Preparation of sixteen 3-hydroxy-4- and 7-hydroxy-1-hydrindanones and 3-hydroxy-4- and 8-hydroxy-1-hydroazulenones

Article abstract of DOI:10.1002/ejoc.200600639

3-Hydroxyoctahydro-4H-inden-4-ones and 7-hydroxyoctahydro-1H-inden-1-ones (1, 2 and 3, 4, respectively), as well as the homologous 3-hydroxyoctahydro- 4(1H)-azulenones (5, 6) and 8-hydroxyoctahydro-1(2H)-azulenones (7, 8), were prepared diastereoselective

Full text of DOI:10.1002/ejoc.200600639

FULL PAPER
DOI: 10.1002/ejoc.200600639
Preparation of Sixteen 3-Hydroxy-4- and 7-Hydroxy-1-hydrindanones and
3-Hydroxy-4- and 8-Hydroxy-1-hydroazulenones
Georgia G. Tsantali,[a] John Dimtsas,[a] Constantinos A. Tsoleridis,[a] and
Ioannis M. Takakis*[a]
Keywords: Alcohols / Diastereoselectivity / Elimination / Fused-ring systems / Isomerization / Ketones
3-Hydroxyoctahydro-4H-inden-4-ones and 7-hydroxyocta-
hydro-1H-inden-1-ones (1, 2 and 3, 4, respectively), as well
as the homologous 3-hydroxyoctahydro-4(1H)-azulenones (5,
6) and 8-hydroxyoctahydro-1(2H)-azulenones (7, 8), were
prepared diastereoselectively either from the precursor α,β-
enones 9, 10, 11, and 12 or by an isoxazoline method. Un-
masking of the isoxazolines 13i, 14i, and 14j with O3 proved
a more stereoselective process than hydrogenolysis. In many
cases epimerization with 100% completeness was observed
on passing the epimerizable diastereomers once through a
column filled with silica gel, the trans-fused hydrindanones
thus in most cases furnishing the cis-fused epimers and the
cis-fused hydroazulenones the trans forms. These results
have been corroborated by AM1 theoretical computations,
which indicate that the cis-fused epimers in these hydrind-
anone systems are more stable than the trans-fused variants,
whereas the reverse was calculated for the hydroazulenone
homologues.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
Introduction
The hydroxyhydrindanone[1–4] (1–4) and -hydro-
azulenone[5,6] (5–8) skeletons are found incorporated in a
plethora of natural products or intermediate compounds
leading to them: characteristic examples are to be found
among steroidal compounds,[1] alkaloids,[2] diterpenes,[3,5]
and sesquiterpenes[4,6] (Figure 1). The synthesis of these
and similar compounds, however, is occasionally compli-
cated by epimerization at the juncture of the two rings, usu-
ally furnishing the more stable epimer – cis in hydrind-
anone[7] and trans in hydroazulenone[6l,7f,8] systems – as the
predominant or exclusive product. Furthermore, during
their preparation, many of these and related ketols suffer in
situ dehydration to provide the corresponding α,β-enones
9,[7b,8d,9] 11,[6b,l,8d,9a,9j,10] 10,[9j,11] and 12,[3e,6o] or related en-
ones containing 9–12 as subunits. In view of the importance
of these systems in natural product synthesis and the afore-
mentioned problems, we directed our attention toward the
synthesis of the sixteen diastereomerically pure aldols 1–8.
Figure 1. Hydroxyhydrindanones 1–4, hydroxyhydroazulenones 5–
8, hydrindenones 9, 10, and hydroazulenones 11, 12.
tion of the carbonyl moiety in 9, followed by hydroboration/
oxidation,[12] furnished the acetalols 9b and 9c, which were
conveniently separable by column chromatography on silica
gel. From the product ratios, the preferred side of borane
attack is the less hindered convex (β) side, by a factor of ca.
two. Mild deacetalization of 9b and 9c afforded 1b and 2a.
Preparation of the hydroazulenic aldols 5b and 6a was en-
tirely analogous.
Results and Discussion
Starting from the known[9a,9j] α,β-enones 9 and 11, the
aldols 1, 2, 5, and 6 were each assembled in three to five
simple steps by the sequence illustrated in Scheme 1. Protec-
Swern[13] or PCC[14] oxidation of the hydroxy acetals 9b,
9c, 11b, and 11c to the keto acetals 9d, 9e, 11d, and 11e,
followed by reduction with dibal-H, provided the hydroxy
acetals 9f, 9g, 11f, and 11g, respectively, with notably high
diastereoselectivities observed during the reduction steps.
The cis-fused ketones exclusively furnished α-alcohols,
whereas the trans-fused variants afforded the β-isomers,
[a] Department of Chemistry, University of Thessaloniki,
Thessaloniki 541 24, Greece
E-mail: itakakis@chem.auth.gr
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
258
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 258–265

Hydroxy-hydrindanones and Hydroxy-hydroazulenones
FULL PAPER
Scheme 1. Preparation of aldols 1, 2, 5, and 6.
which suggests that hydride transfer from dibal-H to the Table 1. Heats of formation (∆Hf) of aldols, enones, and keto ace-
tals as calculated by AM1, together with relative energies (∆∆Hf)
carbonyl group takes place from the less hindered β-face in
the cis ketones, but from the α-face in the trans isomers. In
the latter reduction, a rigid chair conformation of the six-
and seven-membered rings forces the acetal functionality
of cis-fused vs. trans-fused isomers.[a]
Compd.
∆Hf
∆∆Hf[b]
–1.32
Compd. ∆Hf
∆∆Hf
1a
–113.54
–112.22
–114.31
–111.91
–118.83
–120.35
–118.89
–118.95
–115.26
–112.98
–114.42
–111.04
7a
8a
7b
8b
9
10
11
12
9d
9e
11d
11e
–116.09
2.98
to point toward the β-face, thus interfering sterically with 2a
–119.07
–119.63
–118.99
–40.62
1b
–2.40
1.52
–0.64
3.80
hydride transfer from this side. In this case, hydride transfer
occurs from the α-face to give the β-alcohols.
2b
5a
Mild hydrolysis of 9f, 9g, 11f, and 11g provided aldols
6a
–44.42
1a, 2b, 5a, and 6b. Isolation by column chromatography was
refrained from in the cases of some of the product aldols,
in order to circumvent the aforementioned epimerization
and elimination obstacles. On attempted purification by
chromatography on a silica gel column, ketones 9e (trans)
and 11d (cis) were epimerized into 9d (cis) and 11e (trans),
respectively. AM1 computations[15] indicated 9d to be more
stable than 9e by 0.50 kcalmol–1 and 11e to be more stable
than 11d by 2.73 kcalmol–1 (Table 1).
Even though the above synthetic steps were straightfor-
ward, hydrolysis of the acetalols proved problematic, the
conditions having to be chosen very carefully so that deace-
talization would proceed to completion without concomi-
tant or subsequent dehydration to give the enones 9 or 11.
5b
6b
3a
4a
3b
4b
0.07
–46.19
4.87
–51.05
–2.28
–3.38
–141.55
–141.05
–145.46
–148.19
–0.50
2.73
[a] Calculations were carried out on the most stable conformations.
In 3a, 4a, 3b, 8a, and 7b, OH was equatorial, and in 4b, 7a, and
8b axial, according to 1H NMR (see Table S1 in the Supporting
Information). In aldols, the hydroxy hydrogen was syn to the car-
bonyl oxygen. [b] ∆∆Hf = ∆Hf(cis)–∆Hf(trans) in kcalmol–1. Nega-
tive differences indicate higher, and positive lower, stability of a
compound relative to its isomer.
Recourse to aq. AcOH (25–50%)/THF or aq. HCl (0.5– rectified this problem (see Exp. Sect.). Under more vigorous
2.5%)/THF (or MeOH) mixtures, stirring at room temp. or conditions (5–10% aq. HCl in THF; reflux 0.5–1 h) all al-
at reflux, and monitoring of the course of hydrolysis partly dols discussed here were dehydrated to enones 9 and 11.
Eur. J. Org. Chem. 2007, 258–265
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
259

G. G. Tsantali, J. Dimtsas, C. A. Tsoleridis, I. M. Takakis
FULL PAPER
Scheme 2. Preparation of isoxazolines 13i, 14i, and 14j.
We set out next to prepare the remaining eight ketols 3, whereas 14i gave a more complex mixture consisting of the
4, 7, and 8, with the carbonyl and hydroxy moieties inter- two epimeric aldols 7a and 8a, together with the enone 12
changed on the two rings relative to the isomers 1, 2, 5, and and an indeterminable quantity of cis- and trans-1-perhy-
6. To this end we employed a well established isoxazoline droazulenones. Side products similar to these had also been
method suitable for the synthesis of hydrindanone and hy- found in a previous investigation.[6j] Further work using
droazulenone aldols[6j,16] in combination with a synthetic these conditions was abandoned.
route similar to that presented in Scheme 1. The ready avail-
ability of keto esters 13 and 14 prompted us to use the se-
quence outlined in Scheme 2 for the preparation of the req-
uisite isoxazolines. The last step involved ring-closure of the
aldoximes with chloramine-T[17] to furnish the known cis-
fused isoxazolines 13i and 14i, previously prepared by nitro-
cycloalkene routes.[16d] Interestingly, the trans-fused isox-
azoline 14j (see below for confirmation of stereochemistry)
was also obtained in low yield, while no analogous trans-
fused product was observed during cyclization of the six-
membered homologue. Theoretically, the intramolecular
1,3-dipolar nitrile oxide cycloaddition may take place on
either face of the double bond, while previous work on sim-
ilar systems had shown a transition state giving rise to the
cis-fused isoxazoline to be favored over that furnishing the
trans-fused isomer.[6j,16c,18] Dreiding models also favored
the cis-fused isoxazoline 13i in this work, but the flexibility
dols 3a, 4a, 7a, and 8.
of the seven-membered ring (in relation to the six-mem-
bered) can overcome the relatively higher energetic barrier
imposed in the transition state and thus provide a small 13i to afford the aldol 3a with H2/W-2 Ra-Ni/MeOH/
amount of the trans-fused epimer 14j. AcOH. When we repeated the exact experimental condi-
Scheme 3. Unmasking of isoxazolines 13i, 14i, and 14j to give al-
Wollenberg[16d] had previously unmasked the isoxazoline
The isoxazolines 13i, 14i, and 14j were unmasked under tions reported, we mainly obtained the starting isoxazoline,
several sets of conditions described in the literature[6j,16,19] but in other runs the use of a small excess of W-2 Ra-Ni
and illustrated in Scheme 3. Hydrogenolysis of 13i with W- furnished mixtures of both epimers 3a and 4a, their pro-
2 Ra-Ni/MeOH/H2O/boric acid[19a] afforded 3a and 4a, portions varying with the quantity of catalyst used. With
260
www.eurjoc.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 258–265

Hydroxy-hydrindanones and Hydroxy-hydroazulenones
FULL PAPER
use of even greater excesses of W-2 Ra-Ni (15- to 20-fold) conditions, 7a and 7b were both completely epimerized to
we obtained 4a exclusively (see Exp. Sect.); apparently, the afford the seemingly more stable aldols 8a and 8b, respec-
imine–enamine tautomeric equilibrium,[16] shown in tively. Indeed, this is an efficacious alternative procedure for
Scheme 4, was completely driven to the side of 4a. Epi- preparing 8a and 8b.
merization during hydrogenolysis of related decalin isox-
Our next efforts focused on the independent synthesis of
3a, 4a, 7a, and 8b, as well as on the synthesis of some aldols
not obtained (or not obtained cleanly) by hydrogenolysis or
ozonolysis (i.e., 3b, 4b, 7b, 8a) from enones 10[9j,16d,20] and
12, as illustrated in Scheme 5. Enones 10 and 12 thus fur-
nished the ene acetals 10a and 12a, respectively, in high
yield, although with use of excess catalyst the deconjugated
isomers 10b and 12b were also obtained. A similar, but re-
versed, isomerization was also observed by Paquette.[20b]
Hydroboration/oxidation of 10a and 12a occurred
mainly from the less hindered convex side as observed pre-
viously (Scheme 1), but with much higher diastereoselectiv-
ity, to furnish 10c and 12c as the major products alongside
10d and 12d. Mild oxidation to the ketones 10e, 12e, 10f,
and 12f went smoothly, followed by dibal-H reduction to
give the corresponding alcohols 10h, 12h/12c, 10g/10d, and
12g/12d in good yields. The high stereoselectivity of the pre-
viously observed reduction (Scheme 1) was seen here only
in the cases of the cis-fused keto acetal 10e and perhaps
12e, but not for the trans-fused diastereomers 10f and 12f.
Nevertheless, the reduction followed the same pattern as
above; that is, hydride transfer took place predominantly
from the less sterically congested side.
azolines is on record.[18a]
Scheme 4. Imine–enamine tautomeric equilibrium affording aldols
3a and 4a.
Unveiling the isoxazolines with O3 (Scheme 3) proved to
be a more stereoselective and reproducible process than hy-
drogenolysis for this type of isoxazolines. Ozonoly-
sis[6j,16c,19b] of 13i thus provided aldol 3a, with spectral
characteristics similar to those observed by Wollenberg,
while isoxazolines 14i and 14j likewise gave the aldols 7a
and 8b, respectively. We know of only one example of an
aldol preparation by unmasking of a hydroazulenic isoxazol-
ine.[6j] All the ozonolysis products were found to have re-
tained the initial stereochemical integrity of the correspond-
ing isoxazolines without any sign of epimerization, but
passage of either 3a or 4a through a column filled with
Mild deacetalization (vide supra) of the hydroxy acetals
neutral silica gel would cause its partial epimerization to afforded the sought aldols. Most gratifyingly, preparation
give an inseparable mixture of 3a/4a ≈ 1:1. Under the same of authentic 8b confirmed the assigned stereochemistry in
Scheme 5. Preparation of aldols 3, 4, 7, and 8.
Eur. J. Org. Chem. 2007, 258–265
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
261

G. G. Tsantali, J. Dimtsas, C. A. Tsoleridis, I. M. Takakis
FULL PAPER
TsOH·H2O (250 mg, 1.31 mmol), and benzene (100 mL) were
heated at reflux with continuous removal of water for 23 h. The
mixture was worked up in the usual fashion (see Supporting Infor-
mation) and purified on a column A (x/y = 20:1) to obtain 9a
isoxazoline 14j, while the results were satisfactory for 4a
and 8a. However, in other cases (3, 4b, 7, and 8b) dehy-
dration was unavoidable (see Exp. Sect.).
Further discussion on these undesirable eliminations is
warranted. If the hydroxy group and its adjacent juncture
hydrogen are syn to each other (syn elimination), the cis-
fused aldols (3b, 7b) are dehydrated more readily than the
corresponding trans-fused epimers (4a, 8a). Dreiding mod-
els indicate that dehydration in the trans-fused aldols, tak-
1
(7.42 g, 81%). H NMR: δ = 1.00 (qd, J = 11.9, J = 4.4 Hz, 1 H),
1.38–1.97 (m, 6 H), 2.14 (m, 1 H), 2.33 (m, 2 H), 2.71 (m, 1 H),
3.84 (m, 1 H), 3.91–4.09 (m, 3 H), 5.58 (m, 1 H) ppm. 13C NMR:
δ = 23.9, 30.5, 31.2, 34.9, 37.1, 45.0, 63.6, 65.3, 107.3, 122.9,
145.4 ppm. IR: ν = 3060, 2925, 1660, 1180, 1042, 932 cm–1. MS
˜
(EI): m/z (%): 180 [M]+ (10), 152 (58), 151 (12), 137 (35), 107 (17),
ing place from the α-side, appears to be more sterically 93 (34), 91 (40), 41 (100). C11H16O2 (180.24) calcd: C 73.30, H 8.95;
found C 72.95, H 8.79.
blocked than in the cis-fused epimers, occurring from the
β-side. If, on the other hand, the aforementioned configura-
tion is anti (anti elimination), the energy of activation re-
quired to reach the transition state is smaller, and elimi-
nation here takes place to a greater extent for both the cis-
(3a, 7a) and the trans-fused (4b, 8b) forms, although it is
still predominant for the cis-fused epimers. Compared to
the previous set of aldols (Scheme 1), elimination was not
a problem except in the case of 5a (anti elimination), where
it occurred, although only to a small extent (10%). Even
so, the yield of 5a was still satisfactory (84%), and chroma-
tographic isolation did not cause any epimerization.
The difference in the ease of dehydration between the two
series of aldols may partly be sought in the thermodynamic
stabilities of the product enones. A priori, it seems that the
types 9 and 11 should be more strained than 10 and 12,
because the former compounds possess double bonds in
their five-membered rings, the latter in their six- and seven-
membered rings. Calculations,[15] shown in Table 1, con-
firmed this hypothesis. In relation to this, we note that some
aldols are not dehydrated at all,[9a,9j,21] while others are only
under vigorous conditions.[9a]
rac-(3ЈS,3aЈS,7aЈS)-Octahydrospiro[1,3-dioxolane-2,4Ј-inden]-3Ј-ol
(9b) and rac-(3ЈR,3aЈR,7aЈS)-Octahydrospiro[1,3-dioxolane-2,4Ј-in-
den]-3Ј-ol (9c): Ene acetal 9a (6.43 g, 35.7 mmol) in anhydrous THF
(50 mL) was hydroborated with BH3·THF (1.0 , 18.0 mL,
18.0 mmol) as described in the literature.[12] The mixture was stirred
at room temp. for 1 h, quenched with water (3.0 mL), and warmed
up to 50 °C, and NaOH (10%, 15 mL) was added, followed by the
addition of H2O2 (35%, 12 mL). After stirring at room temp. for
1 h and the usual workup, the mixture was separated on a col-
umn A (x/y = 10:1, changed to x/y = 5:1 after 5 L had been eluted)
to afford 9b (first fraction, 3.02 g, 43%) and 9c (second fraction,
1.43 g, 20%).
1
Compound 9b: Needles; m.p. 37–39 °C. H NMR: δ = 0.97 (dddd,
J = 13.0, J = 13.0, J = 13.0, J = 3.0 Hz, 1 H), 1.32–1.72 (m, 7 H),
1.82–2.02 (m, 2 H), 2.12–2.27 (m, 2 H), 2.90 (brs, OH), 3.98 (m, 4
H), 4.35 (ddd, J = 8.7, J = 8.7, J = 6.8 Hz, 1 H) ppm. 13C NMR:
δ = 23.0, 28.70, 28.73, 30.6, 31.3, 38.8, 55.0, 64.3, 64.6, 73.7,
111.3 ppm. IR (CHCl ): ν = 3525, 2925, 1161, 1100, 1034,
˜
3
920 cm–1. MS (EI): m/z (%): 199 [M + 1]+ (87), 198 [M]+ (89), 181
(87), 155 (91), 137 (92), 126 (75), 115 (87), 99 (94), 94 (94), 86 (91),
42 (100). C11H18O3 (198.26) calcd: C 66.64, H 9.15; found C 66.38,
H 8.93.
Compound 9c: Off-white semisolid; m.p. 31–33 °C. 1H NMR: δ =
1.02 (m, 1 H), 1.25–1.47 (m, 3 H), 1.48–1.64 (m, 3 H), 1.65–1.86
(m, 4 H), 2.04 (dddd, J = 13.6, J = 8.7, J = 8.7, J = 8.7 Hz, 1 H),
2.27 (brs, OH), 4.01 (m, 4 H), 4.22 (ddd, J = 8.6, J = 8.6, J =
5.4 Hz, 1 H) ppm. 13C NMR: δ = 24.1, 29.2, 31.1, 31.5, 34.8, 41.1,
Theoretical computations[15] (Table 1) are consistent with
previous findings indicating, in general, that cis-hydrind-
anone systems are more stable than trans but also that, in-
versely, trans-hydroazulenone carbocycles are more stable
than the cis forms, with the 7b/8b pair being an exception.
The differences in the calculated stabilities, however, are not
fully justifiable by the 100% completeness of the epimeriza-
tions observed in most cases (i.e., they are too small), sug-
gesting some catalytic action provided by the silica gel
acidic sites.
59.0, 64.2, 65.2, 71.7, 110.6 ppm. IR (CHCl ): ν = 3555, 2920, 1143,
˜
3
1102, 1040, 941 cm–1. MS (EI): m/z (%): 198 [M]+ (89), 181 (59),
155 (97), 137 (81), 126 (56), 115 (97), 99 (96), 94 (46), 86 (82), 41
(100). C11H18O3 (198.26) calcd: C 66.64, H 9.15; found C 66.43, H
9.20.
rac-(3S,3aS,7aS)-3-Hydroxyoctahydro-4H-inden-4-one (1b): Ace-
talol 9b (83 mg, 0.419 mmol), aq. AcOH (50%, 2 mL), and THF
(2 mL) were heated at reflux for 20 min. Purification on a col-
umn C (x/y = 5:1) gave aldol 1b (61 mg, 94%). 1H NMR: δ = 1.20–
1.46 (m, 2 H), 1.53 (m, 1 H), 1.68–1.95 (m, 4 H), 2.07 (m, 1 H),
2.22–2.40 (m, 2 H), 2.50 (dd, J = 5.8, J = 5.5 Hz, 1 H), 2.65 (m, 1
H), 2.79 (brs, OH), 4.50 (q, J = 6.1 Hz, 1 H) ppm. 13C NMR: δ =
In conclusion, we have prepared sixteen dia-
stereomerically pure aldols either by starting the synthesis
from enones 9, 10, 11, and 12 or by unmasking isoxazolines
13i, 14i, and 13j.
Experimental Section
Representative procedures are given as examples. Columns used:
23.1, 28.5, 28.9, 33.3, 40.05, 40.14, 60.8, 74.6, 214.3 ppm. IR: ν =
˜
3418, 2938, 1703, 1461, 1350, 1053, 1018 cm–1. MS (EI): m/z (%):
154 [M]+ (3), 136 (39), 110 (72), 107 (51), 97 (83), 94 (90), 83 (48),
80 (96), 41 (100). C9H14O2 (154.21) calcd: C 70.10, H 9.15; found
C 70.27, H 9.38.
A (85ϫ2.5 cm, filled with 185 g of neutral Merck silica gel, 70–
270 mesh),
B (70ϫ2.0 cm, 82 g), C (46ϫ1.6 cm, 33 g), D
(11ϫ2.0 cm, 11 g). The columns were eluted with petroleum ether
(b.p. 65–69 °C)/ethyl acetate x/y (v:v). Relative ratios of products,
rac-(3aЈS,7aЈS)-Hexahydrospiro[1,3-dioxolane-2,4Ј-inden]-3Ј(3aЈH)-
one (9d): A mixture of pyridinium chlorochromate (PCC),[14]
(3.51 g, 16.3 mmol) and CH2Cl2 (60 mL) was stirred at room temp.
for 15 min and a solution of the hydroxy acetal 9b (2.18 g,
11.0 mmol) in CH2Cl2 (5 mL) was added all at once. The mixture
was further stirred at room temp. for 24 h and chromatographed
1
whenever pertinent, were determined by H NMR integration. All
compounds were obtained as colorless oils. Exceptions to the above
are noted (see also Supporting Information).
1Ј,2Ј,5Ј,6Ј,7Ј,7aЈ-Hexahydrospiro[1,3-dioxolane-2,4Ј-indene]
(9a):
Enone
9
(6.94 g, 51.0 mmol),[9a,9j] ethylene glycol (15 mL),
262
www.eurjoc.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 258–265

Hydroxy-hydrindanones and Hydroxy-hydroazulenones
FULL PAPER
directly (no workup) on a column B (x/y = 5:1) to afford acetalone
(1E)- and (1Z)-3-Cyclohex-2-en-1-ylpropanal Oxime (13h): As de-
9d, (2.10 g, 97%). 1H NMR: δ = 1.32–1.54 (m, 2 H), 1.54–1.79 (m, scribed in a published procedure,[23] enal 13g (3.51 g, 25.4 mmol),
4 H), 1.79–1.94 (m, 1 H), 2.00 (m, 1 H), 2.11–2.39 (m, 2 H), 2.45 hydroxylamine hydrochloride (1.93 g, 27.8 mmol), sodium acetate
(d, J = 7.4 Hz, 1 H), 2.52 (m, 1 H), 3.85–3.97 (m, 4 H) ppm. 2D
trihydrate (4.11 g, 30.2 mmol), water (40 mL), and acetonitrile
1H–1H COSY. 13C NMR: δ = 20.0, 25.2, 26.4, 33.7, 37.3, 37.6, 55.8, (120 mL) were stirred at room temp. for 23 h to afford a ca. 1.1:1
63.9, 65.3, 109.0, 217.4 ppm. 2D 1H–13C COSY. IR: ν = 2941, mixture of (E)/(Z) isomers of 13h (3.73 g, 96%). 1H NMR: δ =
˜
1745, 1156, 1110, 1035, 950 cm–1. MS (EI): m/z (%): 196 [M]+ (15),
1.13–2.16 (m, 19 H), 2.26 (m, 2 H), 2.44 (td, J = 7.9, J = 5.5 Hz,
153 (23), 113 (13), 99 (100), 86 (61). C11H16O3 (196.24) calcd: C 2 H), 5.56 (m, 2 H), 5.69 (m, 2 H), 6.73 [t, J = 5.5 Hz, 1 H, (Z)–
67.32, H 8.22; found C 67.26, H 8.24.
CH=N], 7.44 [t, J = 6.1 Hz, 1 H, (E)–CH=N], 8.49 (br s 1 H,
OH) ppm. 13C NMR: δ = 21.34, 21.36, 22.6, 25.3 (2 C), 27.0, 28.7
(2 C), 32.4, 32.9, 34.6, 34.9, 127.6 (2 C), 131.05, 131.10, 152.3,
rac-(3aЈR,7aЈS)-Hexahydrospiro[1,3-dioxolane-2,4Ј-inden]-3Ј(3aЈH)-
one (9e): Acetalol 9c (806 mg, 4.07 mmol) was oxidized by the
method described by Swern and associates[13] (30 min at –78 °C),
to provide acetalone 9e (773 mg, 97%). White solid; m.p. 83–84 °C.
1H NMR: δ = 1.16 (m, 1 H), 1.34–1.63 (m, 3 H), 1.69–2.15 with
d, J = 13.7 Hz at δ = 1.88 (m, 7 H), 2.29 (m, 1 H), 3.87 (m, 1 H),
4.01 (m, 2 H), 4.29 (m, 1 H) ppm. 13C NMR: δ = 24.0, 27.2, 31.5,
152.9 ppm. IR: ν = 3260, 3108, 3017, 2925, 1648, 1450, 1431, 1314,
˜
1285, 931 cm–1. MS (EI): m/z (%): 154 [M + 1]+ (81), 153 [M]+
(67), 136 (71), 134 (87), 121 (80), 119 (62), 117 (50), 108 (88), 96
(78), 92 (100), 91 (70). C9H15NO (153.22) calcd: C 70.55, H 9.87,
N 9.14; found C 70.76, H 9.99, N 9.11.
37.0, 38.0, 41.6, 60.6, 65.4, 65.7, 108.4, 213.8 ppm. 2D 1H–13
C
rac-(4aS,7aS,7bS)-3,4,4a,5,6,7,7a,7b-Octahydroindeno[1,7-cd]-
isoxazole (13i):[16d] As described in an established procedure,[17]
aldoxime 13h (3.58 g, 23.4 mmol), chloramine-T trihydrate[24]
(7.24 g, 25.7 mmol), and EtOH (450 mL) were heated at reflux for
12 h. Purification on a column A (x/y = 10:1, changed to x/y = 5:1
after 2 L had been eluted), gave the known[16d] isoxazoline 13i
COSY (mixture of 9e + 9d). IR (KBr): ν = 2938, 2888, 1739, 1448,
˜
1359, 1342, 1212, 1179, 1151, 1106, 1053, 1041, 960, 911 cm–1. MS
(EI): m/z (%): 196 [M]+ (16), 153 (100), 133 (9), 113 (13), 109 (22),
99 (21). C11H16O3 (196.24) calcd: C 67.32, H 8.22; found C 67.46,
H 8.30.
1
(2.55 g, 72%). H NMR:[25] δ = 0.86–1.05 (m, 2 H), 1.28 (m, 1 H),
rac-(3ЈR,3aЈS,7aЈS)-Octahydrospiro[1,3-dioxolane-2,4Ј-inden]-3Ј-ol
(9f): A dibal-H solution (1.0  in CH2Cl2, 18.0 mL, 18.0 mmol)
was added slowly by syringe, at –78 °C under anhydrous conditions,
to a solution of the keto acetal 9d (1.75 g, 8.92 mmol) in CH2Cl2
(90 mL). The mixture was stirred for 1 h, allowed to warm to 0 °C
over 2 h, quenched with water (5 mL), and worked up to furnish
the hydroxy acetal 9f diastereoselectively. Purification on a col-
1.52 (m, 1 H), 1.72 (m, 1 H), 1.92–2.11 (m, 2 H), 2.25 (m, 1 H),
2.32–2.52 (m, 3 H), 3.64 (td, J = 8.5, J = 1.0 Hz, 1 H), 4.68 (td, J
1
= 8.7, J = 8.4 Hz, 1 H) ppm. 2D H–1H COSY. 13C NMR:[25] δ =
19.2, 20.4, 27.9, 28.9, 34.2, 36.1, 57.5, 78.4, 172.6 ppm. 2D 1H–13C
COSY. C9H13NO (151.21) calcd: C 71.49, H 8.67, N 9.26; found C
71.26, H 8.93, N 9.11.
1
umn C (x/y = 5:1) afforded 1.43 g (81%). H NMR: δ = 1.30–1.86
rac-(4aS,8aS,8bS)-4,4a,5,6,7,8,8a,8b-Octahydro-3H-azuleno[1,8-
cd]isoxazole (14i)[16] and rac-(4aS,8aR,8bR)-4,4a,5,6,7,8,8a,8b-Oc-
tahydro-3H-azuleno[1,8-cd]isoxazole (14j): These compounds were
prepared from aldoxime 14h (3.26 g, 19.5 mmol), chloramine-T
trihydrate[24] (6.23 g, 22.1 mmol), and EtOH (390 mL) as described
above. Separation on a column A (x/y = 10:1) afforded the
known[16] isoxazoline 14i (2.12 g, 66%) and 14j (77 mg, 2.4%).
(m, 9 H), 1.94 (t, J = 6.9 Hz, 1 H), 2.09 (m, 2 H), 2.42 (d, J =
2.1 Hz, OH), 3.99 (m, 4 H), 4.40 (m, 1 H) ppm. 13C NMR: δ =
22.8, 28.5, 30.5, 32.8, 34.6, 39.0, 51.9, 63.9, 64.5, 73.6, 110.8 ppm.
IR: ν = 3486, 2935, 1109, 1074, 1044, 1020, 930 cm–1. MS (EI): m/z
˜
(%): 198 [M]+ (35), 181 (17), 155 (93), 141 (41), 136 (58), 126 (48),
115 (99), 100 (89), 99 (95), 86 (96), 55 (100). C11H18O3 (198.26)
calcd: C 66.64, H 9.15; found C 66.48, H 9.39.
1
Compound 14i: H NMR: δ = 1.12–2.54 (m, 13 H), 3.81 (dd, J =
3-(2-{2-[(4-Methylphenyl)sulfonyl]hydrazono}cyclohexyl)propyl Ace-
tate (13e): Keto acetate 13d (2.48 g, 12.5 mmol), 4-methylben-
zenesulfonohydrazide (2.39 g, 12.8 mmol), and methanol (30 mL)
were heated at reflux for 4 h. The mixture was cooled and the solid
p-tosylhydrazone derivative 13e was isolated by filtration. The
mother liquor was concentrated and cooled, and a second crop was
isolated (total of 4.48 g, 98%). Recrystallization from EtOH gave
13e as white leaflets; m.p. 123–124 °C. 1H NMR: δ = 1.20–2.50 (m,
19 H) with s at δ = 2.05 and 2.40 ppm, 3.94 (t, J = 6.4 Hz, 2 H),
7.30 (d, J = 8.2 Hz, 2 H), 7.74 (brs, NH), 7.84 (d, J = 8.2 Hz, 2
H) ppm. 13C NMR: δ = 21.0, 21.6, 23.8, 25.9, 26.1, 26.2, 27.4,
33.2, 43.8, 64.6, 128.3, 129.4, 135.4, 143.9, 163.5, 171.2 ppm. IR
11.4, J = 6.8 Hz, 1 H), 4.73 (ddd, J = 11.5, J = 6.8, J = 2.4 Hz, 1
1
H) ppm. 2D H–1H COSY. 13C NMR: δ = 20.1, 23.1, 28.4, 31.0,
31.7, 35.3, 39.3, 61.3, 81.8, 167.6 ppm. 2D 1H–13C COSY.
C10H15NO (165.23) calcd: C 72.69, H 9.15, N 8.48; found C 72.41,
H 9.38, N 8.29.
1
Compound 14j: H NMR: δ = 1.07–1.48 (m, 3 H), 1.55–1.94 (m, 6
H), 2.01–2.23 (m, 2 H), 2.41–2.49 (m, 2 H), 3.35 (t, J = 11.1 Hz, 1
H), 4.67 (td, J = 11.1, J = 5.8 Hz, 1 H) ppm. 2D 1H–1H COSY.
13C NMR: δ = 20.9, 24.7, 30.7, 32.0, 32.5, 33.6, 41.5, 65.3, 81.5,
167.2 ppm. 2D 1H–13C COSY. IR: ν = 1595, 1567, 1469, 1371,
˜
1260, 1220, 1119, 1096, 980, 908 cm–1. C10H15NO (165.23) calcd:
C 72.69, H 9.15, N 8.48; found C 72.95, H 9.01, N 8.53.
(CHCl ): ν = 3280, 3195, 3015, 2920, 1715, 1590, 1440, 1377, 1360,
˜
3
1323, 1243, 1158, 1087, 1030, 1012 cm–1. C18H26N2O4S (366.47)
rac-(3aS,7S,7aR)-7-Hydroxyoctahydro-1H-inden-1-one (3a) and rac-
(3aS,7S,7aS)-7-Hydroxyoctahydro-1H-inden-1-one (4a)
calcd: C 58.99, H 7.15, N 7.64; found C 59.06, H 7.15, N 7.78.
3-Cyclohex-2-en-1-ylpropan-1-ol (13f):[22] As described in a pre-
viously published procedure,[9a] p-tosylhydrazone 13e (4.25 g,
11.6 mmol), MeLi (1.6  in ether, 50 mL, 80 mmol), and TMEDA
(20 mL) in dry THF (120 mL) afforded, after 23 h at room temp.,
A) By Hydrogenolysis of Isoxazoline 13i in the Presence of W-2 Ra-
Ni/B(OH)3: As described in a literature procedure,[19a] isoxazoline
13i (271 mg, 1.79 mmol), boric acid (227 mg, 3.67 mmol), a spatula
tip of W-2 Ra-Ni (ca. 15–20 mg), and MeOH/H2O 5:1 (10 mL)
were stirred under hydrogen for 5 h to furnish a mixture of aldols
the known[22] alkenol 13f, which was purified on a column B (x/y
1
= 10:1), to give 1.61 g (99%). H NMR: δ = 1.16–1.86 (m, 9 H), 3a and 4a (ca. 3:2, 257 mg, 93%). Use of a column B (x/y = 10:1)
1.93–2.14 (m, 3 H), 3.64 (t, J = 6.6 Hz, 2 H), 5.57 (m, 1 H), 5.67
failed on one hand to separate the mixture, while on the other hand
it caused some epimerization (3a/4a ≈ 1:1). The mixture of 3a and
4a obtained above gave enone 10[9j,16d,20] (63%) upon treatment
with methanesulfonyl chloride and 1,5-diazabicyclo[5.4.0]undec-5-
(m, 1 H) ppm. 13C NMR: δ = 21.5, 25.4, 29.1, 30.2, 32.4, 35.0,
63.3, 127.1, 131.8 ppm. IR: ν = 3374, 3016, 2929, 1648, 1449, 1376,
˜
1250, 1057, 1031 cm–1.
Eur. J. Org. Chem. 2007, 258–265
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
263

G. G. Tsantali, J. Dimtsas, C. A. Tsoleridis, I. M. Takakis
FULL PAPER
ene (DBU), as described in the literature.[16d] The same result was
obtained after 3a/4a had been heated at reflux in aq. HCl (5%,
3.0 mL) and THF (5.0 mL) for 15 min (82% yield). In fact, all of
the hydrindene aldols presented in this paper were dehydrated to
10 under the latter conditions, with yields ranging from 75 to 95%,
after purification by column chromatography.
[2]
[3]
a) Y. Hirasawa, H. Morita, M. Shiro, J. Kobayashi, Org. Lett.
2003, 5, 3991–3993; b) C. H. Heathcock, T. A. Blumenkopf,
K. M. Smith, J. Org. Chem. 1989, 54, 1548–1562; c) M. E.
Jung, L. A. Light, J. Am. Chem. Soc. 1984, 106, 7614–7618; d)
D. N. Brattesani, C. H. Heathcock, J. Org. Chem. 1975, 40,
2165–2170; e) W. A. Ayer, B. Altenkirk, Y. Fukazawa, Tetrahe-
dron 1974, 30, 4213–4214.
a) J. Peng, M. A. Avery, M. T. Hamann, Org. Lett. 2003, 5,
4575–4578; b) A.-H. Zhao, S.-H. Li, Q.-S. Zhao, Z.-W. Lin,
H.-D. Sun, Y. Lu, L.-L. Zhang, Q.-T. Zheng, Helv. Chim. Acta
2003, 86, 3470–3475; c) J.-H. Sheu, A. F. Ahmed, R.-T. Shiue,
C.-F. Dai, Y.-H. Kuo, J. Nat. Prod. 2002, 65, 1904–1908; d) J.
Peng, K. Walsh, V. Weedman, J. D. Bergthold, J. Lynch, K. L.
Lieu, I. A. Braude, M. Kelly, M. T. Hamann, Tetrahedron 2002,
58, 7809–7819; e) L. A. Paquette, D. R. Sauer, D. G. Cleary,
M. A. Kinsella, C. M. Blackwell, L. G. Anderson, J. Am.
Chem. Soc. 1992, 114, 7375–7387.
a) A. Arnone, L. Merlini, G. Nasini, O. V. De Pava, F. Zunino,
J. Chem. Soc., Perkin Trans. 1 2001, 610–616; b) M. L. Burgess,
Y. L. Zhang, K. D. Barrow, J. Nat. Prod. 1999, 62, 1542–1544;
c) U. F. Castillo, M. Ojika, M. Alonso-Amelot, Y. Sakagami,
Bioorg. Med. Chem. 1998, 6, 2229–2233; d) A. Padwa, E. A.
Curtis, V. P. Sandanayaka, J. Org. Chem. 1997, 62, 1317–1325;
e) H. Kigoshi, Y. Imamura, K. Mizuta, H. Niwa, K. Yamada,
J. Am. Chem. Soc. 1993, 115, 3056–3065; f) S. Caccamese, V.
Amico, P. Neri, J. Nat. Prod. 1990, 53, 1287–1296; g) M. Ojika,
K. Wakamatsu, H. Niwa, K. Yamada, Tetrahedron 1987, 43,
5261–5274.
B) By Hydrogenolysis of Isoxazoline 13i in the Presence of W-2 Ra-
Ni/AcOH: Under conditions and with reagents identical to those
described by Wollenberg[16d] (except that 1.0 mL of MeOH was
used, instead of 0.5 mL), we obtained mainly starting material. In
a second run, addition of ca. 5 mg of W-2 Ra-Ni (instead of ca.
1 mg) while keeping all other conditions constant, furnished a mix-
ture of both 3a and 4a (88%), with predominance of the latter
(Ͼ70%). In a third run, in which the quantity of W-2 Ra-Ni was
further increased to ca. 15–20 mg, nearly pure 4a (Ͼ95%) was ob-
tained in 90% yield. Column chromatography of pure 4a (column
B, x/y = 10:1) resulted in an epimeric mixture 3a/4a ≈ 1:1.
[4]
C) By Ozonolysis of Isoxazoline 13i: As described in a literature
procedure,[19b] isoxazoline 13i (137 mg, 0.906 mmol), in CH2Cl2/
MeOH (5:1, 25 mL), was subjected to a stream of O3/O2 for 3 h
at –78 °C, stirred for an additional 3 h, and quenched with dimethyl
sulfide. Workup gave pure 3a (101 mg, 72%). Column chromatog-
raphy, however (column B, x/y = 10:1), resulted in an epimeric
mixture 3a/4a ≈ 1:1.
D) By Deacetalization of β-Hydroxy Acetal 10h: A solution of 10h
(71 mg, 0.358 mmol), aq. AcOH (25%, 3.0 mL), and THF (5.0 mL)
was treated as described in the representative procedure (5.0 min at
reflux) to afford a mixture of 10h/10/3a ≈ 1:6:3 (43 mg). Estimated
yields (based on converted starting material): 10 (26 mg, 57%), 3a
(13 mg, 25%).
[5]
a) I. Kuwajima, K. Tanino, Chem. Rev. 2005, 105, 4661–4670
and references cited therein; b) P. Chumkaew, C. Karalai, C.
Ponglimanont, K. Chantrapromma, J. Nat. Prod. 2003, 66,
540–543; c) L.-Y. Wang, N.-L. Wang, X.-S. Yao, S. Miyata, S.
Kitanaka, J. Nat. Prod. 2002, 65, 1246–1251; d) M. J. Chan-
Bacab, L. M. Peña-Rodriguez, Nat. Prod. Rep. 2001, 18, 674–
688; e) W. He, M. Cik, A. Lesage, I. Van der Linden, N.
De Kimpe, G. Appendino, J. Bracke, S. G. Mathenge, F. P. Mu-
dida, J. E. Leysen, L. Van Puyvelde, J. Nat. Prod. 2000, 63,
1185–1187 and references cited therein; f) P. Ramesh, N. S.
Reddy, Y. Venkateswarlu, M. V. R. Reddy, D. J. Faulkner, Tet-
rahedron Lett. 1998, 39, 8217–8220; g) R. G. Powell, D. Weisl-
eder, C. R. Smith Jr, J. Nat. Prod. 1985, 48, 102–107 and refer-
ences cited therein; h) S. M. Kupchan, Y. Shizuri, W. C. Sum-
ner Jr, H. R. Haynes, A. P. Leighton, B. R. Sickles, J. Org.
Chem. 1976, 41, 3850–3853.
E) By Deacetalization of β-Hydroxy Acetal 10d: A solution of 10d
(39 mg, 0.197 mmol), aq. HCl (2.5%, 1.0 mL), and MeOH
(5.0 mL) was stirred at room temp. for 10 h to provide 4a (27 mg,
89%).
Compound 3a: Data similar to those described in the literature,[16d]
with an additional signal in the 13C NMR at δ = 37.6 ppm, missing
1
in the original paper. 2D H–1H COSY (mixture of 3a + 4a). 2D
1H–13C COSY (mixture of 3a + 4a).
[6]
1
a) A. Lhuillier, N. Fabre, E. Cheble, F. Oueida, S. Maurel, A.
Valentin, I. Fourasté, C. Moulis, J. Nat. Prod. 2005, 68, 468–
471; b) G. Appendino, P. Spagliardi, O. Sterner, S. Milligan, J.
Nat. Prod. 2004, 67, 1557–1564; c) F. Xu, T. Morikawa, H.
Matsuda, K. Ninomiya, M. Yoshikawa, J. Nat. Prod. 2004, 67,
569–576; d) S. Glasl, A. Presser, D. Gunbilig, I. Werner, S. Nar-
antuya, E. Haslinger, J. Jurenitsch, W. Kubelka, Phytochemistry
2001, 58, 1189–1194; e) K. Tamemoto, Y. Takaishi, B. Chen,
K. Kawazoe, H. Shibata, T. Higuti, G. Honda, M. Ito, Y.
Takeda, O. K. Kodzhimatov, O. Ashurmetov, Phytochemistry
2001, 58, 763–767; f) Y. Takaya, M. Akasaka, Y. Takeuji, M.-
A. Tanitsu, M. Niwa, Y. Oshima, Tetrahedron 2000, 56, 7679–
7683; g) F. Shimoma, H. Kusaka, H. Azami, K. Wada, T. Su-
zuki, H. Hagiwara, M. Ando, J. Org. Chem. 1998, 63, 3758–
3763; h) A. M. Montaña, K. M. Nicholas, J. Org. Chem. 1990,
55, 1569–1578; i) A. Garcia-Granados, A. Molina, E. Cabrera,
Tetrahedron 1986, 42, 81–87; j) A. P. Kozikowski, B. B. Mugr-
age, B. C. Wang, Z.-B. Xu, Tetrahedron Lett. 1983, 24, 3705–
3708; k) P. A. Grieco, Y. Ohfune, G. F. Majetich, J. Org. Chem.
1983, 48, 360–366 and references cited therein; l) C. H.
Heathcock, C. M. Tice, T. C. Germroth, J. Am. Chem. Soc.
1982, 104, 6081–6091 and references cited therein; m) P. Kok,
N. D. Sinha, P. Sandra, P. J. De Clercq, M. E. Vandewalle, Tet-
rahedron 1982, 38, 2279–2283 and references cited therein; n)
W. Herz, R. Murari, J. F. Blount, J. Org. Chem. 1979, 44, 1873–
1876; o) A. Alexakis, M. J. Chapdelaine, G. H. Posner, A. W.
Compound 4a: H NMR: δ = 1.08–1.38 (m, 3 H), 1.48–1.68 (m, 3
H), 1.68–2.19 (m, 5 H), 2.22–2.53 (m, 1 H), 3.50 (s, 1 H, OH), 3.75
(ddd, J = 9.9, J = 9.2, J = 4.6 Hz, 1 H) ppm. 2D 1H–1H COSY
(mixture of 4a + 3a). 13C NMR: δ = 24.6, 27.3, 31.5, 33.9, 37.3,
41.2, 61.0, 70.3, 220.1 ppm. 2D 1H–13C COSY (mixture of 4a +
3a). IR: ν = 3482, 2915, 1718, 1397, 1164, 1066, 1051, 1007 cm–1.
˜
C9H14O2 (154.21) calcd: C 70.10, H 9.15; found C 69.96, H 8.91.
Supporting Information (see also the footnote on the first page of
this article): Most of the Experimental Section. Two-dimensional
(2D) H–1H COSY and 2D H–13C COSY spectra.
1
1
Acknowledgments
We thank Mr. D. Rigas for obtaining the mass spectra. G. G. T.
thanks the Leonidas Zervas Foundation for a two-year (1994–1996)
scholarship during her Ph.D. work.
[1] a) W. Li, P. L. Fuchs, Org. Lett. 2003, 5, 2849–2852; b) E. S.
Rothman, T. Perlstein, M. E. Wall, J. Org. Chem. 1960, 25,
1966–1968 and references cited therein; c) G. P. Mueller, R. E.
Stobaugh, R. S. Winniford, J. Am. Chem. Soc. 1953, 75, 4888–
4892.
264
www.eurjoc.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 258–265

Hydroxy-hydrindanones and Hydroxy-hydroazulenones
FULL PAPER
Runquist, Tetrahedron Lett. 1978, 19, 4205–4208; p) Y. Kondo,
F. Yoshizaki, F. Hamada, J. Imai, G. Kusano, Tetrahedron Lett.
1977, 18, 2155–2158; q) W. Herz, C. M. Gast, P. S. Subraman-
iam, J. Org. Chem. 1968, 33, 2780–2784 and references cited
therein.
[10]
[11]
a) M. M. M. Rubinger, J. Mann, J. Chem. Res. (S) 1999, 454–
455; b) S. L. Gwaltney II, S. T. Sakata, K. J. Shea, J. Org.
Chem. 1996, 61, 7438–7451; c) S. K. Kim, C. S. Pak, J. Org.
Chem. 1991, 56, 6829–6832; d) G. H. Posner, K. A. Babiak,
G. L. Loomis, W. J. Frazee, R. D. Mittal, I. L. Karle, J. Am.
Chem. Soc. 1980, 102, 7498–7505; e) W. F. Erman, L. C. Stone,
J. Am. Chem. Soc. 1971, 93, 2821–2823.
a) J. J. La Clair, P. T. Lansbury, B.-X. Zhi, K. Hoogsteen, J.
Org. Chem. 1995, 60, 4822–4833; b) J. Wright, G. J. Drtina,
R. A. Roberts, L. A. Paquette, J. Am. Chem. Soc. 1988, 110,
5806–5817.
H. C. Brown, Tetrahedron 1961, 12, 117–138.
A. J. Mancuso, S.-L. Huang, D. Swern, J. Org. Chem. 1978, 43,
2480–2482.
a) G. Piancatelli, A. Scettri, M. D’Auria, Synthesis 1982, 245–
258; b) E. J. Corey, J. W. Suggs, Tetrahedron Lett. 1975, 16,
2647–2650.
[7] a) P. Jankowski, S. Marczak, J. Wicha, Tetrahedron 1998, 54,
12071–12150 and references cited therein; b) M. Tori, M.
Ikawa, T. Sagawa, H. Furuta, M. Sono, Y. Asakawa, Tetrahe-
dron 1996, 52, 9999–10010; c) A. R. Matlin, W. C. Agosta, J.
Chem. Soc., Perkin Trans. 1 1987, 365–368; d) P. E. Peterson,
R. L. Breedlove Leffew, B. L. Jensen, J. Org. Chem. 1986, 51,
1948–1954; e) B. Lo Cicero, F. Weisbuch, G. Dana, J. Org.
Chem. 1981, 46, 914–919 and ref.[8] therein; f) P. W. Concan-
non, J. Ciabattoni, J. Am. Chem. Soc. 1973, 95, 3284–3289 and
references cited therein; g) N. L. Allinger, M. T. Tribble, Tetra-
hedron 1972, 28, 1191–1202 and references cited therein.
[8] a) L. E. Overman, J. P. Wolfe, J. Org. Chem. 2002, 67, 6421–
6429; b) G. L. Lange, C. Gottardo, A. Merica, J. Org. Chem.
1999, 64, 6738–6744; c) J. Castro, A. Moyano, M. A. Pericàs,
A. Riera, J. Org. Chem. 1998, 63, 3346–3351; d) C. Mehta, N.
Krishnamurthy, S. R. Karra, J. Am. Chem. Soc. 1991, 113,
5765–5775; e) L. A. Paquette, Y.-J. Shi, J. Am. Chem. Soc. 1990,
112, 8478–8489; f) M. Sworin, K.-C. Lin, J. Am. Chem. Soc.
1989, 111, 1815–1825; g) H. O. House, G. S. Nomura, D. Van-
Derveer, J. Org. Chem. 1986, 51, 2416–2423 and references
cited therein; h) J. H. Rigby, J. Z. Wilson, J. Am. Chem. Soc.
1984, 106, 8217–8224 and references cited therein; i) S. E. Den-
mark, T. K. Jones, J. Am. Chem. Soc. 1982, 104, 2642–2645; j)
T. Weller, D. Seebach, R. E. Davis, B. B. Laird, Helv. Chim.
Acta 1981, 64, 736–760; k) R. M. Coates, R. L. Sowerby, J.
Am. Chem. Soc. 1972, 94, 5386–5396; l) J. A. Marshall, W. F.
Huffman, J. A. Ruth, J. Am. Chem. Soc. 1972, 94, 4691–4696
and ref.[6] therein.
[9] a) G. G. Tsantali, I. M. Takakis, J. Org. Chem. 2003, 68, 6455–
6458; b) K. Schellhaas, H.-G. Schmalz, J. W. Bats, Chem. Eur.
J. 1998, 4, 57–66; c) E. Piers, R. M. Oballa, J. Org. Chem. 1996,
61, 8439–8447; d) J. Cossy, S. BouzBouz, Tetrahedron Lett.
1996, 37, 5091–5094; e) T. Ohkubo, H. Akino, M. Asaoka, H.
Takei, Tetrahedron Lett. 1995, 36, 3365–3368 and ref.[4] therein;
f) L. A. Paquette, X. Wang, J. Org. Chem. 1994, 59, 2052–2057;
g) A. E. Greene, A. A. Serra, E. J. Barreiro, P. R. R. Costa, J.
Org. Chem. 1987, 52, 1169–1170; h) R. A. Galemmo Jr, L. A.
Paquette, J. Org. Chem. 1985, 50, 1768–1770; i) B. B. Snider,
W. C. Faith, J. Am. Chem. Soc. 1984, 106, 1443–1445; j) S. A.
Bal, A. Marfat, P. Helquist, J. Org. Chem. 1982, 47, 5045–5050.
[12]
[13]
[14]
[15]
[16]
Mopac2000 ver. 1.11, Fujitsu.
a) D. Stanssens, D. De Keukeleire, M. Vandewalle, Tetrahe-
dron: Asymmetry 1990, 1, 547–560; b) D. P. Curran, P. B. Ja-
cobs, Tetrahedron Lett. 1985, 26, 2031–2034; c) A. P. Kozikow-
ski, Acc. Chem. Res. 1984, 17, 410–416 and references cited
therein; d) R. H. Wollenberg, J. E. Goldstein, Synthesis 1980,
757–758 and ref.[6] therein.
[17]
A. Hassner, K. M. L. Rai, Synthesis 1989, 57–59.
[18] a) A. P. Kozikowski, C.-S. Li, J. Org. Chem. 1987, 52, 3541–
3552; b) S. F. Martin, B. Dupre, Tetrahedron Lett. 1983, 24,
1337–1340.
[19] a) D. P. Curran, J. Am. Chem. Soc. 1983, 105, 5826–5833; b)
A. P. Kozikowski, M. Adamczyk, Tetrahedron Lett. 1982, 23,
3123–3126.
[20] a) L. A. Paquette, W. E. Fristad, D. S. Dime, T. R. Bailey, J.
Org. Chem. 1980, 45, 3017–3028; b) L. A. Paquette, R. P. Hen-
zel, R. F. Eizember, J. Org. Chem. 1973, 38, 3257–3268.
[21] W. C. Agosta, S. Wolff, J. Org. Chem. 1975, 40, 1699–1701.
[22] P. K. Claus, F. W. Vierhapper, J. Org. Chem. 1977, 42, 4016–
4023.
[23] R. Grigg, J. Markandu, T. Perrior, S. Surendrakumar, W. J.
Warnock, Tetrahedron 1992, 48, 6929–6952.
[24] Sodium chloro[(4-methylphenyl)sulfonyl]azanide.
[25] There are some differences between our NMR spectra and
those reported.[16d]
Received: July 22, 2006
Published Online: October 31, 2006
Eur. J. Org. Chem. 2007, 258–265
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
265