Synthetic approach to cis and trans-decalins via Diels - Alder reaction and ring-closing metathesis as key steps: Further extension to dioxapropellane derivative by ring-closing metathesis

Article abstract of DOI:10.1016/j.tet.2010.10.080

9,10-Substituted cis and trans-decalins were synthesized by a simple route using the Diels-Alder reaction and ring-closing metathesis (RCM) as key steps. Later, the cis-decalin system has been extended to 3,8-dioxa[8.4.4]propellane derivative by RCM sequence as a key step. Copyright

Full text of DOI:10.1016/j.tet.2010.10.080

Tetrahedron 67 (2011) 501e504
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthetic approach to cis and trans-decalins via DielsdAlder reaction and
ring-closing metathesis as key steps: further extension to dioxapropellane
derivative by ring-closing metathesis
*
Sambasivarao Kotha , Arjun S. Chavan, Mirtunjay Kumar Dipak
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 30 August 2010
Received in revised form 20 October 2010
Accepted 27 October 2010
Available online 12 November 2010
9,10-Substituted cis and trans-decalins were synthesized by a simple route using the DielseAlder re-
action and ring-closing metathesis (RCM) as key steps. Later, the cis-decalin system has been extended to
3,8-dioxa[8.4.4]propellane derivative by RCM sequence as a key step.
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
DielseAlder reaction
Ring-closing metathesis
Decalin
Propellane
Hydrogenation
1. Introduction
approach for the synthesis of decalins and hydrindanes.8 Here, we
devised a simple synthetic approach to cis and trans-decalin de-
Many natural products contain an ortho-condensed system as
part of their molecular framework.1 To this end, decalin and
hydrindane systems that appear more frequently have received
considerable attention. For example the trans-decalin system is
present in steroid and terpenoid natural products, such as dri-
manes, clerodanes, and abietanes.1a The cis-decalin containing
diterpene agelasine-A, shows an antimicrobial activity and inhibits
the activity of the enzyme Na, K-ATPase.2 Similarly, branimycin acts
as antibiotic3 (Fig. 1).
Therefore, design of cis and trans-decalin frames is a challenging
task and more specifically bridge functionalized decalins are more
difficult to prepare. Although the DielseAlder (DA) reaction is the
most common route for the synthesis of decalin derivatives, other
routes are also available.1,4 Recently, Snapper and Shizuka reported
the synthesis of cis-decalin derivatives by two-step process in-
volving allylation and RCM,5 and Mehta has used the RCM strategy
for the synthesis of decalin based sesquiterpenoids.6 To prepare
decalin based systems, Enev et al. had reported the synthesis of
branimycin antibiotics containing cis-decalin frame by employing
RCM strategy.7 Philips and Minger reported a tandem metathesis
rivatives using allylation and metathesis9 as key steps. Further,
utilization of RCM delivers the dioxapropellane system.
CN
H
O
H
H
EtO2C
drimane
clerodane
abietic acid analogs
N
N
O
H2N
H
N
OMe
OH
N
Cl
H
H
O
OH OMe
H
O
MeO
OH
branimycin
agelasine-A
* Corresponding author. Tel.: þ91 22 25767160; fax: þ 91 22 25767152; e-mail
address: srk@chem.iitb.ac.in (S. Kotha).
Fig. 1. Decalin based natural products.
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.10.080

502
S. Kotha et al. / Tetrahedron 67 (2011) 501e504
Carbocylic and heterocyclic-based propellanes are important
obtained by this route is identical to that of the product obtained
via metathesis (Scheme 2).
structural units present in many natural and non-natural targets.10
Ginsburg and Wiberg had reviewed various aspects of small and
medium ring propellane derivatives.11 Koskinen group had
reviewed the literature of natural products containing propellane
ring systems.12
2. Results and discussion
To design propellane derivatives, cis-decalin diester was iden-
tified as a key intermediate. To this end, the DA reaction of sulfolene
(1) and dimethyl acetylenedicarboxylate (DMAD) under heating in
toluene or sealed tube condition was attempted. To our surprise the
DA reaction failed to give the required adduct. Next, an alternate DA
route involving diethyl maleate and sulfolene (1) was attempted.
Unfortunately this route also did not deliver the required DA
adduct.
Scheme 2. Preparation of cis and trans-decalins by RCM.
2.1. cis and trans-Diallylated compounds 5a,b
Subsequently, maleic anhydride (2) was reacted with sulfolene
(1) in diglyme at 150e160 ꢀC to generate the known cyclohexene
derivative 3.13 Ethanolysis of 3 under p-TSA conditions using known
procedure gave the diester 4.14 Allylation of the dianion generated
from 4 gave the cis and trans-diallylated product (5a and 5b) in 3:2
ratio (Scheme 1). These diastereoisomers were separated by silica-
gel column chromatography.
2.4. Synthesis of 3,8-dioxa[8.4.4]propellane by RCM
Having prepared both the cis and trans-decalin derivatives 7a
and 7b, we focused our attention toward the synthesis of 3,8-
dioxapropellane derivative. To this end, diester 7a was reduced
with LAH to deliver the diol 8. The preparation of this diol 8 is
known in the literature from the reduction of 9,10-decalin anhy-
dride by LAH.17 O-Allylation of the diol 8 with allyl bromide in DMF
gave the cis-9,10-bis(allyloxymethyl)decalin (9) in good yield. RCM
of diallyl derivative 9 with the Grubbs’ first generation catalyst
afforded the tricyclic system 10 as a cisetrans olefinic mixture,18
which on hydrogenation gave the saturated dioxapropellane de-
rivative 11 (Scheme 3).
Scheme 1. Preparation of cis and trans-diallylated compounds.
2.2. cis and trans-Decalins by RCM
Both cis- and trans-diallyl derivatives 5a and 5b gave the expec-
ted RCM products 6a and 6b in good yields upon exposure to Grubbs’
second generation catalyst at rt. It is interesting to note that the
trans-diallyl derivative 5b gave the double bond isomerized product
6b under these conditions.15 Further, hydrogenation of these RCM
products with Pd/C gave the cis and trans-decalin derivative 7a and
7b, respectively (Scheme 2). The hydrogenation of trans-decalin
derivative takes comparatively more time than cis-derivative. Thus
we have prepared stereochemically pure cis and trans-decalin sys-
tems in 3:2 ratios by employing allylation and RCM sequence.
Scheme 3. Preparation of 3,8-dioxa[8.4.4]propellane.
3. Conclusion
A simple route for the synthesis of cis and trans-decalin de-
rivatives has been developed by utilizing DA reaction and RCM
sequence as key steps. One of these decalin systems was found to be
useful to prepare dioxapropellane system via the RCM approach.
2.3. cis-Decalin diester by direct alkylation
To establish the structure of cis-decalin derivative 7a, its prep-
aration by an alternate synthetic route based on literature
procedure was attempted.16 Thus, the diester 4 was alkylated with
1,4-dibromobutane using NaHMDS to generate unsaturated
cis-decalin derivative. Subsequent catalytic hydrogenation with
Pd/C in ethanol gave 7a. The 1H NMR spectral data of the compound
4. Experimental section
4.1. General procedures
All the reactions were monitored by employing TLC technique
using appropriate solvent system for development. Reactions

S. Kotha et al. / Tetrahedron 67 (2011) 501e504
503
involving oxygen sensitive reagents or catalysts were performed in
4.1.2. cis-Diethyl
1,4,4a,5,8,8a-hexahydronaphthalene-4a,8a-di-
degassed solvents. Dry tetrahydrofuran (THF) was obtained by dis-
tillation over sodium benzophenone ketyl freshly prior to use.
DichloromethanewasdistilledoverP2O5. Magnesiumsulfate/sodium
sulfate were dried in an oven at 130 ꢀC for 1 day before use. All the
solvent extracts were washed successively with water, brine (satu-
rated sodium chloride solution) and dried over anhydrous magne-
siumsulfate/sodiumsulfate, andconcentratedatreducedpressureon
rotary evaporator. Yields reported are isolated yields of the products
after purification by column chromatography. All the commercial
grade reagents were used without further purification. Infrared (IR)
spectra for solid samples were recorded as KBr pellets and liquid
samples as their film between CsCl plates. Proton Nuclear Magnetic
Resonance (1H NMR) spectra were generally recorded on 400 MHz or
300 MHz spectrometers. Carbon Nuclear Magnetic Resonance (13C
NMR) spectra were recorded on 100 MHz or 75 MHz spectrometer.
NMR samples were generally made in chloroform-d solvent and
carboxylate (6a). To a solution of 5a (25 mg, 0.08 mmol) in DCM
(10 mL), Grubbs’ second generation catalyst (3.46 mg, 5 mol %) was
added under argon at rt. After completion of the reaction (TLC
monitoring, 6 h), the solvent was evaporated under reduced pres-
sure and the residue was purified by a silica-gel column chroma-
tography (3% ethyl acetate/petroleum ether) to give 6a (17.8 mg,
80% yield) as a thick colorless liquid. 1H NMR (400 MHz, CDCl3):
d
5.56 (s, 4H), 4.13 (q, J¼7.0 Hz, 4H), 2.64 (br s, 3H), 2.38 (d,
J¼15.0 Hz, 5H), 1.23 (t, J¼7.0 Hz, 6H) ppm. 13C NMR (100.6 MHz,
CDCl3):
d 175.6, 124.0, 60.5, 44.4, 33.7, 14.2 ppm. IR (KBr): nmax:
2856, 1768, 1438, 913 cmꢂ1. HRMS (QTOF ESþ): m/z [MþH]þ calcd
for C16H23O4: 279.1596; found: 279.1602.
4.1.3. trans-Diethyl
1,2,4a,5,8,8a-hexahydronaphthalene-4a,8a-di-
carboxylate (6b). To a solution of 5b (55 mg, 0.18 mmol) in DCM
(10 mL), Grubbs’ second generation catalyst (7.6 mg, 5 mol %) was
added under argon at rt. After completion of the reaction (TLC
monitoring, 6 h), the solvent was evaporated under reduced pressure
and the residue was purified by a silica-gel column chromatography
(3% ethyl acetate/petroleum ether) to give 6b (37 mg, 76% yield) as
chemical shifts were reported in
d scale using tetramethylsilane
(TMS) as an internal standard. The standard abbreviation s, d, t, q
and m, refer to singlet, doublet, triplet, quartet, and multiplet,
respectively. Coupling constants (J) are reported in Hertz. Analytical
thin-layer chromatography (TLC) was performed on (10ꢁ5 cm) glass
plates coated with silica gel (containing 13% calcium sulfate as
a binder). Silica gel is coated on glass plates using ‘Sandwich Tech-
nique.’ In this process, two equally sized clean glass plates are im-
mersedinuniformlystirred silicagelsuspensioninanorganicsolvent
(usually ethyl acetate). Only the exposed surface of the plate is thus
coated with silica gel. The solvent evaporates readily leaving a thin-
layer of silica gel and then the plate is ready for the use. Visualization
of the spots on TLC plates was achieved either by exposure to iodine
vapors or UV light. The products were purified by silica gel
(100e200 mesh) column chromatography.
a thick colorless liquid. 1H NMR (400 MHz, CDCl3):
d 5.58e5.68 (m,
4H), 5.01 (t, J¼7.3 Hz, 1H), 4.11e4.16 (m, 1H), 3.98e4.08 (m, 2H),
2.62e2.73 (m, 6H),1.21 (t, J¼7.0 Hz, 3H), 2.26 (dd, J1¼13.7 Hz,
J2¼8.8 Hz, 1H), 2.12 (dd, J1¼16.8 Hz, J2¼2.7 Hz, 1H), 1.27 (t, J¼7.0 Hz,
3H) ppm. 13C NMR (100.6 MHz, CDCl3):
d 175.0, 173.7, 134.8, 125.3,
123.9,118.6, 60.7, 60.4, 50.3, 45.5, 35.9, 34.2, 34.2, 28.4,14.1,14.0 ppm.
IR (KBr): nmax: 2848, 1758, 1442, 911 cmꢂ1. HRMS (QTOF ESþ): m/z
[MþH]þ calcd for C16H23O4: 279.1596; found: 279.1591.
4.2. General procedure for the hydrogenation
To a solution of unsaturated diester in ethanol, 10% palladium/
charcoal was added and the reaction mixture was stirred at rt for
required time (monitored by NMR) under 1 atm hydrogen pressure.
Then, the reaction mixture was filtered through Celite and washed
with ethyl acetate (20 mL). The solvent was removed under re-
duced pressure and the crude product was purified by silica-gel
column chromatography. Elution of the column with 5% ethyl ac-
etate/petroleum ether gave the hydrogenated product.
4.1.1. Diethyl 1,2-diallylcyclohex-4-ene-1,2-dicarboxylate (5a,b). To
a cooled solution (at 0 ꢀC) of diethyl tetrahydropthalate (4) (250 mg,
1.35 mmol) in THF (10 mL) was added NaHMDS (1 M solution in
hexane) (4 mL, 4 mmol) in drop-wise manner. After half an hour the
solution became red in color. Allyl bromide (0.46 mL, 5.43 mmol)
was added slowly at 0 ꢀC. After completion of the reaction (TLC
monitoring, 10 h), the reaction mixture was quenched with aque-
ous saturated NH4Cl solution (2 mL) and the solvent was evapo-
rated under reduced pressure. The residue was partitioned
between water (50 mL) and ether (25 mL). The aqueous portion was
extracted with ether (3ꢁ25 mL). The combined organic layer was
washed with brine and dried over anhydrous Na2SO4. The solvent
was evaporated under reduced pressure and the resulting residue
was purified by a silica-gel column chromatography (3% ethyl ac-
etate/petroleum ether) to gave cis and trans 5a (189 mg) and 5b
(126 mg), respectively, in 3:2 ratio as a thick pale yellow liquid. The
overall yield is 76%.
4.2.1. cis-9,10-Bis(carboethoxy)decalin (7a). (Reaction time 2 days,
yield 99%). Mp 44e46 ꢀC.
1H NMR (400 MHz, CDCl3):
d
4.12 (q, J¼7.0 Hz, 4H), 2.40 (br s, 2H),
1.90 (brs, 2H),1.80e1.25(m,12H),1.23(t, J¼7.0 Hz, 6H) ppm.13C NMR
(100 MHz, CDCl3):
d 177.0, 60.1, 47.7, 31.0 (br s), 22.0, 14.3 ppm. IR
(KBr): nmax: 2943, 1718, 1265, 1142, 1032 cmꢂ1. HRMS (QTOF ESþ):
m/z [MþH]þ calcd for C16H27O4: 283.1909; found: 283.1900.
4.2.2. trans-9,10-Bis(carboethoxy)decalin (7b). (Reaction time
days, yield 99%). Mp 102e104 ꢀC.
3
Spectral data for compound 5a. 1H NMR (400 MHz, CDCl3):
d
5.54e5.64 (m, 4H), 4.95e5.04 (m, 4H), 4.15e4.27 (m, 2H),
1H NMR (400 MHz, CDCl3):
d
4.26e4.18 (dq, J1¼7.0 Hz, J2¼3.7 Hz,
3.95e4.12 (m, 2H), 2.55e2.68 (m, 4H), 2.21 (dd, J1¼13.7 Hz,
2H), 4.06e3.98 (dq, J1¼7.0 Hz, J2¼3.7 Hz, 2H), 2.03 (m, 2H), 1.88 (m,
J2¼8.8 Hz, 2H), 2.08 (dd, J1¼16.7 Hz, J2¼2.7 Hz, 2H), 1.22 (t, J¼7.0 Hz,
2H), 1.64e1.28 (m, 4H), 1.25 (t, J¼7.2 Hz, 8H), 0.89 (t, J¼7.0 Hz,
6H) ppm. 13C NMR (100.6 MHz, CDCl3):
d
173.7, 134.8, 123.9, 118.6,
6H) ppm. 13C NMR (100 MHz, CDCl3):
d 174.9, 60.3, 52.0, 32.7, 26.2,
60.7, 50.3, 36.0, 28.4, 14.1 ppm. IR (neat): nmax 3056, 2917, 1745,
1438, 1199, 913 cmꢂ1. HRMS (QTOF ESþ): m/z [MþNa]þ calcd for
C18H26O4Na: 329.1729; found: 329.1737.
20.6, 18.5, 14.9, 14.2 ppm. IR (KBr): nmax: 2963, 1715, 1265, 1140,
1033 cmꢂ1. HRMS (QTOF ESþ): m/z [MþH]þ calcd for C16H27O4:
283.1909; found: 283.1918.
Spectral data for compound 5b. 1H NMR (400 MHz, CDCl3):
d
5.54e5.67 (m, 4H), 5.03e5.07 (m, 4H), 4.09e4.20 (m, 4H), 2.89
4.2.3. cis-9,10-Bis(hydroxymethyl)decalin (8). To a suspension of
LAH (862 mg, 22.69 mmol) in dry THF (30 mL), cis-9,10-bis(car-
boethoxy)decalin (7a) (1.6 g, 5.67 mmol) was added by dissolving
in dry THF (15 mL) under nitrogen and the reaction mixture was
refluxed for 7 h. After completion of the reaction (TLC monitoring),
the reaction mixture was cooled to 0 ꢀC and quenched with ethyl
acetate and stirred for 30 min at rt. Then, the organic layer was
(dd, J1¼13.1 Hz, J2¼6.4 Hz, 2H), 2.46 (d, J¼17.4 Hz, 2H), 2.27 (dd,
J1¼13.1 Hz, J2¼8.3 Hz, 2H), 2.04 (d, J¼17.7 Hz, 2H), 1.25 (t, J¼7.0 Hz,
6H) ppm. 13C NMR (100.6 MHz, CDCl3):
d 173.8, 133.5, 124.3, 118.5,
60.5, 50.5, 37.2, 30.0, 14.0 ppm. IR (neat): nmax 3054, 2912, 1750,
1438, 1199, 911 cmꢂ1. HRMS (QTOF ESþ): m/z [MþH]þ calcd for
C18H27O4: 307.1909; found: 307.1899.

504
S. Kotha et al. / Tetrahedron 67 (2011) 501e504
washed with water (2e3 times), brine and dried over Na2SO4, and
concentrated under reduced pressure. The crude product was
washed with petroleum ether afforded 8 as pure white solid (1.03 g,
92%). Mp 152e156 ꢀC. (lit. mp 152 ꢀC and 180e182 ꢀC).17 1H NMR
Acknowledgements
We thank DST, New Delhi for the financial support and SAIF,
Mumbai for recording the spectral data. S.K. thanks DST for the
award of J.C. Bose fellowship. A.S.C. and M.K.D. thank CSIR (New
Delhi) for award of the research fellowship.
(400 MHz, CDCl3):
d 4.08 (br s, 2H), 3.29 (br s, 2H), 2.73 (br s, 2H),
2.15e1.40 (m, 16H) ppm. 13C NMR (65.5 MHz, CDCl3):
d 68.1, 39.2,
30.3, 21.6 ppm.
References and notes
4.2.4. cis-9,10-Bis(allyloxymethyl)decalin (9). To a suspension of
NaH (242 mg, 10.1 mmol) in DMF (25 mL), cis-9,10-bis(hydrox-
ymethyl)decalin (8) (500 mg, 2.52 mmol) was added. Then, the
reaction mixture was cooled to 0 ꢀC and allyl bromide (917 mg,
7.57 mmol) was added dropwise. Finally, the reaction mixture was
stirred at rt for 24 h and after completion of the reaction (TLC
monitoring), the reaction was quenched with NH4Cl, extracted with
ethyl acetate, washed with water, brine and dried over Na2SO4, and
concentrated under reduced pressure. The crude product was pu-
rified by silica-gel column chromatography. Elution of the column
with 2% ethyl acetate/petroleum ether gave 9 (517 mg, 74%). 1H
1. (a) Varner, M. A.; Grossman, R. B. Tetrahedron 1999, 55, 13867; (b) Vandewalle,
M.; Clerco, P. D. Tetrahedron 1985, 41, 1767; (c) Takashi, T. Synthesis 2000, 611;
(d) Singh, V.; Iyer, S. R.; Pal, S. Tetrahedron 2005, 61, 9197; (e) Nakadate, S.;
Nozawa, K.; Horie, H.; Fujii, Y.; Nagai, M.; Hosoe, T.; Kawai, K.-I.; Yaguchi, T.;
Fukushima, K. J. Nat. Prod. 2007, 70, 1510; (f) Oguchi, T.; Watanabe, K.; Ohkubo,
K.; Abe, H.; Katoh, T. Chem.dEur. J. 2009, 15, 2826; (g) Yao, G.; Vidor, N. B.; Foss,
A. P.; Chang, L. C. J. Nat. Prod. 2007, 70, 901.
2. Nakamura, H.; Wua, H.; Ohizumia, Y.; Hiratab, Y. Tetrahedron Lett. 1984, 25,
2989.
3. Mulzer, J.; Castagnolo, D.; Felzmann, W.; Marchart, S.; Pilger, C.; Enev, V. S.
Chem.dEur. J. 2006, 12, 5992.
4. Kim, W. H.; Lee, J. H.; Aussedat, B.; Danishfsky, S. J. Tetrahedron 2010, 66, 6391.
5. Shizuka, M.; Snapper, M. L. Angew. Chem., Int. Ed. 2008, 47, 5049.
6. Mehta, G.; Kumaran, R. S. Tetrahedron Lett. 2003, 44, 7055.
7. Enev, V. S.; Drescher, M.; Mulzer, J. Org. Lett. 2008, 10, 413; (b) Marchart, S.;
Mulzer, J.; Enev, V. S. Org. Lett. 2007, 9, 813; (c) Marchart, S.; Gromov, A.; Mulzer,
J. Angew. Chem., Int. Ed. 2010, 49, 2050.
NMR (400 MHz, CDCl3):
5.23 (q, J¼1.8 Hz, 1H), 5.15 (q, J¼1.8 Hz, 1H), 5.12 (q, J¼1.8 Hz, 1H),
3.92 (td, J¼2.1 Hz, 1.8 Hz, 4H), 3.57 (br s, 2H), 3.20 (br s, 2H),
d
5.94e5.84 (m, 2H), 5.28 (q, J¼1.8 Hz, 1H),
1.90e1.20 (m, 16H) ppm. 13C NMR (100 MHz, CDCl3):
d 135.6, 116.2,
8. Minger, T. L.; Phillips, A. J. Tetrahedron Lett. 2002, 43, 5357.
74.5, 72.4, 39.0, 32.0(br s), 21.8 ppm. IR (neat): nmax: 2926, 2863,
1468, 1094, 920 cmꢂ1. HRMS (QTOF ESþ): m/z [MþH]þ calcd for
C18H31O2: 279.2324; found: 279.2318.
9. (a) Grubbs, R. H. Handbook of Metathesis; Wiley-VCH: Weinheim, 2003; Vol.
1e3; (b) Grubbs, R. H.; Schrock, R. R.; Furstner, A. Advanced Synthesis & Catal-
€
ysis, Olefin Metathesis; Wiley-VCH: Weinheim, 2007; Vol. 349, pp 1e265; (c)
Chauvin, Y. Angew. Chem., Int. Ed. 2006, 45, 3741; (d) Schrock, R. R. Angew. Chem.,
Int. Ed. 2006, 45, 3748; (e) Grubbs, R. H. Angew. Chem., Int. Ed. 2006, 45, 3760; (f)
Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem., Int. Ed. 2005, 44, 4490; (g)
Kotha, S.; Lahiri, K. Synlett 2007, 2767; (h) Grubbs, R. H. Tetrahedron 2004, 60,
4.2.5. 3,8-Dioxa[8.4.4]octadec-5-ene (10). A solution of cis-9,10-bis
(allyloxymethyl)decalin (9) (150 mg, 0.54 mmol) in dry DCM
(15 mL) was degassed with nitrogen for 5 min and then Grubbs first
generation catalyst (5 mmol %) was added and the reaction mixture
was stirred at rt for 24 h. After completion of the reaction (TLC
monitoring), solvent was evaporated under vacuum and the crude
product was purified by silica-gel column chromatography. Elution
of the column with 2% ethyl acetate/petroleum ether gave 10 as
a cisetrans olefinic mixture (99 mg, 73%). Mp 150e154 ꢀC. 1H NMR
€
7117; (i) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012; (j) Hoveyda, A. H.;
Zhugralin, A. R. Nature 2007, 450, 243; (k) Mori, M. J. Mol. Cat. A: Chem. 2004, 213,
73; (l) Astruc, D. New J. Chem. 2005, 29, 42; (m) Kotha, S.; Mandal, K. Chem.dAsian
J. 2008, 4, 354; (n) Kotha, S.; Sreenivasachary, N. Indian J. Chem., Sect. B 2001, 40,
763; (o) Casterlenas, R.; Fischmeister, C.; Bruneau, C.; Dixneuf, P. H. J. Mol. Catal. A:
Chem. 2004, 213, 31; (p) Clavier, H.; Grela, K.; Kirschning, A.; Mauduit, M.; Nolan,
S. P. Angew. Chem., Int. Ed. 2007, 46, 6786; (q) Deshmukh, P. H.; Blechert, S. Dalton
Trans. 2007, 2479.
10. (a) Ginsburg, D. Propellanes: Structure and Reactions; Chemie, GmbH: D-6940,
Weinheim, 1975; (b) Ginsburg, D. Propellanes: Structure and Reactions (Sequel-I);
Chemie, GmbH: D-6940, Weinheim, 1975; (c) Ginsburg, D. Propellanes: Struc-
ture and Reactions (Sequel-II); Chemie, GmbH: D-6940, Weinheim, 1980; (d)
Kotha, S.; Dipak, M. K. Chem.dEur. J. 2006, 12, 4446; (e) Nguyen, T. X.; Ko-
bayashi, Y. J. Org. Chem. 2008, 73, 5536; (f) Shi, Q. W.; Sauriol, F.; Mamer, O.;
Zamir, L. O. Chem. Commun. 2003, 68.
11. (a) Ginsburg, D. Acc. Chem. Res. 1969, 2, 121; (b) Ginsburg, D. Acc. Chem. Res.
1972, 5, 249; (c) Ginsburg, D. Top. Curr. Chem. 1987, 137, 1; (d) Ginsburg, D. Acc.
Chem. Res. 1974, 7, 286; (e) Ginsburg, D. Tetrahedron 1974, 30, 1487; (f) Wiberg,
K. B. Acc. Chem. Res. 1984, 17, 379; (g) Wiberg, K. B. Acc. Chem. Res. 1996, 29, 229;
(h) Wiberg, K. B. Chem. Rev. 1989, 89, 975.
12. Pihko, A. J.; Koskinen, A. M. P. Tetrahedron 2005, 61, 8769.
13. Harwood, L. M.; Moody, C. J. Experimental Organic Chemistry: Principles and
Practice; Blackwell Scientificlication: Victoria, 1989; 624e625.
14. Cope, A. C.; Herrick, E. C. p 304 Organic Syntheses; 1963; Coll. Vol. 4 Vol. 30, p 29
(1950).
15. (a) Schmidt, B. Eur. J. Org. Chem. 2004, 1865 and references cited therein.
16. (a) Bilyard, K. G.; Garratt, P. J.; Hunter, R.; Lete, E. J. Org. Chem. 1982, 47, 4731; (b)
Bilyard, K. G.; Garratt, P. J.; Zahler, R. Synthesis 1980, 389; (c) Rae, I. D.; Serelis,
A. K. Aust. J. Chem. 1941, 1, 43.
(400 MHz, CDCl3):
d
5.73 (t, J¼2.6 Hz, 2H), 3.97 (s, 4H), 3.43 (br s,
4H), 1.90e1.20 (m, 16H) ppm. 13C NMR (65.5 MHz, CDCl3):
d
129.6,
74.1, 71.1, 39.0, 32.0 (br s), 21.7(br s) ppm. IR (KBr): nmax: 2925, 2861,
1467, 1265, 1103 cmꢂ1. HRMS (QTOF ESþ): m/z [MþH]þ calcd for
C16H27O2: 251.2011; found: 251.2008.
4.2.6. 3,8-Dioxa[8.4.4]propellane (11). To a solution of 3,8-dioxa
[8.4.4]octadec-5-ene (10) (50 mg, 0.20 mmol) in ethanol (10 mL),
10% palladium/charcoal was added and the reaction mixture was
stirred at rt for 24 h under 1 atm hydrogen pressure. Then, the
reaction mixture was filtered through Celite and washed with ethyl
acetate (20 mL), after the removal of solvent under reduced pres-
sure crude product was obtained. The crude product was purified
by silica-gel column chromatography. Elution of the column with
2% ethyl acetate/petroleum ether gave 11 as a white solid (45 mg,
17. (a) Shea, K. J.; Greeley, A. C.; Nguyen, S.; Beauchamp, P. D.; Aue, D. H.; Wit-
zemant, J. S. J. Am. Chem. Soc. 1986, 108, 5901; (b) Altman, J.; Babad, E.; Itzchaki,
J.; Ginsburg, D. Tetrahedron 1966, 22, 279.
87%). Mp 110e112 ꢀC. 1H NMR (400 MHz, CDCl3):
(s, 4H), 1.95e1.40 (m, 20H) ppm. 13C NMR (65.5 MHz, CDCl3):
d
3.42 (s, 4H), 3.40
76.5,
d
€
18. (a) Delgado, M.; Martin, J. D. J. Org. Chem. 1999, 64, 4798; (b) Furstner, A.;
71.0, 39.0, 29.9(br s), 26.5, 21.9 ppm. IR (KBr): nmax: 2920, 2859,1117,
1012 cmꢂ1. HRMS (QTOF ESþ): m/z [MþH]þ calcd for C16H29O2:
253.2168; found: 253.2163.
Langemann, K. Synthesis 1997, 792; (c) Abell, A. D.; Alexander, N. A.; Aitken, S.
G.; Chen, H.; Coxon, J. M.; Jones, M. A.; McNabb, S. B.; Taylor, A. M. J. Org. Chem.
2009, 74, 4354.