction, a
one-pot reaction.
3 Reviews on fenestrane chemistry: (a) D. Kuck, in Advances in
Theoretically Interesting Molecules, ed. R. P. Thummel, JAI Press,
Greenwich, CT, 1998, vol. 4, p. 81; (b) M. Thommen and R. Keese,
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Organic Chemistry, ed. B. Halton, JAI Press, Greenwich, CT, 1993, vol.
3, p. 229; (d) W. C. Agosta, in The Chemistry of Alkanes and
Cycloalkanes, ed. S. Patai and Z. Rappoport, Wiley, New York, 1992,
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1991, 47, 3665; (f) K. Krohn, in Organic Synthesis Highlights, ed. J.
Mulzer, H.-J. Altenbach, M. Braun, K. Krohn and H.-U. Reissig, VCH,
Weinheim, 1991, p. 121; (g) B. R. Venepalli and W. C. Agosta, Chem.
Rev., 1987, 87, 399; (h) R. Keese, in Organic Synthesis; Modern Trends,
ed. O. Chizhov, Blackwell, Oxford, 1987, p. 43.
This work was supported by grant No. 2000-2-12200-001-1
from the Basic Research Program of the Korea Science and
Engineering
Foundation
(KOSEF),
KOSEF
(1999-1-122-001-5), and KOSEF through the Center for
Molecular Catalysis. SUS and DHK thank the Ministry of
Education for the Brain Korea 21 Fellowship.
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Notes and references
‡ Compound 2a (0.20 g, 0.69 mmol) was dissolved in 15 ml of THF. The
solution was cooled to 0 °C. To the solution was added NaH (40 mg, 50 wt%
in oil). After the solution was stirred for 1 h, hexa-2,4-dienyl bromide (0.17
g, 1.05 mmol) was added to the solution. The resulting solution was stirred
for 12 h and was quenched with diethyl ether and sat. NH4Cl solution. The
ether layer was separated, dried over anhydrous MgSO4, concentrated and
the residue separated on a silica gel eluting with hexane and diethyl ether
1
(v/v, 10:1). Yield: 0.23 g (89%). 1a: H NMR (CDCl3, 300 MHz): d 7.39
(m, 4 H), 7.28 (m, 6 H), 6.27 (dd, 15.0, 10.0 Hz, 1 H), 6.00 (dd, 15.0, 10.0
Hz, 1 H), 5.70 (m, 2 H), 4.37 (dd, 13.0, 5.4 Hz, 1 H), 4.26 (s, 1 H), 4.08 (dd,
13.0, 7.2 Hz, 1 H), 2.65 (d, 17.0 Hz, 1 H), 2.47 (d, 17.0 Hz, 1 H), 1.71 (d,
6.2 Hz, 3 H), 1.20 (s, 3 H), 1.19 (s, 3 H) ppm; 13C NMR (CDCl3, 75 MHz):
d133.6, 131.7, 131.6, 130.9, 129.8, 128.2, 128.1, 127.5, 126.7, 124.1, 122.9,
87.9, 86.9, 82.6, 75.4, 69.7, 39.1, 29.4, 23.7, 22.8, 18.0 ppm; exact mass
calc. 368.2140, obsd. 368.2137.
§ Compound 1a (0.25 g, 0.68 mmol), 15 ml of CH2Cl2, and Co2(CO)8 (12
mg, 0.035 mmol) were put in a high pressure reactor (100 ml). After the
solution was bubbled with nitrogen for 1 min, the reactor was pressurized
with 30 atm of CO. The reactor was heated at 130 °C for 18 h. After the
reactor was cooled to rt, excess gas was released and the reaction mixture
was transferred into a one-neck flask (50 ml). Removal of the solvent
followed by chromatography on a silica gel column eluting with hexane and
diethyl ether (v/v, 5+1) gave 3a in 84% yield (0.23 g, 0.58 mmol).
¶ 1H NMR (CDCl3, 300 MHz): d 7.60–7.24(m, 10 H), 6.04 (m, 1 H), 5.73
(m, 1 H), 4.16 (dd, 8.7, 5.5 Hz, 1 H), 3.84 (dd, 8.7, 5.5 Hz, 1 H), 3.70 (s, 1
H), 2.90 (m, 1 H), 2.72 (m, 1 H), 2.68 (d, 15.0 Hz, 1 H), 2.43 (d, 15.0 Hz,
1 H), 1.22 (d, 7.3 Hz, 3 H), 1.04 (s, 3 H), 0.00 (s, 3 H) ppm; 13C NMR
(CDCl3, 75 MHz): d 209.2, 180.7, 139.2, 137.9, 134.8, 131.3, 129.8, 128.9,
128.3, 127.7, 126.6, 89.6, 75.3, 70.3, 65.9, 48.0, 43.9, 42.7, 36.8, 25.9, 23.3,
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11 See the Supporting Information.†
12 A referee suggested this reaction pathway. The authors thank the referee
for this suggestion.
CHEM. COMMUN., 2002, 56–57
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