Synthesis and transformations of new annulated pyranosides using the Pauson-Khand reaction

Article abstract of DOI:10.1016/S0008-6215(01)00211-7

The synthesis and transformations of new annulated pyranosides are described. These adducts were prepared by Pauson-Khand reaction on differently functionalized prop-2-ynyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosides (1-8). Compound 1 with a free hydroxyl group at C-4 afforded significant amounts of the hydrogenolysis product 12 in addition to the normal adduct 13. The C-4 O-protected similar precursors (2-8) gave PK products in yields ranging from 39 to 63%. Pauson-Khand adduct 19 provided intermediate 23 after selective manipulation. The oxidation plus decarbonylation synthetic sequence applied to intermediate 23 gave a poor yield of compound 24 using Wilkinson's catalyst. The t-butyl hydroperoxide promoted decarbonylation of product 23 afforded formate 25 in a typical Baeyer-Villiger rearrangement. The Ferrier-II reaction on intermediate 45, readily available from compound 9, afforded the hydrindane-type derivative 46 in 34% yield using a Ferrier-II type reaction.

Full text of DOI:10.1016/S0008-6215(01)00211-7

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Carbohydrate Research 335 (2001) 71–90
Synthesis and transformations of new annulated
pyranosides using the Pauson–Khand reaction
Jose´ Marco-Contelles,* Juliana Ruiz-Caro
Laboratorio de Radicales Libres (CSIC), Instituto de Qu´ımica Organica General, C/Juan de la Cier6a 3,
ES-28006 Madrid, Spain
Received 21 May 2001; accepted 17 June 2001
Abstract
The synthesis and transformations of new annulated pyranosides are described. These adducts were prepared by
Pauson–Khand reaction on differently functionalized prop-2-ynyl-2,3-dideoxy-a- -erythro-hex-2-enopyranosides
D
(1–8). Compound 1 with a free hydroxyl group at C-4 afforded significant amounts of the hydrogenolysis product
12 in addition to the normal adduct 13. The C-4 O-protected similar precursors (2–8) gave PK products in yields
ranging from 39 to 63%. Pauson–Khand adduct 19 provided intermediate 23 after selective manipulation. The
oxidation plus decarbonylation synthetic sequence applied to intermediate 23 gave a poor yield of compound 24
using Wilkinson’s catalyst. The t-butyl hydroperoxide promoted decarbonylation of product 23 afforded formate 25
in a typical Baeyer–Villiger rearrangement. The Ferrier-II reaction on intermediate 45, readily available from
compound 9, afforded the hydrindane-type derivative 46 in 34% yield using a Ferrier-II type reaction. © 2001
Elsevier Science Ltd. All rights reserved.
Keywords: Annulated pyranosides; Pauson–Khand reaction; Carbocycles by Ferrier-II reaction; Hanessian–Hullar transforma-
tion
1. Introduction
ton (A) (Scheme 1), whose careful and con-
trolled transformation has afforded adducts of
type (B).6–9 These compounds are promising
candidates for the synthesis of molecules with
the cyclopenta[c]pyran skeleton (C) found in
Previous studies in our laboratory have
been concerned with the development of new
synthetic routes to polycyclic hydrocarbons
from carbohydrates via free radical cyclization
strategies.1,2 Simultaneously we have examined
the preparation of annulated pyranosides via
Pauson–Khand (PK) reaction3–5 on prop-2-
ynyl-2,3-dideoxy-a- -erythro-hex-2-enopyran-
D
osides. This protocol has resulted in the
synthesis of a series of molecules with the
perhydro 1,7-dioxacyclopent[cd]indene skele-
* Corresponding author. Tel.: +34-91-5622900; fax: +34-
91-5644853.
E-mail address: iqoc21@iqog.csic.es (J. Marco-Contelles).
Scheme 1. Possible synthetic strategies for the transformation
of adducts of type B.
0008-6215/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0008-6215(01)00211-7

72
J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
2. Results and discussion
In order to implement the oxidation and
decarbonylation strategy for the synthesis of
compounds of type C from products with
structure B (Scheme 1), we designed precur-
sors (1–4) (Scheme 2) with protecting groups
at the primary hydroxyl group after which the
PK reaction could be easily removed in order
to attack the oxidation and the decarbonyla-
tion protocol.
The synthesis of precursor 113 was accom-
plished in high yield by using standard silyla-
tion conditions from known diol 118 (Scheme
4) prepared from 3,4,6-tri-O-acetyl-1,5-anhy-
dro-2-deoxy-arabino-hex-1-enitol tri-O-acetyl-
D
-glucal (10).
Scheme 2. Precursors for the Pauson–Khand reaction.
All new compounds showed excellent ana-
lytical and spectroscopic values (see Tables 1
1
and 2 for the H and 13C NMR data of
compounds 2–8, 26, 27 and 29).
The PK reaction of substrate 1 afforded a
mixture of compounds 12 and 1313 in low
combined chemical yield (Scheme 4). Com-
pound 12 was isolated as a diastereomerically
pure a anomer and the absolute configuration
at C-1 was established in its derivative 14 by
Scheme 3. Precursor for the Hanessian–Hullar reaction.
the natural products known as iridoids,10 and
for the synthesis of the biologically interesting
hydrindanes (E).11
In this paper we describe our results on the
oxidation and decarbonylation strategy for
the synthesis of compounds of type C from
conveniently functionalized intermediates (B),
and the synthesis of compounds of type E
from annulated pyranosides of type D via
Ferrier-II reaction.12
1
analysis of the H NMR spectrum which
showed an nOe effect between proton H-1 (a
broad singlet at 6.18 ppm) and H-7a (3.46
ppm, br d, J7a,4a 6.0 Hz). Consequently,
product 12 is the product of the partial hy-
drogenolysis of the OꢀC(2) bond in product
13, with retention of the configuration at C-
7a. This is a rather unusual reactivity on PK
reactions, already reported by Russian re-
searchers,14 that we have also occasionally
observed in other prop-2-ynyl-2,3-dideoxy-a-
Critical to this approach is the success of
the cobalt-promoted cycloannulation of pre-
cursors 1–8 (Scheme 2) and the selective ma-
nipulation of PK adduct 9 (Scheme 3).9
D
-erythro-hex-2-enopyranosides with a free
hydroxyl group at C-4.8
Scheme 4. Synthesis and Pauson–Khand reaction of precursor 1. Reagents: (a) ClTBDMS, imidazole, DMAP, CH2Cl2; (b) (i)
Co2(CO)8; (ii) NMO·H2O; (c) Ac2O, py, rt.

Table 1
1H NMR (300 MHz, CDCl3) data (l) for 2,3-dideoxy-a-
D
-erythro-2-hex-2-enopyranosides (2–8, 26–29)
H-5 H-6 H-6%
5.29, dm, J4,5 3.93, ddd, J5,6 3.77, dd, J6,6 3.72, dd
H-1
H-2
H-3
H-4
H-7
H-7%
H-9
OSiMe2CMe3
0.07, 0.91
2
3
4
5
6
7
8
5.23, br s
5.17, br s
5.23, m
5.27, br s
5.32, s
5.92, br d,
J2,3 10.3
6.06, br d,
J2,3 10.2
6.13, br d,
J2,3 10.3
5.90–5.79
5.87, dt,
J
5.75, dt,
J
4.32, d, J7,9
2.3
4.30, d, J7,9
2.3
4.34, d, J7,9
2.4
4.50, dd, J7,7% 4.41, dd, J7%,9 2.48, t
15.8, J7,9 2.4 2.4
2.44, t
2.42, t
2.46, t
1,3=J3,4 2.2 9.5
5.3, J5,6% 2.7
11.4
4.15, dd, J4,5 3.88–3.73, m
1,3=J3,4 2.2 9.5
5.81, ddd, J1,3 4.11, dd, J4,5 3.97–3.72, m
0.08, 0.90
0.14, 0.97
2.6, J3,4 1.7
8.6
/
5.17, dm, J4,5 3.90, dt, J5,6
3.40, dd, J6,6% 3.17, dd
9.0
9.0, J5,6% 2.4
10.9
5.97, dt, J2,3 5.86, ddd, J1,3 5.44, dq, J4,5 4.08, dt, J5,6
3.45, dd, J6,6% 3.23, dd
4.52, dd, J7,7% 4.45, dd, J7%,9 2.48, t
15.6, J7,9 2.4 2.4
4.30, d, J7,9
10.2, J 1.1
6.14, br d,
J2,3 10.3
6.06, br d,
J2,3 10.3
2.0, J3,4 2.7
5.78, dt,
J
5.77, dt,
J
9.0, J 1.6
9.0, J5,6% 2.5
10.8
5.20, m
5.22, br s
4.12, dm, J4,5 3.87, ddd, J5,6 3.88, dd, J6,6% 3.77, dd
5.1, J5,6% 2.6 12.6
3.90, dq, J4,5 3.70, ddd, J5,6 3.55, dd, J6,6% 3.27, dd
1,3=J3,4 2.0 9.0, J 2.0 7.3, J5,6% 2.4 10.6
5.70, dt, 4.17–4.10, m 3.78, ddd, J5,6 4.31, dd, J6,6% 4.25, dd
1,3=J3,4 2.5
2.46, t
1,3=J3,4 2.0 8.9
2.4
4.44, dd, J7,7% 4.37, dd, J7%,9 2.44, t
15.7, J7,9 2.4 2.4
4.18, d, J7,9
3
26 5.09, br s
5.94, br d,
J2,3 10.2
2.41, t
J
4.7, J5,6% 2.4,
J4,5 9.5
11.1
2.4
(
27 5.14, m
29 5.21, m
5.85, br d,
J2,3 10.3
5.98, br d,
J2,3 10.2
5.77, dt, J1,3
1.8, J3,4 2.6
5.84, dt,
5.18, dq, J4,5 4.18–4.02, m
9.4, J 1.5
5.43, dq, J4,5 4.25–4.10, m
4.20, d, J7,9
2.4
4.27, d, J7,9
2.4
2.43, t
2.46, t
7
9
J1,3=J3,4 2.1 11.1, J 1.7

74
J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
Table 2
13C NMR (75 MHz, CDCl3) data (l) for 2,3-dideoxy-a-
D-erythro-2-hex-2-enopyranosides (2–8, 26–29)
C-1
C-2
C-3
C-4
C-5
C-6
C-7
C-8
C-9
OSi(Me)2C(Me)3
2
3
4
5
6
7
8
26
27
29
92.3
92.4
92.4
92.7
92.6
92.9
92.8
92.6
92.4
92.6
129.9
132.3
131.2
129.4
129.4
131.1
130.2
133.4
129.3
129.3
127.3
125.9
126.1
127.5
127.5
125.9
126.3
125.8
127.2
127.4
65.5
69.5
70.2
69.6
69.7
70.1
74.5
63.1
64.9
65.3
69.8
70.9
70.8
69.1
69.1
70.0
69.4
70.0
66.9
67.2
62.6
62.4
62.6
5.1
5.3
62.1
7.3
69.0
68.2
58.3
54.7
54.5
54.4
55.4
55.3
54.9
55.1
54.9
55.0
55.2
79.2
79.4
79.4
79.1
79.0
79.4
79.3
79.1
68.2
79.0
74.1
74.3
74.3
74.9
75.0
74.6
74.7
74.7
74.8
74.9
25.9, 18.4, −5.4, −5.5
25.8, 18.3, −5.3, −5.4
25.9, 18.3, −5.4, −5.3
Scheme 5. Synthesis and Pauson–Khand reaction of precursor 2. Reagents: (a) Ac2O, py, rt; (b) (i) Co2(CO)8; (ii) NMO·H2O; (c)
DIBALH, −78 °C, toluene.
Scheme 6. Synthesis and Pauson–Khand reaction of precursor 3. Reagents: (a) MOMCl, NaH, DMF, rt; (b) (i) Co2(CO)8; (ii)
NMO·H2O; (c) DIBALH, −78 °C, toluene.
of ketone 17 in toluene afforded alcohol 18 in
moderate yield.8
Prompted by this unsatisfactory result, we
prepared a series of 4-O-protected enyne pre-
cursors. Acetylation of alcohol 1 gave 2 {1H
Compound 1 was transformed into precur-
sor 4 {1H NMR: (l) [OCH2 (4.70/4.58, d, d, J
13
NMR: (l) [(OCOCH3 (2.07, s); C NMR: (l)
13
11.6 Hz) C6H5 (7.43–7.29, m)]; C NMR: (l)
[OCO (170.3) CH3 (21.0)]} (Scheme 5). The
PK reaction on this molecule provided enone
15 in good yield. This product was identical to
the compound previously isolated after acety-
lation of compound 13 (Scheme 4). The
DIBALH-mediated reduction of ketone 15
gave diol 16 in moderate yield, but with high
stereoselectivity, as only one isomer at C-4
was detected.8
[OCH2 (70.7) C6H5 (138.1–127.6)]} by stan-
dard O-benzylation conditions. Subsequent
PK reaction to give ketone 19 followed by
DIBALH reduction and benzoylation of alco-
hol 20 afforded benzoate 21, whose final desi-
lylation gave free primary alcohol 22 in
satisfactory yield (Scheme 7).
The oxidation of alcohol 22 using the
Dess–Martin method15 gave the aldehyde 23
in good yield (83%) (Scheme 8). This com-
pound was isolated as a mixture of isomers in
a 2:1 ratio which, without separation, were
submitted to decarbonylation16 using the
Wilkinson’s catalyst,17–19 to give compound 24
The synthesis of compound 3 {1H NMR:
(l) [CH3 (3.39) OCH2 (4.73/4.69, d, d, J 7.0
Hz]; 13C NMR: (l) [CH3 (55.6) OCH2
(96.3)O)]} from precursor 1, and the subse-
quent PK reaction have been carried out as
shown in Scheme 6. The DIBALH reduction

J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
75
mixture of epimeric aldehydes 23 is the result
of a Baeyer–Villiger reaction mediated by t-
butyl hydroperoxide with retention of the
configuration at C-6.21
In order to implement the strategy for the
synthesis of compounds E via intermediates D
from compounds of type B (Scheme 1), three
possibilities were faced for the synthesis of
suitable iodide or bromide precursors: (i)
Sodium iodide reaction with C-6ꢀO-tosyl,
prop-2-ynyl-2,3-dideoxy-a- -erythro-hex-2-
D
Scheme 7. Synthesis and Pauson–Khand reaction of precur-
sor 4. Reagents: (a) NaH, BnBr, Bu4NF, THF; (b) (i)
Co2(CO)8; (ii) NMO·H2O; (c) DIBALH, −78 °C, toluene; (d)
ClBz, py, rt; (e) Bu4NF, THF.
enopyranosides, followed by PK reaction; (ii)
the direct iodination of free C-6 hydroxy,
prop-2-ynyl-2,3-dideoxy-a- -erythro-hex-2-
D
enopyranosides, followed by PK reaction; and
(iii) the Hanessian–Hullar (HH) transforma-
22
tion on benzylidene derivatives.
In order to explore the first alternative, we
prepared iodide 5 {1H NMR: (l) [OCOCH3
(2.11, s)]; 13C NMR: (l) [OCO (170.2) CH3
(21.0)]} from diol 118 via intermediates 26 {1H
NMR: (l) [CH3 (2.42, s) C6H4 (7.79/7.33, d, d,
J 8.5 Hz) OSO2]; 13C NMR: (l) [(CH3 (21.6)
C6H4 (145.0–127.9) OSO2)]} and 27 {1H
NMR: (l) [CH3 (2.43, s) C6H4 (7.77/7.33, d, d,
Scheme 8. Oxidation of compound 22 and decarbonylation of
intermediate 23. Reagents: (a) Dess–Martin; (b) RhCl(PPh3)3,
toluene, rt; (c) t-Bu2O2, toluene, 110 °C.
13
J 8.3 Hz) OSO2; OCOCH3 (1.99)]; C NMR:
(l) [(CH3 (21.6) C6H4 (144.9–128.0) OSO2);
OCO (170.0) CH3 (20.8)]}, as shown in
Scheme 9. The PK reaction of precursor 5
afforded compound 28 in 44% yield.
in poor yield (6%). Reaction of 23 with t-butyl
hydroperoxide20 afforded the formate 25 in
17% yield. In the NMR spectra, we could
detect a singlet at 8.05 ppm for HC(O)O and
a signal at 160.1 ppm for HC(O)O. The abso-
lute configuration at C-6 was tentatively as-
A similar protocol starting from tosylate 26
afforded intermediate 29 {1H NMR: (l) [CH3
(2.31, s) C6H4 (7.73/7.20, d, d, J 8.3 Hz)
1
13
signed as R by inspection of the H NMR
OSO2; OCOC6H5 (7.91–7.43)]; C NMR: (l)
spectrum which showed proton H-6 at 6.35
ppm as a doublet with a vicinal coupling
constant (6.7 Hz) for an axial–equatorial ar-
rangement of protons H-6 and H-5. A clear
nOe effect between these protons confirmed
this assignment. The formation of the
diastereomerically pure formate 25 from the
[(CH3 (21.6) C6H4 (144.9–128.0) OSO2; OCO
(165.4) C6H5 (144.9–128.4)]}, which was
transformed into precursor 6 {1H NMR: (l)
[OCOC6H5 (8.02–7.45, m)]; 13C NMR: (l)
[OCO (165.6) C6H5 (133.5–128.4)]}, whose
PK reaction gave adduct 30 in 55% yield
(Scheme 10).
Scheme 9. Synthesis and Pauson–Khand reaction of precursor 5. Reagents: (a) ClTs, py; (b) Ac2O, py, rt; (c) NaI, DMF; (d) (i)
Co2(CO)8; (ii) NMO·H2O.

76
J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
Scheme 10. Synthesis and Pauson–Khand reaction of precursor 6. Reagents: (a) ClBz, py; (b) NaI, DMF; (c) (i) Co2(CO)8; (ii)
NMO·H2O.
scribed by Chre´tien (sodium hydride in
DMF),25 but a complex reaction resulted. The
use of silver fluoride23 for the same purpose
gave a mixture of product 44 (18%) and the
desired molecule 45 in very poor yield (3%).
The use of iodide 43 in the same experimental
conditions gave enol-ether 45 in 30% yield
(Scheme 15). The reaction of this compound
with mercuric chloride in acetone at reflux12
We used this intermediate for the synthesis
of a suitable Ferrier-II reaction precursor as
follows. The reaction of compound 30 with
DIBALH followed by benzoylation of alcohol
31 gave iodide 32. The reaction of this com-
pound with silver fluoride23 in pyridine did not
afford the desired enol-ether, but the unex-
pected perbenzoate 33 (Scheme 11).
In view of this result, we prepared the
analogous intermediate 37 (Scheme 13) from
precursor 8 (Scheme 1) as follows. Desilyla-
tion (90%) of compound 4 gave alcohol 7 {1H
NMR: (l) [OCH2 (4.69/4.56, d, d, J 11.6 Hz)
C6H5 (7.48–7.27, m), OH (2.11, br s)]; 13C
NMR: (l) [OCH2 (71.0) C6H5 (137.8–127.8)]}
(Scheme 12). The PK reaction of precursor 7
afforded adduct 34 in 47% yield.
1
gave compound 46 in 34% yield. In the H
NMR spectrum of compound 46, we could
observe signals for
a
methylene group
[C(6)H2] at 2.93 and 2.84 ppm, as doublets of
doublets, a signal at 4.52–4.49 ppm for
HꢀC(7)ꢀOH (m) and H-7a, at 3.37 ppm show-
ing a vicinal coupling constant with H-7 equal
to 4.0 Hz, a typical value for an axial–equato-
rial orientation of protons, suggesting that the
Iodination of 7 under Garegg’s conditions24
provided compound 8 {1H NMR: (l) [OCH2
(4.69/4.54, d, d, J 11.6 Hz) C6H5 (7.39–7.30,
m)]; 13C NMR: (l) [OCH2 (70.9) C6H5
(137.5–127.9)]} (Scheme 12), whose PK reac-
tion gave adduct 35 in 55% yield (Scheme 13).
Unfortunately, the benzoylated derivative 37,
prepared from the alcohol 36, afforded the
useless derivative 38, under silver fluoride
reaction.23
13
hydroxyl group at C-7 is a located. In the C
Finally, we tested the benzylidene approach.
We started with precursor 9 (Scheme 3), a
compound recently described by us.9 Hydroly-
sis with methanol in mild acid conditions gave
the intermediate 39 (71% yield) and the fully
deprotected tetrol 40 (11%). Diol 39 gave per-
benzoate 41 in convenient chemical yield. All
these compounds showed excellent analytical
and spectroscopic data, in good agreement
with these structures (Scheme 14).
Scheme 11. Reduction of intermediate 30. Reagents: (a)
DIBALH, −78 °C, THF; (b) ClBz, py, rt; (c) AgF, py,
100 °C.
The HH reaction of compound 41 gave the
expected benzoate/bromide 42 in moderate
yield (Scheme 15). We then submitted ben-
zoate 42 to the elimination conditions de-
Scheme 12. Synthesis and PK reaction of precursor 7.
Reagents: (a) Bu4NF, THF; (b) I2, Ph3P, imidazole, (c) (i)
Co2(CO)8; (ii) NMO·H2O.

J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
77
Scheme 13. Pauson–Khand reaction of precursor 8. Reagents: (a) (i) Co2(CO)8; (ii) NMO·H2O; (b) DIBALH, −78 °C, toluene;
(c) ClBz, py; (d) AgF, py.
Scheme 14. Transformations of precursor 9. Reagents: (a) MeOH, p-TsOH; (b) (from 39) ClBz, py, rt.
Scheme 15. Synthesis and Ferrier-II reaction of intermediate 45. Reagents: (a) NBS, BaCO3, CCl4; (b) NaI, ethylmethylketone;
(c) AgF, py [from 42:44 (18%) and 45 (3%); from 43:44 (19%) and 45 (30%)]; (d) (from 45) HgCl2, acetone, reflux; (e) Ac2O, py,
rt.
NMR spectrum, we observed signals for CO
(201.7 ppm), C-6 (42.6 ppm) and C-7 (68.4
ppm). The formation of product 46 is note-
worthy because this is the first example of a
Ferrier-II type reaction on a cyclopentanean-
nulated methyl 5,6-enopyranoside.
In summary, we conclude that the synthesis
of hydrindene derivatives from carbohydrates
following the HH protocol plus Ferrier-II re-
action is possible, but the yields were low.
Work is now in progress in our laboratory in
order to improve these results, and will be
reported in due course.
3. Experimental
General methods.—Reactions were moni-
tored by TLC using precoated silica gel alu-
minum plates containing
a
fluorescent
indicator (E. Merck, 5539). Detection was
done by UV (254 nm) followed by charring
with H2SO4–AcOH spray, 1% aq KMnO4 so-
lution or 0.5% phosphomolybdic acid in 95%
EtOH. Anhydrous Na2SO4 was used to dry
organic solutions during work-ups and the
removal of solvents was carried out under
vacuum with a rotary evaporator. Flash-

78
J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
column chromatography was performed using
Silica Gel 60 (230–400 mesh, E. Merck) and
hexane–EtOAc mixtures as eluent unless oth-
(0.14 M) and treated with tetrabutylammo-
nium fluoride (3 equiv) at rt for 24 h. The
solvent was eliminated and the residue submit-
ted to chromatography to give the product.
General method for the synthesis of iodides
from tosylates/bromides.—The compound was
dissolved in dry DMF, treated with NaI (12
equiv) and warmed at 80 °C for 6 h. The
mixture was diluted with EtOAc, washed with
a 10% aq sodium thiosulfate solution and
brine. The organic layer was dried, filtered,
evaporated and the residue was submitted to
chromatography.
General method for the iodination of alco-
hols.—To a solution of the alcohol in dry
toluene, triphenylphosphine (3 equiv), imida-
zole (3 equiv) and iodine (2 equiv) were added,
and the mixture was heated at reflux for 10
min. Then, the mixture was diluted with an aq
satd NaHCO3 solution and a 5% aq Na2S2O3
solution. The organic layer was dried, filtered
and evaporated. The residue was submitted to
chromatography.
General method for tosylation.—The com-
pound, dissolved in dry pyridine, cooled in an
ice bath, under Ar, was treated with p-tolue-
nesulfonyl chloride (1.1 equiv) and a catalytic
amount of DMAP. The mixture was stirred
for 6 h until complete reaction. The solvent
was removed and the residue was dissolved in
EtOAc, washed with brine, dried, filtered,
evaporated, and the residue was submitted to
chromatography.
General method for acetal mediated acid hy-
drolysis.—The compound was dissolved in
MeOH (0.093 M), cooled at −78 °C and
treated with p-TsOH (cat.). The reaction was
warmed at 0 °C, and after complete reaction,
solid NaHCO3 was added, the suspension was
filtered, the solvent was eliminated and the
residue was submitted to chromatography.
General method for O-benzylation.—The
compound, dissolved in dry THF or DMF
(0.2 M), under Ar and at 0 °C, was treated
with sodium hydride (1.5 equiv, 60% disper-
sion in oil), a catalytic amount of tetra-
butylammonium iodide and BnBr (1.1 equiv).
After stirring at rt for 15 h, the reaction was
complete and some drops of AcOH were
added. Then the mass was filtered over Celite.
The solvent was evaporated, diluted with wa-
1
erwise stated. H spectra were recorded with a
Varian VXR-300(400)S spectrometers, using
13
tetramethylsilane as internal standard and C
NMR spectra were recorded with a Bruker
WP-200-SY. Values with (*) can be
interchanged.
General method for the Pauson–Khand reac-
tion.—To a solution of the corresponding pre-
cursor in dry CH2Cl2 (0.025 M), under Ar and
at rt, Co2CO8 (1.1 equiv) was added and the
mixture was stirred until complete reaction
(ꢀ30 min). Then the mixture was cooled at
0 °C and commercially available NMO·H2O
(6.3 equiv) was added in one pot. After 3 h at
rt, the crude was filtered over Celite 545,
washed with CH2Cl2, and the solvent was
evaporated under diminished pressure. The
residue was purified by flash chromatography
eluting with hexane–EtOAc mixtures.
General method for acetylation.—The com-
pound was treated with a mixture of 1:1
Ac2O–pyridine at rt overnight. The solvent
was evaporated and the residue was submitted
to chromatography.
General method for benzoylation.—The
compound was dissolved in dry pyridine (0.1
M), cooled in an ice bath, under Ar and
stirring. Recently distilled BzCl (1.1 equiv)
was slowly added. The mixture was stirred at
rt overnight. The solvent was evaporated and
the residue was diluted with EtOAc, washed
with diluted HCl, brine, dried, filtered, evapo-
rated, and the residue was submitted to
chromatography.
General method for oxidation (Dess–Mar-
tin).—To a solution of the alcohol, in dry
CH2Cl2 (0.28 M), a commercially available
solution of the Dess–Martin reagent (1.1
equiv) in CH2Cl2 (0.06 M) was added, and the
mixture was stirred at rt for 6 h. Then the
reaction was diluted with Et2O and aq NaOH
(1.3 M) was incorporated. The mixture was
stirred for 10 min, and the organic phase was
separated, washed with brine, dried, filtered,
evaporated, and the residue was submitted to
chromatography.
General method for desilylation reactions.—
The compound was dissolved in dry THF

J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
79
Pauson–Khand reaction of precursor 1.—
Following the ‘General method for the Pau-
son–Khand reaction’ , enyne 1 (170 mg, 0.57
mmol) afforded products 12 (10 mg, 5%) and
13 (28 mg, 15%) after chromatography (from
hexane to 3/2 hexane–EtOAc). Following the
‘General method for acetylation’, 12 (3 mg,
0.009 mmol), gave product (1R,3R,4S,
4aS,7aS)-1,4-bis-acetoxy-3-[((1,1-dimethyl-
ethyl)dimethylsilyloxy)methyl] - 7 - methyl - 3,4,
4a,7a - tetrahydro - cyclopenta[c]pyran - 5(1H)-
one (14, 3 mg, 90%) after chromatography
(17:3 hexane–EtOAc): oil; [h]2D5 +5° (c 0.06,
CHCl3); IR (film) w 2930, 2857, 1747, 1700,
ter, extracted with CH2Cl2 several times, and
washed with brine. The organic layer was
dried, filtered, and evaporated. Flash chro-
matography gave the benzylated compound.
General method for the reduction with
DIBALH.—The ketone was dissolved in dry
THF or in toluene (0.092 M) and cooled at
−78 °C under Ar. DIBALH (1.1 equiv, 1.0 M
in toluene) was added and stirred at this tem-
perature. After 3 h, more DIBALH (1.9 equiv)
was added. When the reaction was complete
(TLC), MeOH was added to destroy the ex-
cess of reagent and the mixture was warmed
at rt. The suspension was filtered, washed with
toluene and evaporated. The crude reaction
mixture was submitted to chromatography.
General method for the elimination of halides
(Br/I) with AgF.—To a solution of the com-
pound in dry pyridine (0.15 M), AgF (1.5
equiv) was added and the mixture was heated
at 100 °C. After complete reaction, the mix-
ture was cooled, diluted with CH2Cl2, filtered,
1625, 1372, 1234, 837 cm−1
;
1H NMR
(CDCl3): l 6.18 (s, 1 H, H-1), 5.95 (t, J 1.6
Hz, 1 H, H-6), 5.10 (ddd, J3,4 7.9, J3,3a 5.5,
J3,3a% 3.3 Hz, 1 H, H-3), 4.44 (dd, J4,3 7.9, J4,4a
2.1 Hz, 1 H, H-4), 3.83 (dd, J3a%,%3a 11.2, J3a%,3
3.3 Hz, 1 H, H-3a%), 3.72 (dd, J3a,3a% 11.2, J3a,3
5.5 Hz, 1 H, H-3a), 3.46 (br d, J7a,4a 6.0 Hz, 1
H, H-7a), 3.06 (dd, J4a,7a 6.0, J4a,4 2.1 Hz, 1 H,
H-4a), 2.25 (s, 3 H, CH3), 2.18, 2.15 (2×
OCOCH3), 0.88 [s, 9 H, (CH3)2SiC(CH3)3],
0.07 [s, 6 H, (CH3)2SiC(CH3)3]; MS (70 eV):
m/z 355 (50), 295 (64), 253 (100), 235 (49), 161
(64), 117 (87), 75 (50). Anal. Calcd for
C20H32O7Si: C, 58.23; H, 7.82. Found: C,
58.35; H, 7.53. Following the ‘General
method for acetylation’, 1313 (17.6 mg, 0.054
mmol) gave (4aS,5S,6R,7aS,7bS)-5-(acetoxy)-
6 - [((1,1 - dimethylethyl)dimethylsilyloxy)-
methyl]-5,6,7a,7b-tetrahydro-2H-1,7-dioxa-
cyclopent[cd]inden-4(4aH)-one (15, 13 mg,
63%) after chromatography (4:1 hexane–
EtOAc): oil; [h]D25 −67° (c 0.75, CHCl3); IR
(KBr) w 2930, 2857, 1748, 1720, 1651, 1372,
concentrated, and purified
by
chro-
matography.
General method for the Hanessian–Hullar
reaction.—To a solution of compound in dry
CCl4 (0.055 M) at reflux, NBS (1.1 equiv) and
BaCO3 (0.42 equiv) were added. After 90 min,
the mixture was cooled, filtered, diluted with
CH2Cl2, and extracted with brine. The organic
phase was separated, dried (Na2SO4), filtered,
evaporated, and submitted to chromatography
to give the product.
Prop-2-ynyl
methylethyl)dimethylsilyl]-h-
2,3-dideoxy-6-O-[(1,1-di-
-erythro-hex-2-
D
enopyranoside (1).—To a solution of diol 118
(2.03 g, 0.011 mmol) in dry CH2Cl2 (0.12 M),
cooled at 0 °C, under Ar, t-butyldimethylsilyl
chloride (1 equiv), imidazole (1.1 equiv) and
4-dimethylaminopyridine (cat.) were added.
The mixture was warmed at rt and stirred for
8 h, diluted with CH2Cl2, washed with an aq
satd solution of NaHCO3 and brine. The or-
ganic phase was dried, filtered, and the solvent
was removed. The crude product was submit-
ted to chromatography (4:1 hexane–EtOAc)
to give product 1 (3.08 g, 94%), which showed
physical and spectroscopic data identical to
those described for this compound in litera-
ture.13
1
1233, 1137, 1044, 1015 cm−1; H NMR (300
MHz, CDCl3): l 6.21 (br s, 1 H, H-3), 5.63 (d,
J7a,7b 6.5 Hz, 1 H, H-7a), 5.11 (dd, J5,6=J5,4a
9.4 Hz, 1 H, H-5), 4.85 (dt, J2%,2 15.3, J 1.4 Hz,
1 H, H-2%), 4.67 (dt, J2,2% 15.3, J 2.0 Hz, 1 H,
H-2), 3.76 (dd, J6a,6a% 11.4, J6a%,6 2.5 Hz, 1 H,
H-6a%), 3.70 (dd, J6a,6a% 11.4, J6a,6 2.5 Hz, 1 H,
H-6a), 3.64 (dt, J6,5 9.4, J6,6a=J6,6a% 2.5 Hz, 1
H, H-6), 3.52 (dd, 1 H, J7b,4a 8.9, J7b,7a 6.5 Hz,
1 H, H-7b), 3.45–3.40 (m, 1 H, H-4a), 2.07 (s,
3 H, OCOCH3), 0.86 [s, 9 H, (CH3)2SiC-
(CH3)3], 0.03 [s, 6 H, (CH3)2SiC(CH3)3]; 13C
NMR (75 MHz, CDCl3): l 206.2 (C-4), 181.0
(C-2a), 169.9 (OCOCH3), 126.1 (C-3), 96.5

80
J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
25.7 [(CH3)2SiC(CH3)3], 18.1 [(CH3)2SiC-
(CH3)3], −5.6 [2 C, (CH3)2SiC(CH3)3]; MS
(70 eV): m/z 175 (39), 129 (24), 117 (38), 107
(92), 89 (19), 79 (100), 59 (17), 41(17). Anal.
Calcd for C16H28O5Si: C, 58.50; H, 8.59.
Found: C, 58.65; H, 8.72.
(C-7a), 70.1 (C-6), 65.9 (C-2), 65.8 (C-5), 62.4
(C-6a), 47.9 (C-4a), 46.3 (C-7b), 25.8
[(CH3)2SiC(CH3)3], 20.8 (OCOCH3), 18.2
[(CH3)2SiC(CH3)3], −5.5, −5.6 [2 C,
(CH3)2SiC(CH3)3]; MS (70 eV): m/z 309 (45),
251 (87), 223 (50), 195 (44), 177 (46), 129 (46),
117 (100), 75 (97), 43(77). Anal. Calcd for
C18H28O6Si: C, 58.67; H, 7.66. Found: C,
58.55; H, 7.43.
Prop-2-ynyl
methyl) - 6 - O - [(1,1 - dimethyllethyl)dimethyl-
silyl)]-h- -erythro-hex-2-enopyranoside (3).—
2,3-dideoxy-4-O-(methoxy-
D
To a solution of compound 1 (2.0 g, 6.7
mmol) in dry DMF (0.18 M) cooled at a 0 °C
under Ar, sodium hydride (402 mg, 10.05
mmol, 1.5 equiv, 60% dispersion in oil) and
MOMCl (0.76 mL, 10.05 mmol, 1.5 equiv)
were added. The mixture was stirred at rt.
After 90 min, some drops of AcOH were
added, the solvent was removed, and the
crude product was submitted to chromatogra-
phy (9:1 hexane–EtOAc) to give 3 (1.69 g,
74%): oil; [h]2D5 +107° (c 2.64, CHCl3); IR
(KBr) w 2150, 1255, 1097, 1036, 963, 837, 777
cm−1; MS (70 eV): m/z 168 (24), 118 (24), 117
(100), 89 (36), 81 (23), 45 (70). Anal. Calcd for
C17H30O5Si: C, 59.62; H, 8.83. Found: C,
59.55; H, 8.92.
Prop-2-ynyl
4-O-acetyl-2,3-dideoxy-6-O-
-erythro-
[(1,1-dimethylethyl)dimethylsilyl]-h-
D
hex-2-enopyranoside (2).—Following the
‘General method for acetylation’, 1 (1.23 g,
4.12 mmol) afforded acetate 2 (1.40 g, 99%)
after chromatography (9:1 hexane–EtOAc):
oil; [h]2D5 +158° (c 2.44, CHCl3); IR (KBr) w
1742, 1372, 1235, 1127, 1094, 1038, 837, 778
cm−1; MS (70 eV): m/z 223 (16), 117(100), 89
(16), 75 (25), 43(24). Anal. Calcd for
C17H28O5Si: C, 59.97; H, 8.29. Found: C,
59.73; H, 8.14.
Pauson–Khand reaction of precursor 2.—
Following the ‘General method for the Pau-
son–Khand reaction’, enyne 2 (475 mg, 1.4
mmol) afforded product 15 (325 mg, 63%)
after chromatography (4:1 hexane–EtOAc), a
compound identical in all the physical and
spectroscopic data to the compound obtained
by acetylation of the PK reaction product 13.
(4S,4aR,5S,6R,7aS,7bS)-6-[((1,1-Dimethy-
ethyl)dimethylsilyoxy)methy] - 4,4a,5,6,7a,7b-
hexahydro - 2H - 1,7 - dioxacyclopent[cd]indene-
4,5-diol (16).—Following the ‘General
method for the reduction with DIBALH in
toluene’, ketone 15 (127 mg, 0.34 mmol) gave
diol 16 (50 mg, 45%) after flash chromatogra-
phy (13:9 hexane–EtOAc): mp 69–72 °C; [h]D25
−105° (c 0.48, CHCl3); IR (KBr) w 3307,
Pauson–Khand reaction of precursor (3).—
Following the ‘General method for the Pau-
son–Khand reaction’, enyne 3 (235 mg, 0.69
mmol) gave enone (4aS,5S,6R,7aS,7bS) 5-
(methoxymethyl) - 6 - [((1,1 - dimethylethyl)di-
methylsilyloxy)methyl] - 5,6,7a,7b - tetrahydro-
2H-1,7-dioxacyclopent[cd]inden-4(4aH)-one
(17, 137 mg, 54%) after chromatography
(from 4:1 to 3:2 hexane–EtOAc): oil; IR (film)
w 2930, 2857, 1750, 1717, 1471, 1254, 1110,
1029, 836 cm−1; 1H NMR (300 MHz, CDCl3):
l 6.21 (br s, 1 H, H-3), 5.56 (d, J7a,7b 4.9 Hz,
1 H, H-7a), 4.83 (d, J 7.0 Hz, 1 H, OCH2O),
4.82 (dm, J2%,2 15.4 Hz, 1 H, H-2%), 4.72 (d, J
7.0 Hz, 1 H, OCH2O), 4.66 (dm, J2,2% 15.4 Hz,
1 H, H-2), 4.17 (t, J5,6 =J5,4a 8.7 Hz, 1 H,
H-5), 3.78 (dd, J6a,6a% 11.7, J6a%,6 2.4 Hz, 1 H,
H-6a%), 3.74 (dd, J6a,6a% 11.7, J6a,6 2.4 Hz, 1 H,
H-6a), 3.58 (dt, J6,5 9.0, J6,6a=J6,6a% 2.4 Hz, 1
H, H-6), 3.48 (s, 3 H, OCH3), 3.47–3.31 (m, 2
H, H-4a, H-7b), 0.88 [s, 9 H, (CH3)2SiC-
(CH3)3], 0.06 [s, 6 H, (CH3)2SiC(CH3)3]; 13C
NMR (75 MHz, CDCl3): l 207.1 (C-4), 180.1
(C-2a), 126.4 (C-3), 96.3 (OCH2O)*, 95.9 (C-
7a)*, 72.2 (C-6), 68.6 (C-4), 65.5 (C-2), 62.6
(C-6a), 56.3 (OCH3), 48.5 (C-4a)*, 48.1
1
1255, 1080, 1063, 1038, 838, 775 cm−1; H
NMR (300 MHz, CDCl3): l 5.78 (br s, 1 H,
H-3), 5.40 (d, J7a,7b 4.8 Hz, 1 H, H-7a), 5.30
(br s, 1 H, H-4), 4.31 (dm, J2%,2 13.6 Hz, 1 H,
H-2%), 4.02–3.89 (m, 2 H, H-6, H-5), 3.84 (dd,
J6a,6a% 10.7, J6a,6 4.4 Hz, 1 H, H-6a), 3.79 (dd,
J6a%,6a 10.7, J6a%,6 6.3 Hz, 1 H, H-6a%), 3.08 (q,
J
4a,4=J4a,5=J4a,7b 6.2 Hz, 1 H, H-4a), 0.89 [s,
9 H, (CH3)2SiC(CH3)3], 0.072 [s, 6 H,
(CH3)2SiC(CH3)3]; 13C NMR (75 MHz,
CDCl3): l 144.3 (C-2a), 127.8 (C-3), 95.4 (C-
7a), 84.9 (C-4), 77.2 (C-6), 66.9 (C-5), 64.9
(C-2), 62.9 (C-6a), 49.6 (C-7b), 44.6 (C-4a),
(C-7b)*,
25.9
[(CH3)2SiC(CH3)3],
18.3

J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
81
(4aS,5S,6R,7aS,7bS) - 6 - [((1,1 - Dimethyl-
ethyl)dimethylsilyloxy)methyl] - 5 - phenylmeth-
oxy-5,6,7a,7b-tetrahydro-2H-1,7-dioxacyclo-
[(CH3)2SiC(CH3)3], −5.4, −5.2 [2 C, (CH3)2-
SiC(CH3)3]; MS (70 eV): m/z 313 (29), 251
(47), 197 (90), 89 (42), 75 (38), 45 (100). Anal.
Calcd for C18H30O6Si: C, 58.35; H, 8.16.
Found: C, 58.44; H, 8.02.
pent[cd]inden-4(4aH)-one
(19).—Following
the ‘General method for the Pauson–Khand
reaction’, precursor 4 (474 mg, 1.22 mmol)
gave 19 (208 mg, 39%) after chromatography
(7:3 hexane–EtOAc): oil; [h]2D5 −20° (c 4.14,
CHCl3); IR (film) w 2928, 2856, 1716, 1652,
(4S, 4aR,5S,6R,7aS,7bS)-5-(Methoxy-
methyl) - 6 - [((1,1 - dimethylethyl)dimethylsilyl-
oxy)methyl]-4,4a,5,6,7a,7b-hexahydro-2H-1,7-
dioxacyclopent[cd]indene (18).—Following the
‘General method for reduction with DIBALH,
17 (343 mg, 0.9 mmol) afforded alcohol 18
(182 mg, 53%) after chromatography (from
4:1 to 7:3 hexane–EtOAc): oil; [h]2D5 −93° (c
1.23, CHCl3); IR (film) w 3494, 2930, 2855,
1
1462, 1114, 1015, 836, 778 cm−1; H NMR
(300 MHz, CDCl3): l 7.44–7.26 (m, 5 H,
C6H5), 6.21 (br s, 1 H, H-3), 5.55 (d, J7a,7b 6.4
Hz, 1 H, H-7a), 4.98 (d, J 10.6 Hz, 1 H,
OCH2Ph), 4.81 (d, J2%,2 15 Hz, 1 H, H-2%), 4.64
(dt, J2,2% 15.3, J 1.8 Hz, 1 H, H-2), 4.49 (d, J
10.6 Hz, 1 H, OCH2C6H5), 4.00 (t, J5,6=J5,4a
8.9 Hz, 1 H, H-5), 3.81 (dd, J6a,6a% 11.2, J6a%,6
2.5 Hz, 1 H, H-6a%), 3.74 (dd, J6a,6a% 11.2, J6a,6
1
1471, 1274, 1025, 948, 836, 777 cm−1; H
NMR (300 MHz, CDCl3): l 5.73 (s, 1 H,
H-7), 5.40 (m, 1 H, H-4), 5.37 (d, J7a,7b 4.9 Hz,
1 H, H-7a), 4.77 (d, J 6.4, Hz, 1 H, OCH2O),
4.70 (d, J 6.4 Hz, 1 H, OCH2O), 4.61 (d, JꢀOH,4
7.1 Hz, 1 H, OH), 4.54 (dd, J2%,2 12.8, J 1.6
Hz, 1 H, H-2%), 4.24 (dm, J2,2% 12.8 Hz, 1 H,
H-2), 4.13 (dt, J6,5 6.7, J6,6a=J6,6a% 3.2 Hz, 1
H, H-6), 4.05 (t, J5,6 =J5,4a 6.7 Hz, 1 H, H-5),
3.78 (dd, J6a,6a% 11.2, J6a%,6 3.2 Hz, 1 H, H-6a%),
3.73 (dd, J6a,6a% 11.2, J6a,6 3.2 Hz, 1 H, H-6a),
2.5 Hz, 1 H, H-6a), 3.56 (dt, J6,5 8.9, J6,6a
=
J6,6a% 2.5 Hz, 1 H, H-6), 3.43 (dd, J4a,5 8.9,
J4a,7b 6.6 Hz, 1 H, H-4a), 3.40–3.35 (m, 1 H,
H-7b), 0.90 [s, 9 H, (CH3)2SiC(CH3)3], 0.06 [s,
6 H, (CH3)2SiC(CH3)3]; 13C NMR (75 MHz,
CDCl3): l 206.6 (C-4), 179.7 (C-2a), 137.7-
127.6 (OCH2C6H5), 126.0 (C-3), 96.3 (C-7a),
72.4 (OCH2C6H5), 71.4 (C-5)*, 71.2 (C-6)*,
65.5 (C-2), 62.6 (C-6a), 8.1 (C-7b)*, 48.0 (C-
4a)*, 25.8 [(CH3)2SiC(CH3)3], 18.2 [(CH3)2SiC-
(CH3)3], −5.5, −5.3 [2 C, (CH3)2SiC(CH3)3];
MS (70 eV): m/z 359 (25), 243 (40), 91 (100),
75 (31), 73 (31), 65 (22). Anal. Calcd for
C23H32O5Si: C, 66.31; H, 7.74. Found: C,
66.42; H, 7.53.
3.45 (s, 3 H, OCH3), 3.23 (dt, J4a,7b 7.7, J4a,5
=
J4a,4 6.6 Hz, 1 H, H-4a), 3.12–3.07 (m, 1 H,
H-7b), 0.88 [s, 9 H, (CH3)2SiC(CH3)3], 0.06 [s,
6 H, (CH3)2SiC(CH3)3]; 13C NMR (75 MHz,
CDCl3): l 143.9 (C-2a), 126.8 (C-3), 96.8
(OCH2O), 95.3 (C-7a), 85.3 (C-4), 73.5 (C-6),
72.8 (C-5), 64.0 (C-2), 62.4 (C-6a), 56.1
(OCH3), 51.6 (C-7b), 41.7 (C-4a), 25.7
[(CH3)2SiC(CH3)3], 18.0 [(CH3)2SiC(CH3)3],
−5.7, −5.4 [2 C, (CH3)2SiC(CH3)3]; MS (70
eV): m/z 253 (16), 207 (64), 137 (26), 117 (57),
91 (38), 89 (32), 75 (46), 45 (100). Anal. Calcd
for C18H32O6Si: C, 58.03; H, 8.66. Found: C,
58.23; H, 8.42.
(4S,4aR,5S,6R,7aS,7bS)-6-[((1,1-Dimethyl-
ethyl)dimethylsilyloxy)methyl] - 5 - (phenylmeth-
oxy)-4,4a,5,6,7a,7b-hexahydro-2H-1,7-dioxa-
cyclopent[cd]indene-4-ol (20).—Following the
‘General method for DIBALH reduction’, ke-
tone 19 (223 mg, 0.54 mmol) gave alcohol 20
(173 mg, 77%) after chromatography (4:1 hex-
ane–EtOAc): oil; [h]2D5 +2° (c 0.42, CHCl3);
IR (film) w 3467, 2929, 2856, 1462, 1254, 1070,
Prop-2-ynyl 4-O-benzyl-2,3-dideoxy-6-O-
[(1,1-dimethylethyl)dimethylsilyl]-h- -erythro-
D
hex-2-enopyranoside (4).—Following the
‘General method for O-benzylation’, 1 (285
mg, 0.96 mmol) gave 4 (364 mg, 98%) after
chromatography (9:1 hexane–EtOAc): oil;
[h]2D5 +133° (c 1.8, CHCl3); IR (KBr) w 2150,
1254, 1095, 1044, 837, 778, 698 cm−1; MS (70
eV): m/z 214 (13), 185 (23), 117 (92), 91 (100),
89 (17), 79 (15), 39 (13). Anal. Calcd for
C22H32O4Si: C, 68.00; H, 8.30. Found: C,
67.85; H, 8.42.
1
1015, 836, 778 cm−1; H NMR (300 MHz,
CDCl3): l 7.36–7.33 (m, 5 H, C6H5), 5.70 (br
s, 1 H, H-3), 5.37 (d, J7a,7b 5.0 Hz, 1 H, H-7a),
5.36–5.32 (m, 1 H, H-4), 4.81 (d, JOH,4 7.8 Hz,
1 H, OH), 4.72 (d, J 11.1 Hz, 1 H,
OCH2C6H5), 4.56 (d, J 10.6 Hz, 1 H,
OCH2C6H5), 4.56 (dm, J2%,2 13.0 Hz, 1 H,
H-2%), 4.25 (ddt, J2,2% 13.0, J 3.7, J 2.1 Hz, 1 H,
H-2), 4.18 (dt, J6,5 6.8, J6,6a=J6,6a% 3.7 Hz, 1

82
J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
(4S,4aR,5S,6R,7aS,7bS) - 4,4a,5,6,7a,7b-
Hexahydro-5-phenylmethoxy-2H-1,7-dioxacy-
clopent[cd]indene-4-ol benzoate (22).—Follow-
ing the ‘General method for desilylation’, 21
(626 mg, 1.27 mmol) afforded alcohol 22 (411
mg, 80%) after chromatography (7:3 hexane–
EtOAc): mp 82–85 °C; [h]2D5 +104° (c 0.31,
CHCl3); IR (KBr) w 2929, 2856, 1719, 1272,
H, H-6), 3.96 (t, J5,6 =J5,6% 6.8 Hz, 1 H, H-5),
3.87 (dd, J6a,6a% 11.0, J6a%,6 3.7 Hz, 1 H, H-6a%),
3.78 (dd, J6a,6a% 11.0, J6a,6 3.7 Hz, 1 H, H-6a),
3.17 (q, J4a,5=J4a,7b =J4a,4 6.8 Hz, 1 H, H-4a),
3.10–3.04 (m, 1 H, H-7b), 0.91 [s, 9 H,
(CH3)2SiC(CH3)3], 0.08 [s, 6 H, (CH3)2SiC-
13
(CH3)3]; C NMR (75 MHz, CDCl3): l 144.1
(C-2a), 137.1–127.8 (OCH2C6H5), 126.7 (C-3),
95.5 (C-7a), 85.6 (C-4), 74.2 (C-5), 72.6 (C-6),
72.3 (OCH2C6H5), 64.2 (C-2), 62.5 (C-6a),
51.2 (C-7b), 41.0 (C-4a), 25.8 [(CH3)2SiC-
(CH3)3], 18.2 [(CH3)2SiC(CH3)3], −5.5, −5.3
[2 C, (CH3)2SiC(CH3)3]; MS (70 eV): m/z 207
(25), 137 (16), 117 (28), 92 (21), 91 (100), 79
(20), 75 (23), 73 (19). Anal. Calcd for
C23H34O5Si: C, 65.99; H, 8.19. Found: C,
65.73; H, 8.01.
1
1114, 1026, 836, 711 cm−1; H NMR (300
MHz, CDCl3): l 7.85 (dd, J 7.0, J 1.7 Hz, 2
H, OCOC6H5), 7.46 (t, J 7.5, J 1.3 Hz, 1 H,
OCOC6H5), 7.07–7.32 (m, 7 H, OCH2C6H5,
OCOC6H5), 6.66 (dq, J4,4a 7.5, J 1.7 Hz, 1 H,
H-4), 5.82 (br s, 1 H, H-3), 5.41 (d, J7a,7b 4.6
Hz, 1 H, H-7a), 4.59 (dd, J2%,2 12.6, J 1.3 Hz,
1 H, H-2%), 4.64 (d, J 11.4 Hz, 1 H,
OCH2C6H5), 4,39 (dt, J6,5 9.6, J6,2H6a 4.3 Hz, 1
H, H-6), 4.34 (d, J 11.4 Hz, 1 H, OCH2C6H5),
4.30 (ddt, J2,2% 12.6, J 3.4, J 2.0 Hz, 1 H, H-2),
3.70–3.64 (m, 3 H, H-5, 2 H6a), 3.56 (ddd,
J4a,7b 8.9, J4a,4 7.5, J4a,5 5.9 Hz, 1 H, H-4a),
3.39 (dm, J7b,4a 8.9 Hz, 1 H, H-7b), 2.17–2.04
(4S,4aR,5S,6R,7aS,7bS)-6-[((1,1-Dimethyl-
ethyl)silyloxy)methyl]-5-(phenylmethoxy)-4,4a,
5,6,7a,7b-hexahydro-2H-1,7-dioxacyclopent-
[cd]indene-4-ol benzoate (21).—Following the
‘General method for benzoylation’, 20 (102
mg, 0.24 mmol) afforded benzoate 21 (72 mg,
60%) after chromatography (9:1 hexane–
EtOAc): oil; [h]D25 +85° (c 0.59, CHCl3); IR
(film) w 2929, 2856, 1719, 1272, 1114, 1026,
13
(br s, 1 H, OH)]; C NMR (75 MHz, CDCl3):
l 166.2 (OCOC6H5), 147.9 (C-2a), 137.1–1276
(OCH2C6H5, OCH2C6H5), 123.4 (C-3), 95.2
(C-7a), 84.7 (C-4), 75.3 (C-5), 72.7 (C-6), 72.2
(OCH2C6H5), 63.6 (C-2)*, 63.3 (C-6a)*, 54.2
(C-7b), 37.4 (C-4a); MS (70 eV): m/z 286 (9),
168 (45), 105 (100), 91 (98), 77 (55), 65 (14).
Anal. Calcd for C24H24O6: C, 70.58; H, 5.92.
Found: C, 70.66; H, 6.23.
1
836, 711 cm−1; H NMR (300 MHz, CDCl3):
l 7.82–7.27 (m, 5 H, OCOC6H5), 7.18–7.12
(m, 5 H, OCH2C6H5); 6.69 (br d, J4,4a 6.0 Hz,
1 H, H-4), 5.79 (br s, 1 H, H-3), 5.47 (d, J7a,7b
4.0 Hz, 1 H, H-7a), 4.62 (d, J 11.4 Hz, 1 H,
OCH2C6H5), 4.58 (d, J2%,2 13.6 Hz, 1 H, H-2%),
4.37 (d, J 11.4 Hz, 1 H, OCH2C6H5), 4.29 (dd,
J2,2% 13.6, J 1.2 Hz, 1 H, H-2), 4.20 (d, J6,5 9.4
Hz, 1 H, H-6), 3.96 (dd, J5,6 9.4, J5,4a 6.0 Hz,
1 H, H-5), 3.75 (s, 2 H, 2 H-6a), 3.51 (q,
Oxidation of intermediate 22.—Compound
22 (132 mg, 0.32 mmol) was oxidized accord-
ing to the Dess–Martin protocol to give
(4S,4aR,5S,6RS,7aS,7bS) - 4 - (benzoyloxy) - 4,
4a,5,6,7a,7b - hexahydro - 5 - (phenylmethoxy)-
2H - 1,7 - dioxacyclopent[cd]inden - 6 - carbalde-
hyde (23, 109 mg, 83%) (as a mixture of
epimers at C-6 in 2:1 ratio) after chromatogra-
phy (1:1 hexane–EtOAc) [IR (KBr) w 3436,
J4a,5=J4a,7b =J4a,4 6.0 Hz, 1 H, H-4a), 3.29–
3.27 (m, 1 H, H-7b), 0.89 [s, 9 H,
(CH3)2SiC(CH3)3], 0.07 [s, 6 H, (CH3)2SiC-
13
(CH3)3]; C NMR (75 MHz, CDCl3): l 166.0
1
(OCOC6H5), 147.7 (C-2a), 138.0–127.1
(OCH2C6H5, OCOC6H5), 123.9 (C-3), 95.6 (C-
7a), 84.6 (C-4), 74.9 (C-6), 72.1 (2 C,
OCH2C6H5, C-5), 63.8 (C-2)*, 63.5 (C-6a)*,
54.5 (C-7b), 37.8 (C-4a), 25.9 [(CH3)2SiC-
(CH3)3], 18.2 [(CH3)2SiC(CH3)3], −5.5, −5.3
[2 C, (CH3)2SiC(CH3)3]; MS (70 eV): m/z 253
(19), 227 (33), 207 (24), 137 (20), 117 (25), 105
(85), 91 (100), 77 (28). Anal. Calcd for
C30H38O6Si: C, 68.93; H, 7.33. Found: C,
68.75; H, 7.41.
2927, 1716, 1450, 1273, 1112 cm−1; H NMR
(300 MHz, CDCl3): l 9.74 and 9.65 (s, 1 H,
CHO), 8.00–7.20 (m, 10 H, OCH2C6H5,
OCOC6H5), 6.60 and 6.20 (m, 1 H, H-4),
5.90–5.80 (m, 2 H, H-3), 5.52 (d, J7a,7b 4.6 Hz,
1 H, H-7a), 5.51 (m, 1 H, H-7a), 4.80–4.20
(m, 5 H, OCH2C6H5, 2 H-2, H-5), 4.85 (dm,
J2%,2 11.5 Hz, 1 H, H-2%), 4.60 (m, 1 H, H-5),
4.52 (dm, J2,2% 11.7 Hz, 1 H, H-2), 4.42 (d, J
11.8 Hz, 1 H, OCH2C6H5), 4,28 (d, J 11.8 Hz,
1 H, OCH2C6H5), 4.02 (d, J6,5 5.7 Hz, 1 H,

J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
83
7.52 (tm, J 7.5 Hz, 1 H, OCOC6H5), 7.37 (t, J
7.5 Hz, 2 H, OCOC6H5), 7.28–7.27 (m, 5 H,
OCH2C6H5), 6.51 (dq, J4,4a 7.1, J 1.5 Hz, 1 H,
H-4), 6.35 (d, J6,5 6.0 Hz, 1 H, H-6), 5.85 (br
s, 1 H, H-3), 5.45 (d, J7a,7b 4.0 Hz, 1 H, H-7a),
4.63 (ddm, J2%,2 12.0, J 1.3 Hz, 1 H, H-2%), 4.56
(d, J 11.8 Hz, 1 H, OCH2C6H5), 4.49 (d, J
11.8 Hz, 1 H, OCH2C6H5), 4.37 (ddt, J2,2% 12.0,
J 3.1, J 1.8 Hz, 1 H, H-2), 3.75 (t, J5,4a=J5,6
6.0 Hz, 1 H, H-5), 3.49 (ddd, J4a,7b 8.3, J4a,4
7.1, J4a,5 6.0 Hz, 1 H, H-4a), 3.33–3.28 (m, 1
H, H-7b); 13C NMR (75 MHz, CDCl3): l
160.1 (OCOC6H5), 145.8 (C-2a), 133.2–127.5
(12 C, OCOC6H5, OCH2C6H5), 125.4 (C-3),
97.7 (C-7a), 94.9 (C-6), 83.9 (C-4), 74.0 (C-5),
72.6 (OCH2C6H5), 65.3 (C-2), 53.2 (C-7b),
39.1 (C-4a); MS (70 eV): m/z 227 (19), 164
(29), 105 (100), 91 (98), 77 (60).
H-6), 4.00–3.98 (m,
1
H, H-6), 3.49
(q, J 5.9 Hz, 1 H, H-4a), 3.60–3.40 (m, 1 H,
H-4a), 3.40–3.00 (m, 2 H, H-7b); 13C NMR
(75 MHz, CDCl3): l 201.8, 199.0 (CHO),
166.1 (2×OCOC6H5), 147.0–126.0 (10 C,
OCOC6H5, OCH2C6H5), 124.0 and 122.1 (C-
3), 98.1 and 95.2 (C-7a), 84.4 and 84.2 (C-6),
78.7 and 77.9 (C-4), 74.0 and 71.9
(OCH2C6H5), 72.6 and 72.1 (C-5), 66.0 and
64.4 (C-2), 52.9 and 50.2 (C-7b), 48.6 and 39.0
(C-4a); MS (70 eV): m/z 377 (4), 257 (20), 165
(14), 105 (100), 91 (98), 79 (43), 77 (64)].
Compound 23 (58 mg, 0,14 mmol) was dis-
solved in dry toluene (4.8 mL, 0.03 M) and
RhCl(PPh3)3 (132 mg, 0.14 mmol, 1 equiv)
was added. The mixture was stirred at rt for
24 h, EtOH was added, the mixture was
filtered, evaporated and the crude was submit-
ted to chromatography (4:1 hexane–EtOAc)
Prop-2-ynyl 2,3-dideoxy-6-O-p-toluenesul-
to
give
(4aS,5S,7aS,7bS)-5,6,7a,7b-tetra-
fonyl-h- -erythro-hex-2-enopyranoside (26).—
D
hydro-5-(phenylmethoxy)-2H-1,7-dioxacyclo-
pent[cd]inden-4-ol benzoate (24, 3.4 mg, 6%)
[1H NMR (300 MHz, CDCl3): l 7.92 (dd, J
7.9, J 1.5 Hz, 2 H, OCOC6H5), 7.50 (tm, J 7.5
Hz, 1 H, OCOC6H5), 7.37–7.24 (m, 7 H,
OCH2C6H5, OCOC6H5), 6.33–6.31 (m, 1 H,
H-4), 5.85 (m, 1 H, H-3), 5,32 (d, J7a,7b 5.1 Hz,
1 H, H-7a), 4.71 (dq, J2%,2 13.4, J 2.0 Hz, 1 H,
H-2%), 4.55 (d, J 11.8 Hz, 1 H, OCH2C6H5),
4.41 (ddt, J2,2% 13.8, J 3.8, J 1.8 Hz, 1 H, H-2),
4.30 (d, J 11.8 Hz, 1 H, OCH2C6H5), 4.03 (dd,
J6,6% 12.2, J6,5 4.2 Hz, 1 H, H-6), 3.54 (ddd,
J5,4a 6.4, J5,6 4.2, J5,6% 1.2 Hz, 1 H, H-5), 3.43
(q, J 6.4 Hz, 1 H, H-4a), 3.36 (dd, J6%,6 12.2,
J6%,5 1.2 Hz, 1 H, H-6%), 3.13–3.11 (m, 1 H,
H-7b)] whose decomposition prevented addi-
tional analysis.
Following the ‘General method for acetyla-
ton’, diol 11 (1.02 g, 5.55 mmol) gave product
26 (1.22 g, 65%) after chromatography (1:1
hexane–EtOAc): oil; [h]2D5 +60° (c 0.43,
CHCl3); IR (KBr) w 3450, 3230, 2060, 1570,
1325, 1160, 1145, 1010, 920 cm−1; MS (70
eV): m/z 283 (14), 155 (25), 124 (100), 91 (74),
85 (96), 57 (41), 39 (38). Anal. Calcd for
C16H18O6S: C, 56.79; H, 5.36; S, 9.48. Found:
C, 56.88; H, 5.39; S, 9.23.
Prop-2-ynyl 4-O-acetyl-2,3-dideoxy-6-O-p-
toluenesulfonyl-h- -erythro-hex-enopyranoside
D
(27).—Following the ‘General method for
acetylation’, 26 (986 mg, 2.9 mmol) gave ace-
tate 27 (952 mg, 86%) after chromatography
(7:3 hexane–EtOAc): mp 53–54 °C; [h]D25
+
132° (c 0.45, CHCl3); IR (KBr) w 3210, 2070,
Decarbonylation of intermediate 23.—Com-
pound 23 (25 mg, 0,062 mmol) was dissolved
in dry toluene (2 mL, 0.03 M), heated at reflux
and t-Bu2O2 (2,3 mL, 0.012 mmol, 20% mol)
was added. After 2 h, the solvent was removed
and the crude was submitted to chromatogra-
phy (1:1 hexane–EtOAc) giving (4S,4aR,5S,
6RS,7aS,7bS) - 4 - benzoyloxy - 4,4a,5,6,7a,7b-
hexahydro-5-phenylmethoxy-2H-1,7-dioxacy-
clopent[cd]inden-6-formate (25, 4.5 mg, 17%):
oil; [h]2D5 +44° (c 0.17, CHCl3); IR (KBr) w
1705, 1330, 1210, 1165, 1150, 1015, 920 cm−1
;
MS (70 eV): m/z 166 (40), 155 (24), 124 (100),
91 (32), 85 (23), 43 (29). Anal. Calcd for
C18H20O7S: C, 56.83; H, 5.30, S, 8.43. Found:
C, 57.14; H, 5.62; S, 8.21.
Prop-2-ynyl
iodo-h- -erythro-hex-2-enopyranoside (5).—
4-O-acetyl-2,3,6-trideoxy-6-
D
Following the ‘General method for the
synthesis of iodides from tosylates’, 27 (517
mg, 1.36 mmol) gave iodide 5 (422 mg, 92%)
after chromatography (9:1 hexane–EtOAc):
mp 27–30 °C; [h]2D5 +161° (c 1.66, CHCl3);
IR (KBr) w 3230, 2060, 1715, 1340, 1200, 1000
cm−1; MS (70 eV): m/z 166 (35), 124 (100), 85
1
3435, 2920, 1718, 1631, 1270, 1113 cm−1; H
NMR (300 MHz, CDCl3): l 8.05 (s, 1 H,
HCOO), 8.00 (dm, J 7.5 Hz, 2 H, OCOC6H5),

84
J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
C16H15O4I: C, 48.26; H, 3.80. Found: C, 48.34;
H, 3.56.
(33), 43 (54), 39 (20). Anal. Calcd for
C11H13O4I: C, 39.30; H, 3.90. Found: C, 39.16;
H, 4.12.
(4aS,5S,6R,7aS,7bS)-5-Benzoyloxy-5,6,7a,
7b-tetrahydro-6-iodomethyl-2H-1,7-dioxacy-
clopent[cd]inden-4(4aH)-one (30).—Following
the ‘General method for the Pauson–Khand
reaction’, 6 (465 mg, 1.17 mmol) gave 30 (277
mg, 55%) after chromatography (7:3 hexane–
(4aS,5S,6R,7aS,7bS) - 5 - Acetyloxy - 5,6,7a,
7b-tetrahydro-6-iodomethyl-2H-1,7-dioxacy-
clopent[cd]inden-4(4aH)-one (28).—Following
the ‘General method for the Pauson–Khand
reaction’, 5 (114 mg, 0.34 mmol) afforded 28
(54 mg, 44%) after chromatography (3:2 hex-
ane–EtOAc): mp\230 °C; [h]2D5 −108° (c
0.20, CHCl3); IR (KBr) w 1715, 1680, 1620,
1
EtOAc): oil; H NMR (300 MHz, CDCl3): l
7.94 (d, J 7.3 Hz, 2 H, OCOC6H5), 7.55 (t, J
7.3 Hz, 1 H, OCOC6H5), 7.42 (t, J 7.7 Hz, 2
H, OCOC6H5), 6.23 (s, 1 H, H-3), 5.65 (d,
J7a,7b 6.1 Hz, 1 H, H-7a), 5.11 (t, J5,6=J5,4a 9.2
Hz, 1 H, H-5), 4.86 (d, J2%,2 15.3 Hz, 1 H,
H-2%), 4.65 (d, J2,2% 15.3 Hz, 1 H, H-2), 3.61–
3.49 (m, 3 H, H-6, H-4a, H-7b), 3.26 (dd,
J6a,6a% 10.9, J6a%,6 2.7 Hz, 1 H, H-6a%), 3.23 (dd,
1
1355, 1205, 1195, 955, 845 cm−1; H NMR
(300 MHz, CDCl3): l 6.21 (s, 1 H, H-3), 5.62
(d, J7a,7b 5.9 Hz, 1 H, H-7a), 4.85 (d, J2%,2 15.3
Hz, 1 H, H-2%), 4.82 (t, J5,6=J5,4a 9.1 Hz, 1 H,
H-5), 4.65 (d, J2,2% 15.3 Hz, 1 H, H-2), 3.54–
3.46 (m, 2 H, H-4a, H-7b), 3.32 (dd, J6a,6a%
11.1, J6a%,6 2.6 Hz, 1 H, H-6a%), 3.37–3.29 (m,
1 H, H-6), 3.19 (dd, J6a,6a% 11.1, J6a,6 5.3 Hz, 1
H, H-6a), 2.09 (s, 3 H, OCOCH3); 13C NMR
(75 MHz, CDCl3): l 205.1 (C-4), 180.6 (C-2a),
169.6 (OCOCH3), 126.1 (C-3), 96.4 (C-7a),
70.4 (C-5), 66.8 (C-6), 65.9 (C-2), 48.0 (C-
7b)*, 45.7 (C-4a)*, 20.6 (OCOCH3), 6.7 (C-
6a); MS (70 eV): m/z 237 (41), 177 (32), 152
(22), 95 (19), 43 (100), 39 (15). Anal.Calcd for
C12H13O5I: C, 39.58; H, 3.60. Found: C, 39.91;
H, 3.90.
13
J6a,6a% 10.9, J6a,6 5.3 Hz, 1 H, H-6a); C NMR
(75 MHz, CDCl3): l 204.9 (C-4), 180.6 (C-2a),
165.2 (OCOC6H5), 133.3–128.4 (OCOC6H5),
126.1 (C-3), 96.3 (C-7a), 70.6 (C-5), 67.1 (C-
6), 65.9 (C-2), 48.0 (C-7b)*, 45.9 (C-4a)*, 6.8
(C-6a). Anal. Calcd for C17H15O5I: C, 47.91;
H, 3.55. Found: C, 47.83; H, 3.41.
(4S,4aR,5S,6R,7aS,7bS) - 4,4a,5,6,7a,7b-
Hexahydro-6-iodomethyl-2H-1,7-dioxacyclo-
pent[cd]inden-4,5-diol dibenzoate (32).—Fol-
lowing the ‘General method for the reduction
with DIBALH’, 30 (117 mg, 0.27 mmol) in
THF gave alcohol 31 (32 mg, 27%) after
chromatography (7:3 hexane–EtOAc). Com-
pound 31 (26 mg, 0.061 mmol) gave diben-
zoate 32 (11.5 mg, 35%) Following the
‘General method for benzoylation’, after chro-
matography (7:3 hexane–EtOAc): oil; IR
Prop-2-ynyl 4-O-benzoyl-2,3-dideoxy-6-O-
p-toluenesulfonyl-h- -erythro-hex-2-enopyran-
D
oside (29).—Following the ‘General method
for benzoylation’, tosylate 26 (1 g, 2.96 mmol)
gave 29 (1.23 g, 94%) after chromatography
(9:1 hexane–EtOAc): mp 70–73 °C; [h]D25
+
194° (c 1.12, CHCl3); IR (KBr) w 1690, 1570,
1420, 1335, 1235, 1160, 1145, 1075, 1065,
1015, 995 cm−1; MS (70 eV): m/z 228 (63),
105 (100), 91 (19), 77 (27). Anal. Calcd for
C23H22O7S: C, 62.43; H, 5.01; S, 7.25. Found:
C, 62.50; H, 5.23; S, 7.40.
(KBr) w 2926, 1717, 1280, 1113, 1027 cm−1
;
1H NMR (300 MHz, CDCl3): l 7.77–7.25 (m,
10 H, 2×OCOC6H5), 6.46 (dm, J4,4a 6.4 Hz, 1
H, H-4), 5.88 (br s, 1 H, H-3), 5.58 (d, J7a,7b
4.8 Hz, 1 H, H-7a), 5.35 (t, J5,6 =J5,4a 6.4 Hz,
1 H, H-5), 4.78 (dq, J2%,2 13.4, J 1.8 Hz, 1 H,
H-2%), 4.48 (ddt, J2,2% 13.4, J 3.5, J 2.2 Hz, 1 H,
H-2), 4.26 (dt, J6,5 6.4, J6,6a 5.5 Hz, 1 H, H-6),
3.73 (q, J4a,4 J4a,5 J4a,7b 6.4 Hz, 1 H, H-4a),
3.39 (dd, J6a,6a% 10.9, J6a%,6 5.5 Hz, 1 H, H-6a%),
3.34 (dd, J6a,6a% 10.9, J6a,6 5.5 Hz, 1 H, H-6a),
3.38–3.31 (m, 1 H, H-7b); 13C NMR (75
Prop-2-ynyl 4-O-benzoyl-2,3,6-trideoxy-6-
iodo-h- -erythro-hex-2-enopyranoside (6).—
D
Following the ‘General method for the
synthesis of iodides from tosylates’, 29 (196
mg, 0.44 mmol) gave iodide 6 (145 mg, 82%)
after chromatography (19:1 hexane–EtOAc):
oil; [h]2D5 +178° (c 1.52, CHCl3); IR (KBr) w
3293, 2118, 1721, 1451, 1316, 1261, 1108,
1026, 958, 711 cm−1; MS (70 eV): m/z 150
(51), 149 (81), 132 (52), 115 (48), 107 (45), 105
(100), 91 (61), 43 (73). Anal. Calcd for
MHz, CDCl3):
l
165.8, 165.78 (2×
OCOC6H5), 146.6 (C-2a), 133.1–128.16 (10 C,
2×OCOC6H5), 122.3 (C-3), 94.2 (C-7a), 84.3
(C-4), 73.4 (C-6), 67.9 (C-5), 64.7 (C-2), 51.0

J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
85
forded ketone 34 (45 mg, 47%) after chro-
(C-7b), 40.7 (C-4a), 3.9 (C-6a); MS (70 eV):
m/z 532 (5), 410 (12), 405 (9), 287 (47), 133
(28), 105 (100), 77 (71). Anal. Calcd for
C24H21O6I: C, 54.15; H, 3.98. Found: C, 54.27;
H, 3.77.
matography
(1:4
hexane–EtOAc):
mp
131–134 °C; [h]2D5 +2° (c 0.09, CHCl3); IR
(KBr) w 3452, 1712, 1656, 1123, 1019, 977, 746
1
cm−1; H NMR (300 MHz, CDCl3): l 7.41–
7.30 (m, 5 H, OCH2C6H5), 6.24 (s, 1 H, H-3),
5.53 (d, J7a,7b 5.9 Hz, 1 H, H-7a), 5.01 (d, J
10.9 Hz, 1 H, OCH2C6H5), 4.84 (d, J2%,2 15.4
Hz, 1 H, H-2%), 4.64 (d, J2,2% 15.4 Hz, 1 H,
H-2), 4.51 (d, J 10.9 Hz, 1 H, OCH2C6H5),
3.83 (t, J5,6=J5,4a 8.9 Hz, 1 H, H-5), 3.72 (dd,
J6a,6a% 11.6, J6a%,6 3.3 Hz, 1 H, H-6a%), 3.64–3.57
(m, 2 H, H-6, H-6a), 3.50–3.42 (m, 2 H, H-4a,
H-7b), 2.09 (br s, 1 H, OH); 13C NMR (75
MHz, CDCl3): l 206.0 (C-4), 179.8 (C-2a),
137.1–128.0 (OCH2C6H5), 126.2 (C-3), 96.2
(C-7a), 72.5 (C-5), 72.0 (OCH2C6H5), 69.7 (C-
6), 65.7 (C-2), 62.6 (C-6a), 47.9 (C-7b)*, 4780
(C-4a)*; MS (70 eV): m/z 196 (43), 132 (27),
108 (34), 91 (100), 65 (35). Anal. Calcd for
C17H18O5: C, 67.54; H, 6.00. Found: C, 67.25;
H, 6.28.
(4S,4aR,5S,6R,7aS,7bS) - 6 - [(Benzoyloxy)-
methyl]-4,4a,5,6,7a,7b-hexahydro-2H-1,7-di-
oxa-cyclopent[cd]indene-4,5-diol
dibenzoate
(33).—Following the ‘General method for the
reaction of silver fluoride’, 32 (5 mg, 0.009
mmol) in anhyd pyridine (0.5 mL, 0.01 M)
with silver fluoride (2 mg, 0.014 mmol, 1.5
equiv) afforded 33 (2 mg, 36%): oil; [h]2D5 −5°
(c 0.3, CHCl3); IR (KBr) w 2927, 1719, 1271,
1
1113, 1026, 710 cm−1; H NMR (300 MHz,
CDCl3): l 7.99 (dm, J 7.1 Hz, 2 H), 7.75 (dm,
J 7.1 Hz, 2 H), 7.55 (t, J 7.5 Hz, 1 H), 7.49 (t,
J 7.3 Hz, 1 H), 7.45–7.21 (m, 10 H) [3×
C6H5], 6.47–6.45 (m, 1 H, H-4), 5.88 (br s, 1
H, H-3), 5.62 (d, J7a,7b 4.8 Hz, 1 H, H-7a),
5.45 (t, J5,4a=J5,6 5.7 Hz, 1 H, H-5), 4.78 (dd,
J2,2% 13.2, J 1.5 Hz, 1 H, H-2), 4.61 (q, J6,5=
J6,6a=J6,6a% 5.7 Hz, 1 H, H-6), 4.54 (dd, J6a%,6a
Prop-2-ynyl 4-O-benzyl-2,3,6-trideoxy-6-
11.9, J6a%,6 5.7 Hz, 1 H, H-6a%), 4.49 (dd, J6a,6a%
11.9, J6a,6 5.7 Hz, 1 H, H-6a), 4.47 (m, 1 H,
H-2), 3.73 (q, J4a,7b=J4a,5 =J4a,4 5.7 Hz, 1 H,
H-4a), 3.41–3.36 (m, 1 H, H-7b); 13C NMR
(75 MHz, CDCl3): l 166.2, 165.7 (3 C, 3×
OCOC6H5), 146.6 (C-2a), 133.2–128.2 (15 C,
3×C6H5), 122.7 (C-3), 95.0 (C-7a), 84.4 (C-4),
72.6 (C-6), 66.3 (C-5), 64.8 (C-2), 63.2 (C-6a),
51.5 (C-7b), 41.6 (C-4a); MS (70 eV): m/z 526
(1), 282 (7), 254 (6), 160 (50), 132 17), 105
(100). Anal. Calcd for C31H26O8: C, 70.71; H,
4.98. Found: C, 70.59; H, 4.73.
iodo-h- -erythro-hex-2-enopyranoside (8).—
D
Following the ‘General method for iodination
of alcohols’, 7 (1.28 g, 4.7 mmol) gave iodide
8 (1.51 g, 84%) after chromatography (19:1
hexane–EtOAc): oil; [h]2D5 +162°° (c 5.39,
CHCl3); IR (film) w 3290, 2920, 2863, 2220,
1123, 1075, 1027, 956, 698 cm−1; MS (70 eV):
m/z 214 (76), 185 (29), 123 (31), 95 (29), 91
(100), 65 (29), 39 (34). Anal. Calcd for
C16H17O2I: C, 52.19; H, 4.65. Found: C, 52.36;
H, 4.72.
(4aS,5S,6R,7aS,7bS)-5,6,7a,7b-Tetrahydro-
6-iodomethyl-5-phenylmethoxy-2H-1,7-dioxa-
cyclopent[cd]inden-4(4aH)-one (35).—Follow-
ing the ‘General method for the Pauson–
Khand reaction’, iodide 8 (1.44 g, 3.75 mmol)
gave ketone 35 (847 mg, 55%) after chro-
matography (1:1 hexane–EtOAc): mp 113–
116 °C; [h]2D5 +17° (c 1.35, CHCl3); IR (film)
w 2965, 1708, 1650, 1221, 1125, 1107, 1012,
Prop-2-ynyl 4-O-benzyl-2,3-dideoxy-h- -
D
erythro-hex-2-enopyranoside (7).—Following
the ‘General method for desilylation’, 4 (990
mg, 2.55 mmol) gave alcohol 7 (720 mg, 90%)
after chromatography (7:3 hexane–EtOAc):
oil; [h]2D5 +158° (c 0.69, CHCl3); IR (film) w
3400, 3289, 2916, 2200, 1454, 1398, 1138,
1042, 957, 699 cm−1; MS (70 eV): m/z 214
(91), 185 (65), 123 (66), 95 (57), 91(100), 67
(53), 39 (78). Anal. Calcd for C16H16O4: C,
70.06; H, 5.88. Found: C, 69.94; H, 5.81.
(4aS,5S,6R,7aS,7bS)-5,6,7a,7b-Tetrahydro-
6-hydroxymethyl-2H-1,7-5-phenylmethoxydi-
oxacyclopent[cd]inden-4(4aH)-one (34).—Fol-
lowing the ‘General method for the Pauson–
Khand reaction’, 7 (88 mg, 0.32 mmol) af-
1
971, 874, 766, 701 cm−1; H NMR (300 MHz,
CDCl3): l 7.45–7.26 (m, 5 H, OCH2C6H5),
6.23 (s, 1 H, H-3), 5.59 (d, J7a,7b 5.6 Hz, 1 H,
H-7a), 5.07 (d, J 10.0 Hz, 1 H, OCH2C6H5),
4.83 (d, J2%,2 15.4 Hz, 1 H, H-2%), 4.65 (dt, J2,2%
15.4, J 1.6 Hz, 1 H, H-2), 4.50 (d, J 10.0 Hz,
1 H, OCH2C6H5), 3.78 (t, J5,6=J5,4a 8.5 Hz, 1
H, H-5), 3.53–3.45 (m, 2 H, H-4a, H-7b), 3.41

86
J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
7.09–7.20 (m, 5 H, OCH2C6H5), 6.63 (ddt,
J4,4a 5.7, J4,2 3.5, J4,2%=J4,3 1.7 Hz, 1 H, H-4),
5.80 (br s, 1 H, H-3), 5.54 (d, J7a,7b 4.4 Hz, 1
H, H-7a), 4.70 (d, J 10.5 Hz, 1 H,
OCH2C6H5), 4.60 (dd, J2%,2 12.5, J2%,4 1.5 Hz, 1
H, H-2%), 4.40 (d, J 10.5 Hz, 1 H, OCH2C6H5),
4.32 (ddt, J2,2% 12.5, J2,4 3.5, J 1.7 Hz, 1 H,
H-2), 4.04 (dt, J6,5 9.0, J6,6a 3.3 Hz, 1 H, H-6),
3.68 (dd, J5,6 9.0, J5,4a 5.7 Hz, 1 H, H-5), 3.59
(dt, J4a,7b 8.9, J4a,4=J4a,5 5.7 Hz, 1 H, H-4a),
3.48 (dd, J6a%,6a 10.5, J6a%,6 3.3 Hz, 1 H, H-6a%),
3.42–3.37 (m, 1 H, H-7b), 3.40 (dd, J6a,6a%
10.5, J6a,6 3.3 Hz, 1 H, H-6a); 13C NMR (75
MHz, CDCl3): l 165.9 (OCOC6H5), 148.1 (C-
2a), 137.2-127.4 (OCOC6H5, OCH2C6H5),
123.2 (C-3), 95.3 (C-7a), 84.7 (C-4), 77.0 (C-
5), 72.6 (OCH2C6H5), 71.0 (C-6), 63.6 (C-2),
54.6 (C-7b), 36.7 (C-4a), 12.2 (C-6a); MS (70
eV): m/z 269 (31), 227 (12), 197 (19), 168 (32),
105 (100), 91(100), 79 (45), 77 (62). Anal.
Calcd for C24H23O5I: C, 55.61; H, 4.47.
Found: C, 55.81; H, 4.67.
(dd, J6a,6a% 10.6, J6a%,6 3.0 Hz, 1 H, H-6a%), 3.36
(dd, J6a,6a% 10.6, J6a,6 3.0 Hz, 1 H, H-6a), 3.20
13
(dt, J6,5 8.5, J6,6a=J6,6a% 3.0 Hz, 1 H, H-6); C
NMR (75 MHz, CDCl3): l 205.8 (C-4), 179.6
(C-2a), 137.0–128.1 (OCH2C6H5), 126.1 (C-3),
96.4 (C-7a), 75.7 (C-5), 72.6 (OCH2C6H5),
67.8 (C-6), 65.8 (C-2), 48.1 (C-7b)*, 47.5 (C-
4a)*, 9.6 (C-6a); MS (70 eV): m/z 306 (61),
179 (21), 151 (17), 133 (31), 107 (32), 91 (100),
65 (29). Anal. Calcd for C17H17O4I: C, 49.53;
H, 4.16. Found: C, 49.80; H, 4.45.
(4S,4aR,5S,6R,7aS,7bS) - 4,4a,5,6,7a,7b-
Hexahydro-6-iodomethyl-2H-5-phenylmeth-
oxy-1,7-dioxacyclopent[cd]inden-4-ol (36).—
Following the ‘General method for with
DIBALH reduction’, 35 (770 mg, 1.87 mmol)
afforded 36 (542 mg, 70%) after chromatogra-
phy (7:3 hexane–EtOAc): oil; [h]2D5 +8° (c
0.95, CHCl3); IR (KBr) w 3447, 1010, 699
1
cm−1; H NMR (300 MHz, CDCl3): l 7.38–
7.29 (m, 5 H, OCH2C6H5), 5.72 (br s, 1 H,
H-3), 5.39 (d, J7a,7b 4.5 Hz, 1 H, H-7a), 5.40–
5.37 (m, 1 H, H-4), 4.75 (d, JOH,4 6.7 Hz, 1 H,
OH), 4.73 (d, J 10.7 Hz, 1 H, OCH2C6H5),
4.68 (d, J 10.7 Hz, 1 H, OCH2C6H5), 4.52 (dd,
J2%,2 11.0, J 1.3 Hz, 1 H, H-2%), 4.21 (dm, J2,2%
11.0 Hz, 1 H, H-2), 3.95 (dt, J6,5 7.9, J6,2H6a 4.0
Hz, 1 H, H-6), 3.81 (t, J5,4a=J5,6 7.9 Hz, 1 H,
H-5), 3.47 (dd, J6a%,6a 10.6, J6a%,6 4.2 Hz, 1 H,
H-6a%), 3.34 (dd, J6a,6a% 10.6, J6a,6 4.0 Hz, 1 H,
H-6a), 3.25–3.15 (m, 2 H, H-4a, H-7b); 13C
NMR (75 MHz, CDCl3): l 144.2 (C-2a),
136.2-128.2 (OCH2C6H5), 126.7 (C-3), 95.1 (C-
7a), 85.7 (C-4), 77.8 (C-5), 73.0 (OCH2C6H5),
69.5 (C-6), 63.9 (C-2), 51.5 (C-7b), 38.7 (C-
4a), 9.2 (C-6a); MS (70 eV): m/z 153 (14), 107
(17), 91 (100), 79 (26), 65 (16). Anal. Calcd for
C17H19O4I: C, 49.29; H, 4.62. Found: C, 49.34;
H, 4.32.
Reaction of intermediate 37 with sil6er
fluoride.—Following the ‘General method for
the elimination reaction with this reagent’, 37
(35 mg, 0.068 mmol) gave (4S,4aR,5S,6R,7aS,
7bS) - 6 - (benzoyloxy)methyl - 4,4a,5,6,7a,7b-
hexahydro-5-phenylmethoxy-2H-1,7-dioxacy-
clopent[cd]inden-4-ol benzoate (38, 11.5 mg,
33%) after chromatography (7:3 hexane–
EtOAc): oil; IR (KBr) w 2920, 1717, 1274,
1
1113 cm−1; H NMR (300 MHz, CDCl3): l
7.90 (d, J 8.4 Hz, 2 H), 7.78 (d, J 8.4 Hz, 2 H),
7.47 (t, J 7.4 Hz, 2 H), 7.40 (t, J 7.4 Hz, 1 H),
7.33 (t, J 7.7 Hz, 2 H), 7.23 (t, J 7.7 Hz, 2 H)
[2×OCOC6H5], 6,99 (s, 5 H, OCH2C6H5),
6.60 (dm, J4,4a 7.6 Hz, 1 H, H-4), 5.77 (br s, 1
H, H-3), 5.41 (d, J7a,7b 4.2 Hz, 1 H, H-7a),
4.64–4.52 (m, 1 H, H-6), 4.53 (dm, J2%,2 12.5
Hz, 1 H, H-2%), 4.49 (d, J 11.4 Hz, 1 H,
OCH2C6H5), 4.36 (d, J2H6a,6 2.9 Hz, 2 H, 2
H-6a), 4.27 (d, J 11.4 Hz, 1 H, OCH2C6H5),
4.25 (dm, J2,2% 12.5 Hz, 1 H, H-2), 3.80 (dd,
J5,6 9.0, J5,4a 5.9 Hz, 1 H, H-5), 3.53 (dt, J4a,7b
8.9, J4a,4 =J4a,5 7.6 Hz, 1 H, H-4a), 3.33–3.30
(4S,4aR,5S,6R,7aS,7bS) - 4,4a,5,6,7a,7b-
Hexahydro - 6 - iodomethyl - 5 - phenylmethoxy-
2H-1,7-dioxacyclopent[cd]inden-4-ol benzoate
(37).—Following the ‘General method for
benzoylation’, alcohol 36 (61mg, 0.15 mmol)
gave benzoate 37 (60 mg, 72%) after chro-
matography (7:3 hexane–EtOAc): mp 105–
108 °C; [h]2D5 +125° (c 0.95, CHCl3); IR
(KBr) w 2921, 1712, 1265, 1116, 1014, 717
13
(m, 1 H, H-7b); C NMR (75 MHz, CDCl3):
l 166.2 (2×OCOC6H5), 147.8 (C-2a), 132.9-
127.5 (15 C, 2×OCOC6H5, OCH2C6H5),
123.9 (C-3), 95.2 (C-7a), 84.7 (C-4), 73.0 (C-
5), 72.0 (2 C, OCH2C6H5, C-6), 64.8 (C-6a),
63.8 (C-2), 54.4 (C-7b), 37.4 (C-4a); MS (70
1
cm−1; H NMR (300 MHz, CDCl3): l 7.74
(dd, J 8.2, J 1.1 Hz, 2 H), 7.43 (tm, J 7.5 Hz,
1 H), 7.25 (d, J 7.7 Hz, 1 H) [OCOC6H5],

J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
87
m/z 107 (21), 95 (37), 94 (22), 91 (21), 79 (50),
78 (100), 77 (24), 67 (28), 66 (20), 61 (20).
Anal. Calcd for C11H18O6: C, 53.65; H, 7.37.
Found: C, 53.36; H, 7.39.
eV): m/z 390 (7), 105 (100), 91 (91), 77 (44).
Anal. Calcd for C31H28O7: C, 72.64; H, 5.51.
Found: C, 72.77; H, 5.34.
Reaction of intermediate 9 with MeOH.—
Following the ‘General method for the hy-
drolysis with MeOH in acidic conditions’, 9
(70 mg, 0.23 mmol) gave (1R,2aR,6aS,
6bR,7S,9aS) - 1,2a,3,5,6a,6b,9a - octahydro - 7-
hydroxy-1-methoxy-6-phenyl-4,6-dioxacyclo-
hexa[e]cyclopenta[c]pyran-9-MeOH (39, 57.4
mg, 71%) and (1R,3R,4S,4aR,5S,7aS)-1,3,4,
4a,5,7a-hexahydro-4,5-dihydroxy-cyclopenta-
[cd]pyran-3,7-dimethanol (40, 6 mg, 11%) af-
ter chromatography (from hexane to EtOAc).
Compound 39: oil; IR (KBr) w 3414, 1380,
(1R,2aR,6aS,6bR,7S,9aS) - 7 - Benzoyloxy-
1,2a,3,5,6a,6b,7,9a - octahydro - 1 - methoxy - 5-
phenyl - 4,6 - dioxacyclohexa[e]cyclopenta[c]-
pyran-9-methanol benzoate (41).—Following
the ‘General method for the benzoylation re-
action’, 39 (185 mg, 0.55 mmol) afforded 41
(285 mg, 95%) after chromatography (9:1 hex-
ane–EtOAc): mp 60–63 °C; [h]2D5 +107° (c
0.25, CHCl3); IR (KBr) w 1719, 1269, 1103,
1026, 712 cm−1; 1H NMR (300 MHz, CDCl3):
l 8.10–7.20 (m, 15 H, 2×OCOC6H5, C6H5),
6.23 (d, J8,7 1.8 Hz, 1 H, H-8), 6.09 (dd, J7,6b
7.1, J7,8 1.8 Hz, 1 H, H-7), 5.54 (s, 1 H, H-5),
5.08 (dd, J9%,9%% 16.0, J9%%,8 1.3 Hz, 1 H, H-9%%),
4.97 (d, J9%,9%% 16.0 Hz, 1 H, H-9%), 4.62 (d, J1,9a
8.3 Hz, 1 H, H-1), 4.37 (dd, J3%,3 9.9, J3%,2a 4.9
Hz, 1 H, H-3%), 4.20 (td, J2a,6a =J2a,3 9.9, J2a,3%
4.9 Hz, 1 H, H-2a), 4.05 (dd, J6a,2a 9.9, J6a,6b
7.1 Hz, 1 H, H-6a), 3.75 (t, J3,3%=J3,2a 9.9 Hz,
1 H, H-3a), 3.59 (s, 3 H, OCH3), 3.10 (q,
1
1101, 1084, 1025, 761, 702 cm−1; H NMR
(300 MHz, CDCl3): l 7.51–7.38 (m, 5 H,
C6H5), 5.81 (d, J8,7 2.3 Hz, 1 H, H-8), 5.61 (s,
1 H, H-5), 4.92 (br t, J7,8=J7,OH 2.3 Hz, 1 H,
H-7), 4.56 (d, J1,9a 7.8 Hz, 1 H, H-1), 4.38 (dd,
J3%,3 10.0, J3%,2a 4.4 Hz, 1 H, H-3%), 4.31 (br dd,
J9%%,9% 14.8, J9%%,OH 6.0 Hz, 1 H, H-9%%), 4.25 (br
dd, J9%,9%% 14.8, J9%,OH 6.0 Hz, 1 H, H-9%), 4.15–
4.04 (m, 2 H, H-2a, H-6a), 3.77 (t, J3,3%=J3,2a
10.0 Hz, 1 H, H-3), 3.54 (s, 3 H, OCH3),
2.78–2.74 (m, 2 H, H-6b, H-9a), 2.45 (d, JOH,7
2.3, Hz, 1 H, OH), 2.34 (t, JOH,9% 6.0 Hz, 1 H,
OH); 13C NMR (75 MHz, CDCl3): l 151.0
(C-9), 137.5–126.3 (C6H5), 128.1 (C-8), 107.2
(C-1), 102.7 (C-5), 79.2 (C-6a), 75.7 (C-7),
70.3 (C-3), 67.8 (C-2a), 61.5 (C-9%), 57.0
(OCH3), 50.2 (C-9a)*, 43.3 (C-6b)*; MS (70
eV): m/z 256 (75), 179 (31), 134 (25), 121 (36),
107 (95), 105 (100), 91 (63), 79 (78), 78 (86), 77
(52). Anal. Calcd for C18H22O6: C, 64.66; H,
6.63. Found: C, 64.32; H, 6.56. Compound 40:
oil; [h]2D5 +41° (c 0.95, MeOH); IR (KBr) w
3429, 3250, 1375, 1097, 1056, 1031, 989, 890
cm−1; 1H NMR (300 MHz, CDCl3): l 6.08 (d,
J6,7% 1.8 Hz, 1 H, H-6), 5.03–4.80 (m, 1 H,
H-5), 4.67 (d, J1,7a 8.4 Hz, 1 H, H-1), 4.44 (dd,
J7,7%% 15.8, J7%,6 1.8 Hz, 1 H, H-7%), 4.29 (br d,
J7%%,7% 15.8 Hz, 1 H, H-7%%), 4.10–3.99 (m, 3 H,
H-3a, H-4, H-3), 3.81 (dd, J3a,3a% 11.4, J3a%,3 5.5
Hz, 1 H, H-3a%), 3.67 (s, 3 H, OCH3), 2.79 (q,
J6b,9a=J6b,7=J6b,9a 7.1 Hz, 1 H, H-6b), 2.90
(dd, J9a,1 8.3, J9a,6b 7.1 Hz, 1 H, H-9a); 13C
NMR (75 MHz, CDCl3): l 166.0, 165.9 (2×
OCOC6H5), 147.7 (C-9), 137.1–126.2 (2×
OCOC6H5, C6H5), 126.9 (C-8), 106.4 (C-1),
102.8 (C-5), 77.9 (C-6a), 77.0 (C-7), 69.8 (C-
3), 67.0 (C-2a), 62.5 (C-9%), 56.9 (OCH3), 50.5
(C-9a), 42.1 (C-6b); MS (70 eV): m/z 149 (16),
132 (15), 105 (100), 77 (24). Anal. Calcd for
C32H30O8: C, 70.84; H, 5.57. Found: C, 70.98;
H, 5.80.
Hanessian–Hullar reaction of intermediate
41.—Following the ‘General method for the
Hanessian–Hullar reaction’, 41 (285 mg, 0.53
mmol)
gave
(1R,3R,4S,4aR,5S,7aS)-4,5-
dibenzoyloxy - 3 - bromomethyl - 1,3,4,4a,5,7a-
hexahydro-1-methoxy-cyclopenta[c]pyran-7-
methanol benzoate (42, 208.6 mg, 64%) after
chromatography (9:1 hexane–EtOAc): mp
41–44 °C; [h]2D5 +72° (c 0.8, CHCl3); IR (film)
w 1721, 1451, 1270, 1095, 1069, 1026, 709
1
J
4a,7a=J4a,4=J4a,5 7.0 Hz, 1 H, H-4a), 2.67
cm−1; H NMR (300 MHz, CDCl3): l 8.07–
(dd, J7a,1 8.4, J7a,4a 7.0 Hz, 1 H, H-7a); 13C
NMR (75 MHz, CDCl3): l 152.5 (C-7), 128.4
(C-6), 108.0 (C-1), 79.8 (C-3)*, 76.6 (C-5),
68.0 (C-4)*, 63.6 (C-3a), 61.6 (C-7%), 56.7
(OCH3), 50.6 (C-7a), 46.9 (C-4a); MS (70 eV):
7.28 (m, 15 H, 3×OCOC6H5), 6.13 (d, J6,5 1.8
Hz, 1 H, H-6), 5.98 (dd, J5,4a 7.7, J5,6 1.8 Hz,
1 H, H-5), 5.28 (dd, J4,3 10.0, J4,4a 7.7 Hz, 1 H,
H-4), 5.10 (dd, J7%,7%% 15.8, J7%%,6 1.5 Hz, 1 H,
H-7%%), 4.94 (d, J7%,7%% 15.8 Hz, 1 H, H-7%), 4.71

88
J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
mg, 30%) after chromatography (4:1 hexane–
EtOAc). Compound 44: mp 37–40 °C; [h]D25
+89° (c 0.11, CHCl3); IR (KBr) w 1721, 1272,
(d, J1,7a 8.4 Hz, 1 H, H-1), 4.46 (ddd, J3,4 10.0,
J3,3a 7.7, J3,3a% 2.3 Hz, 1 H, H-3), 3.64 (s, 3 H,
OCH3), 3.56 (dd, J3a%,3a 11.0, J3a%,3 2.3 Hz, 1 H,
H-3a%), 3.42 (dd, J3a,3a% 11.0, J3a,3 7.7 Hz, 1 H,
H-3a), 3.36 (q, J4a,7a =J4a,4=J4a,5 7.7 Hz, 1 H,
H-4a), 2.80 (dd, J7a,1 8.4, J7a,4a 7.7 Hz, 1 H,
H-7a); 13C NMR (75 MHz, CDCl3): l 165.9,
165.6, 165.6 (3×OCOC6H5), 147.9 (C-7);
133.5–128.4 (18 C, 3×OCOC6H5), 126.1 (C-
6), 106.2 (C-1), 77.3 (C-5), 75.3 (C-3), 70.4
(C-4), 62.4 (C-7%), 56.8 (OCH3), 49.9 (C-7a),
42.0 (C-4a), 32.1 (C-3a); MS (70 eV): m/z 297
(11), 258 (10), 106 (10), 105 (100), 77 (21).
Anal. Calcd for C32H29BrO8: C, 61.85; H,
4.70. Found: C, 62.05; H, 4.63.
1
1097, 1069, 1026, 709 cm−1; H NMR (300
MHz, CDCl3): l 8.13–7.23 (m, 20 H, 4×
C6H5), 6.19 (br d, J6,5 2.0 Hz, 1 H, H-6), 6.01
(dd, J5,4a 7.8, J6,6 2.0 Hz, 1 H, H-5), 5.52 (dd,
J4,3 9.8, J4,4a 7.8 Hz, 1 H, H-4), 5.14 (dd, J7%,7%%
15.8, J7%%,6 1.4 Hz, 1 H, H-7%%), 4.98 (d, J7%,7%%
15.8 Hz, 1 H, H-7%), 4.74 (d, J1,7a 8.4 Hz, 1 H,
H-1), 4.68–4.59 (m, 2 H, H-3a%, H-3), 4.45
(dd, J3a,3a% 12.7, J3a,3 6.5 Hz, 1 H, H-3a), 3.61
(s, 3 H, OCH3), 3.43 (q, J4a,7a =J4a,4=J4a,5 7.8
Hz, 1 H, H-4a), 3.01 (dd, J7a,1 8.4, J7a,4a 7.8
13
Hz, 1 H, H-7a); C NMR (75 MHz, CDCl3):
(1R,3R,4S,4aR,5S,7aS)-4,5-Dibenzoyloxy-
1,3,4,4a,5,7a-hexahydro-3-iodomethyl-1-meth-
oxy-cyclopenta[c]pyran-7-methanol benzoate
(43).—Following the ‘General method for the
iodination’, bromide 42 (345 mg, 0.56 mmol)
gave 43 (272 mg, 73%) after chromatography
(17: 3 hexane–EtOAc,): oil; IR (KBr) w 1720,
l 166.1–165.7 (4×OCOC6H5), 147.8 (C-7),
133.3–128.3 (24 C, 4×OCOC6H5), 126.3 (C-
6), 106.2 (C-1), 77.6 (C-5), 73.5 (C-3), 68.8
(C-4), 64.4 (C-3a), 62.5 (C-7%), 56.8 (OCH3),
49.8 (C-7a), 43.0 (C-4a); MS (70 eV): m/z 149
(16), 132 (15), 105 (100), 77 (24). Anal. Calcd
for C39H34O10: C, 70.69; H, 5.17. Found: C,
70.52; H, 5.13. Compound 45: oil; IR (KBr) w
1
1631, 1270, 1093, 710 cm−1; H NMR (300
MHz, CDCl3): l 8.08–7.51 (m, 15 H, 3×
OCOC6H5), 6.15 (d, J6,5 1.8 Hz, 1 H, H-6),
5.99 (dd, J5,4a 7.5, J5,6 1.8 Hz, 1 H, H-5), 5.21
(dd, J4,3 9.4, J4,4a 7.8 Hz, 1 H, H-4), 5.12 (dd,
J7%,7%% 15.9, J7%%,6 1.6 Hz, 1 H, H-7%%), 4.96 (br d,
J7%,7%% 15.9 Hz, 1 H, H-7%), 4.73 (d, J1,7a 8.4 Hz,
1 H, H-1), 4.39 (td, J3,4=J3,3a 9.4, J3,3a% 2.4
Hz, 1 H, H-3), 3.69 (s, 3 H, OCH3), 3.40 (dd,
J3a%,3a 10.9, J3a%,3 2.4 Hz, 1 H, H-3a%), 3.37 (q,
2920, 1720, 1451, 1268, 1109, 1026, 709 cm−1
;
1H NMR (300 MHz, CDCl3): l 8.10–7.29 (m,
15 H, 3×OCOC6H5), 6.20 (dm, J5,4a 8.0 Hz, 1
H, H-5), 6.06 (q, J 1.6 Hz, 1 H, H-6), 6.03 (d,
J4,5 4.6 Hz, 1 H, H-4), 5.19 (d, J1,7a 5.6 Hz, 1
H, H-1), 5.13 (dq, J7%%,7% 14.8, J7%%,6 1.2 Hz, 1 H,
H-7%%), 4.99 (dm, J7%,7%% 14.8 Hz, 1 H, H-7%), 4.58
(d, J3a%,3a 0.8 Hz, 1 H, H-3a%), 4.58 (d, J3a,3a% 0.8
Hz, 1 H, H-3a), 3.54 (s, 3 H, OCH3), 3.36
(ddd, J4a,7a 9.2, J4a,5 8.0, J4a,4 4.6 Hz, 1 H,
H-4a), 3.27–3.22 (m, 1 H, H-7a); 13C NMR
(75 MHz, CDCl3): l 166.2, 166.0, 165.1 (3×
OCOC6H5), 142.9 (C-7), 153.5 (C-3), 133.3–
128.1 (18 C, OCOC6H5), 129.0 (C-6), 101.3
(C-1), 92.1 (C-3a), 77.6 (C-5), 67.4 (C-4), 61.8
(C-7%), 56.8 (OCH3), 49.7 (C-7a), 40.7 (C-4a);
MS (70 eV): m/z 192 (6), 105 (100), 77 (22).
Anal. Calcd for C32H30O8: C, 70.84; H, 5.57.
Found: C, 70.72; H, 5.41.
Ferrier reaction of intermediate 45.—Com-
pound 45 (43 mg, 0.08 mmol) was dissolved in
dry acetone (2.6 mL, 0.03M), HgCl2 (24 mg,
0.08 mmol, 1 equiv) was added, and the mix-
ture was refluxed for 2 h 30 min; then, more
HgCl2 (24 mg, 0.08 mmol, 1 equiv) was added,
and the reaction was warmed for 2 h. The
mixture was cooled, water was added and the
J
4a,7a=J4a,4=J4a,5 7.5 Hz, 1 H, H-4a), 3.20
(dd, J3a,3a% 10.9, J3a,3 9.4 Hz, 1 H, H-3a), 2.98
(dd, J7a,1 8.4, J7a,4a 7.5 Hz, 1 H, H-7a); 13C
NMR (75 MHz, CDCl3): l 165.9, 165.9, 165.6
(3×OCOC6H5), 147.9 (C-8), 133.5–128.4 (15
C, 3×OCOC6H5), 126.0 (C-6), 106.3 (C-1),
77.3 (C-5), 75.7 (C-3), 71.8 (C-4), 62.5 (C-7%),
56.9 (OCH3), 50.1 (C-7a), 42.3 (C-4a), 4.8
(C-3a); MS (70 eV): m/z 481 (24), 259 (12),
237 (24), 106 (28), 105 (100), 77 (62), 51 (14).
Anal. Calcd for C32H29IO8: C, 57.50; H, 4.37.
Found: C, 57.62; H, 4.59.
Reaction of intermediate 43 with AgF.—
Following the ‘General method for the elimi-
nation with this reagent’, 43 (403 mg, 0.6
mmol) afforded 44 (75 mg, 19%) and
(1R,4S,4aR,5S,7aS)-4,5-dibenzoyloxy-1,4,4a,
5,7a-pentahydro-1-methoxy-3-methylene-cy-
clopenta[c]pyran-7-methanol benzoate (45, 99

J. Marco-Contelles, J. Ruiz-Caro / Carbohydrate Research 335 (2001) 71–90
89
OCOCH3); 13C NMR (75 MHz, CDCl3): l
200.5 (C-5), 169.9 (2 C), 165.9, 165.6 (3×
OCOC6H5, OCOCH3), 145.3 (C-1), 133.4–
128,3 (18 C, 3×OCOC6H5), 129.0 (C-2), 77.2
(C-3), 71.9 (C-4), 68.4 (C-7), 61.3 (C-1a), 49.7
(C-3a), 42.0 (C-7a), 40.3 (C-6), 21.3
(OCOCH3); MS (70 eV): m/z 387 (7), 264 (42),
160 (23), 105 (100), 77 (53). Anal. Calcd for
C32H28O9: C, 69.06; H, 5.07. Found: C, 69.19;
H, 5.31.
mass was extracted with EtOAc. The organic
phase was washed with an aq NaHCO3 solu-
tion, brine, dried with Na2SO4, filtered and the
solvent was evaporated. The residue was sub-
mitted to chromatography (from 3:2 hexane
to hexane–EtOAc) affording (3S,3aS,7aS)-1-
benzoyloxymethyl-3,4-bis-(benzoyloxy)-3,3a,4,
6,7,7a-hexahydro-7-hydroxy-5H-inden-5-one
(46, 15.7 mg, 34%): oil; [h]2D5 +161° (c 0.29,
CHCl3); IR (film) w 3444, 2929, 2869, 1715,
1671, 1601, 1451, 1315, 1267, 1108, 1070,
1026, 711 cm−1; 1H NMR (300 MHz, CDCl3):
l 8.07 (dd, J 7.8, J 0.8 Hz, 2 H), 7.92 (dd, J
7.2, J 1.2 Hz, 2 H), 7.87 (dd, J 7.2, J 1.3 Hz,
2 H), 7,60 (tm, J 7.5 Hz, 1 H), 7.56–7.40 (m,
6 H), 7.32 (br t, J 7.7 Hz, 2 H), 6.21–6.19 (m,
2 H, H-4, H-2), 6.16 (d, J3,3a 7.7, J3,2 2.5 Hz, 1
H, H-3), 5.10 (br s, 2 H, 2 H-1a), 4.52–4.49
(m, 1 H, H-7), 3.32 (q, J3a,3=J3a,7a=J3a,4 7.7
Hz, 1 H, H-3a), 3.37 (dd, J7a,3a 7.7, J7a,7 4.0
Hz, 1 H, H-7a), 2.93 (dd, J6,6% 16.2, J6,7 3.3 Hz,
1 H, H-6), 2,84 (dd, J6%,6 16.2, J6%,7 6.1 Hz, 1 H,
H-6%), 2.71 (d, JꢀOH,7 3.2 Hz, 1 H, OH); 13C
NMR (75 MHz, CDCl3): l 201.7 (C-5), 166.3
(3×OCO C6H5), 147.4 (C-1), 133.5–128.3 (18
C, 3×OCOC6H5), 127.9 (C-2), 77.2 (C-3),
72.6 (C-4), 68.4 (C-7), 61.9 (C-1a), 52.2 (C-
7a), 43.2 (C-3a), 42.6 (C-6); MS (70 eV): m/z
404 (3), 282 (15), 160 (57), 106 (309, 105 (100),
77 (62). Anal. Calcd for C30H26O8: C, 70.03;
H, 5.09. Found: C, 69.94; H, 4.92.
Acknowledgements
J.R.C. is a fellow of the CAM.
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