Synthesis of highly oxygenated carbocyclic derivatives: decalins and cyclohexanes from sugar allyltins

Article abstract of DOI:10.1016/j.tetasy.2007.10.016

Sugar allyltin derivatives are readily converted into the carbobicyclic compounds with precisely defined stereochemistry. Model functionalization of the carbocyclic skeleton in such precursors with the decalin structure provides either highly oxygenated bi- or monocarbocyclic derivatives.

Full text of DOI:10.1016/j.tetasy.2007.10.016

Available online at www.sciencedirect.com
Tetrahedron: Asymmetry 18 (2007) 2674–2679
Synthesis of highly oxygenated carbocyclic derivatives: decalins
and cyclohexanes from sugar allyltins
*
´
Sławomir Jarosz, Marcin Nowogrodzki and Marta Kołaczek
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warszawa, Poland
Received 27 September 2007; accepted 10 October 2007
Abstract—Sugar allyltin derivatives are readily converted into the carbobicyclic compounds with precisely defined stereochemistry.
Model functionalization of the carbocyclic skeleton in such precursors with the decalin structure provides either highly oxygenated
bi- or monocarbocyclic derivatives.
ꢀ 2007 Elsevier Ltd. All rights reserved.
1. Introduction
OH
SnBu3
ref.6
ref. 1
Bu3Sn
Over the past few years, we have described a general meth-
odology for the preparation of highly oxygenated carbobi-
cyclic derivatives from sugar allyltins 2 and 3, which are
readily available from the corresponding allylic alcohols 1
(Fig. 1).1 These organometallics can be regarded as precur-
sors of either fully oxygenated bicyclic (decalins and perhy-
droindanes) or monocyclic (cyclohexane and cylopentane)
sugar mimetics.
O
O
OMe
O
3
2
BnO
1
ZnCl2
140 °C
O
O
O
P
O
OMe
The synthesis and biological properties of such monocar-
bocyclic derivatives are very well documented.2 However,
the chemistry of the bicyclic analogues is almost unex-
plored. Mehta and Ramesh described a convenient route
to the racemic, fully oxygenated bicyclo[4.3.0]nonanes
and bicyclo[4.4.0]decanes and found that such derivatives
might possess interesting inhibitory glucosidase activity.3
The highly oxygenated decalin skeleton can also be found
in the structure of macrolide antibiotics such as nargenicin
A, the synthesis of which in enantiomerically pure form
was realized by Roush in 1996.4
OMe
4
BnO
BnO
BnO
6
5
Ph3P=CHCOR
RCHO
OBn
OBn
hydrindane
skeleton
COR
OBn
decalin
8
R
O
7
OBn
skeleton
Our methodology,1 as shown in Figure 1, allows us to
obtain enantiomerically pure bicyclic derivatives with the
hydrindane and decalin structures. The sugar allyltin
derivatives (either primary 2 or secondary 3) undergo a
controlled fragmentation to E-dienoaldehydes 5 upon
treatment with a Lewis acid (the best being ZnCl2),5,6 while
cis only
trans from 5
cis from 6
Figure 1. Synthesis of highly oxygenated carbobicyclic derivatives from
sugar allyltins.
at high temperature (boiling xylene) the secondary ones 3
are converted into Z-dienoaldehyde 6 (the primary ana-
logues 2 remain unchanged under these conditions).6 These
highly reactive dienes are precursors of enantiomerically
*
Corresponding author. Tel.: +48 22 343 23 22; fax: +48 22 632 66 81;
e-mail: sljar@icho.edu.pl
0957-4166/$ - see front matter ꢀ 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2007.10.016

S. Jarosz et al. / Tetrahedron: Asymmetry 18 (2007) 2674–2679
2675
cleavage
R1
OBn
6
H
OBn
OBn
R
R
5
R1 = halogen, OR
B
H
A
1
8
oxidation at this position is not possible
10
H
O
O
oxidation(?)
O
HO
O
2
2
insertion of
oxygen atom
H
H
12
Ph
LDA
1
1
O
6
6
H
Figure 3. Possible routes of functionalization of the bicyclic precursor 12.
OMOM
OBn
OR
10
BnO
OH
9
Ph
H
B (via a Baeyer–Villiger oxidation12 of the C1-carbonyl
LDA
H
H
generation of
anion from Bn
and opening of
the oxirane
group), see Figure 3.
O
H
These two approaches which open the routes to carbocyclic
sugar mimics will be discussed.
OMOM
OBn
BnO
11
Figure 2. Attempts to oxidize the allylic methylene group.
2.1. Model synthesis of highly functionalized cyclohexane
derivative from adduct 12
pure carbobicycles with well-defined structures. We were
able to prepare cis-decalins 7 and trans- or cis-hydrindanes
8 in good yields (Fig. 1).
The Baeyer–Villiger oxidation,13 which directly converts
ketones to esters (lactones) upon their treatment with per-
oxy reagents, was the most obvious choice for the transfor-
mation of ring B. We decided to apply the simplest oxidant,
that is, m-chloroperbenzoic acid (MCPBA) to introduce an
oxygen atom into the cyclohexane ring B. To avoid possi-
ble epoxidation of the double bond in 12, the olefin was
converted into cis-diol 13 via simple osmylation, which
provided diol 13 as the only product in 72% isolated yield.
Its structure was proven by NMR experiments performed
on diacetate 13a, in which the NOESY correlation peak
between H-4 and H-6 was observed§ (see Scheme 1).
,
1
Proper functionalization of the allylic system either in 7 or
8 should afford the fully oxygenated derivatives including
also the analogues containing heteroatoms other than
oxygen. For example, osmylation of the double bond in
such carbobicyclic precursors led to the cis-diols, while
epoxidation, followed by the opening of the epoxide ring
provided trans-diols in good yields.8 However, derivatiza-
tion of the allylic methylene group in such derivatives
was found to be troublesome. Direct allylic oxidation (or
bromination) did not give any expected product. The
well-known base-induced isomerization of the correspond-
ing epoxides9 was also not applicable to our precursors; for
example, treatment of epoxide 9 with LDA led to the rear-
rangement product 11 instead of the desired allylic alcohol
10 (Fig. 2).10
Treatment of keto-diol 13 with MCPBA resulted in
formation of the Baeyer–Villiger product [m/z: 641.2743 =
C36H42O9Na (M+Na+)]. From two possible structures 14
and 15 the latter was excluded on the basis of the NMR
data. In the COSY spectrum of the Baeyer–Villiger prod-
uct, the lowest resonance (d = 5.31 ppm) corresponded to
the low field signal at d = 4.05 ppm.; moreover it was cou-
pled to only one proton (H-2). These results pointed
unequivocally at the structure 14 and excluded 15 in which
the lowest resonance should be coupled to two high field
resonating protons: H-9 and H-5. Although we were
unable to assign the configuration at the new stereogenic
centre (C-2),– structure 14 was proposed (and not the
epimer at the C-2 position), which is based on the well-
known fact that the configuration is retained during the
Baeyer–Villiger oxidation.14
Herein, we report the functionalization of the decalin of
type 7 leading either to highly oxygenated bicyclic or
monocylic compounds.
2. Results and discussion
Adduct 12 (readily obtained from the corresponding D-glu-
co-configurated allyltin according to Ref. 11) was chosen as
a precursor of a highly oxygenated decalin (after function-
alization of the C6–C8 allylic system in ring A) and a highly
functionalized cyclohexane. The monocyclic derivatives can
be obtained from 12 either by transformation of ring Aà or
§ These protons are in cis-relationship and are relatively close to each
other. In the alternative structure, no such correlation is possible.
Moreover, the stereochemical outcome of this reaction (attack of OsO4
from the ‘upper’ side) is analogous to one observed earlier by us for a
similar bicyclic compound (see Ref. 8).
– For reasons of clarity, we keep the numbering as in precursors 12 and 13
and the extra oxygen atom in ring B in compound 14 is assigned the ‘1a’
label.
The synthesis of enantiomerically pure derivatives of this type of sugars
was first reported by Herczegh, who used a ‘classical’ approach, see Ref.
7.
à This obvious alternative: cleavage of the C6–C7 bond will not be
discussed in this Letter.

2676
S. Jarosz et al. / Tetrahedron: Asymmetry 18 (2007) 2674–2679
Recently we have applied the well established selenium
RO
H
OBn
H
methodology15 for the opening of the epoxide ring in 17,
which provided the expected allylic alcohol 21 in good yield
(Scheme 2).16
H
RO
H
OBn
OBn
OBn
6
4
AcO
AcO
OBn
OBn
i.
H
O
O
NOESY
The isomeric (to 17) epoxide 20 might be a convenient pre-
cursor of olefin 22, a useful building block for the stereose-
lective synthesis of carbobicyclic derivatives bearing a
quaternary carbinol centre. Thus, treatment of oxirane 20
with the phenylselenide anion followed by oxidative
work-up provided alcohol 22 in good yield (Scheme 2).
Its structure was thoroughly verified by NMR analysis per-
formed on its acetate derivative 22a. The signal of the H-7
proton occurring at d = 5.30 ppm correlated to the olefinic
H-6 (d = 6.06 ppm) and two high field resonances (d = 1.85
and 1.45 ppm) in the COSY spectrum of 22a. These two
high field protons correlated to the secondary carbon at
d = 29.2 ppm proving the presence of the CH2– group at
the C-8 position.
O
R
O
12
13a
iii.
13. R = H
13a. R = Ac
ii.
OH
OH
OBn
OBn
OBn
OBn
OBn
H
H
HO
HO
H
4
(S)
5
H
H
H
OBn
2
COSY
1
H
O
O
10
9
O
H
1a
O
O
O
δ > 5.0 ppm
O
O
δ > 5.0 ppm
14
15
Compound 22 is (or should be) a convenient precursor of
highly oxygenated decalins bearing a quaternary carbinol
centre (at C-5) or carbasugars (via a cleavage of the double
bond followed by reduction of the resulting ketone into the
5-CH2 group).
not formed
lowest H resonance δ = 5.31 (d, J = 3.8 Hz)
1H-1H correleation to δ = 4.05 ppm
t
Scheme 1. Reagents and conditions: (i) THF, H2O, BuOH, NMO, OsO4
(cat.), 72%; (ii) Ac2O, py, quant.; (iii) MCPBA, NaHCO3, CH2Cl2, 65%.
Exploring the synthetic potential of the ‘allyltin approach’
to highly oxygenated carbobicycles, we turned our atten-
tion to allylic alcohol 21 with the (R)-configuration at the
carbinol (C-6) centre. Besides the obvious functionalization
of the double bond (osmylation, aminohydroxylation,
epoxidation) this compound can be converted into the C-
6 epimer by simple inversion of the configuration at this
stereogenic centre, which will open a route to new, config-
urationally different, highly oxidized decalins. Treatment of
alcohol 21 with the Mitsunobu reagent17 gave quite unex-
pectedly two products: the desired SN2 product 24a and
the rearranged SN20 alcohol 23 (Scheme 3), although it is
known that the SN20 reaction under the Mitsunobu condi-
tions are very rare.18,19
2.2. Approach to highly oxygenated decalis: functionalization
of the allylic C6–C8 fragment in 12
As pointed out in the Introduction (see also Refs. 1 and
10), the most obvious choice for the oxidation of the allylic
methylene group, that is, direct oxidation or base-catalyzed
rearrangement of the corresponding epoxides, is not appli-
cable to our bicyclic compounds. A solution to this prob-
lem is provided by the highly regioselective opening of
the oxirane ring in the epoxides derived from the bicyclic
olefin 16. Reaction of the nucleophile ðAcOꢀ; N3ꢀÞ with
epoxides 17 and 20 furnished the corresponding trans-diols
or azidoalcohols 18 and 19 in high yields (Fig. 4).8
OBn
HO
OBn
OBn
(R)
H
O
H
H
OBn
OBn
OBn
OBn
O-
OBn
OBn
ref. 16
H 5
H
1
H
H
H
ref. 8
H
ArSe
10
9
17
OBn
OBn
17
OBn
16
1'
O
O
2'
O
21
O
O
R
O
COSY
Nu
H
OBn
+
H
6
COSY
5
RO
H
OBn
OBn
OH
Nu
R
7
H
1
O
8 H
i.
Nu
20
HO
Nu
H
OBn
O
R
R
O
22. R = H
22a. R = Ac
20
18
Nu = N3, OAc
19
Figure 4. Model study on the oxidation of the precursors of highly
Scheme 2. Reagents and conditions: (i) (1) PhSe–SePh, NaBH4, EtOH; (2)
oxygenated decalins.
H2O2, 71% overall.

S. Jarosz et al. / Tetrahedron: Asymmetry 18 (2007) 2674–2679
2677
the attack of the carboxylic acid (ArCOOH = p-nitrobenz-
oic acid) on the allylic system (as activated by the Mitsun-
obu reagent alcohol 21) occurred on the opposite site
(inversion) in an SN2 mode and from the same side (reten-
tion) in an SN20 mode (Scheme 3).
i
21
inversion
ii
RCOO
H
OBn
OBn
H
H
OBn
OBn
OBn
OBn
The addition of the nucleophile from the same side as the
pre-existing OH grouping is in agreement with the recent
observation on such allylic Mitsunobu rearrangements, ob-
H
H
H
+
RCOO
OBn
served during the synthesis of conduritols (Fig. 6).k,
OBn
19
O
O
O
O
23
The expected SN2 compound, alcohol 24, was obtained as
acetate 24b, however, as the only product in the reaction of
the corresponding mesylate with acetate anion. Compound
24b was different from acetate 21-Ac; in the NOESY spec-
trum of 24b no correlation between the H-6 and H-4 was
seen (which were visible in the spectrum of the starting car-
binol 21).
retention
24a. R = p-NO2C6H4-
24b. R = Ac
i, MsCl/py then AcCOONa only 24b;
ii, Ph3P/DEAD/p-NO2-C6H4-COOH ratio 23 : 24a =3 : 2.
Scheme 3.
Work on functionalization of all allylic alcohols 21 and 22
and those obtained after hydrolysis of esters (23 and 24) is
currently in progress and will be reported in due course.
The structure of the rearranged product 23 was proven by
NMR experiments. In the COSY spectrum, the correlation
peak between the olefinic (H-6) and high-field H-5 signals
was observed. The relative cis-relationship between the
H-8 and H-2 was assigned by the corresponding correlation
peak in the NOESY spectrum (Fig. 5). This showed that
3. Conclusion
We have explored the route leading to highly functional-
ized decalins and cyclohexanes from sugar allyltin deriva-
tives. We have observed that the Mitsunobu reaction,
proceeding in most cases in an SN2 mode, afforded a rear-
ranged (SN20) product when applied to the bicyclic allylic
alcohols. Such rearrangements, although reported in the
literature, are rare under the Mitsunobu conditions.
COSY
H
OR
5
H
OR
6
2 OR
H
8
RO
H
R
ArCOO
H
NOESY
23. Ar = p-NO2C6H4-
4. Experimental
4.1. General
Figure 5. Assignment of the configuration of the rearranged Mitsunobu
product.
NMR spectra were recorded with a Bruker AM 500 spec-
trometer for solutions in CDCl3 (internal Me4Si). Most
of the resonances were assigned by COSY (1H–1H) and/
SN2
O
1
or HETCOR and DEPT correlations. The H- and 13C-
O
OBz
PhCO2H
aromatic resonances occurring at the typical d values were
omitted for simplicity. Mass spectra were recorded with an
ESI/MS Mariner (PerSeptive Biosystem) mass spectro-
meter. Optical rotations were measured with a Digital
Jasco polarimeter DIP-360 (k = 589 nm) for solutions in
CHCl3 (c = 1) at room temperature. Column chromato-
graphy was performed on silica gel (Merck, 70-230 or
230–400 mesh). Methylene chloride was distilled from
CaH2 and THF from potassium prior to use. Organic solu-
tions were dried over anhydrous magnesium or sodium
sulfate.
ArCO2
O
Mitsunobu
reagent
O
OBz
+
Ph3P
R-OH
O
PhCO2H
SN2'
O
O
OBz
O2CAr
k This rearrangement is, however, rather an exception. For similar cyclic
allylic alcohols the Mitsunobu inversion proceeded without any
rearrangement (see Ref. 20).
Figure 6. The example of the allylic rearrangement under Mitsunobu
conditions.

2678
S. Jarosz et al. / Tetrahedron: Asymmetry 18 (2007) 2674–2679
4.2. (2R,3S,4R,5R,6S,7R,9S,10R)-{2,3,4-Tri-O-benzyl-6,7-
dihydroxy-1-keto-9-[(10R)-5,5-dimethyl-2,4-dioxolane-10-
yl]}bicyclo[4.4.0]decane 13
solution of epoxide 20 (177 mg, 0.26 mmol) in THF
(2 mL) was added and the mixture was boiled at reflux
for 2 h. After cooling to 5 ꢁC (ice bath), hydrogen peroxide
(30% in water, 1 mL) was added, and the mixture was stir-
red for 24 h at room temperature, and quenched with sat-
urated sodium carbonate (5 mL). Water (100 mL) was
added, and the product was extracted with diethyl ether
(3 · 15 mL). The organic fraction was washed with brine,
dried, concentrated and the product was isolated by col-
umn chromatography (hexane–ethyl acetate, 2:1) to give
olefin 22(126 mg; 71%) as an oil. MS m/z: 699.2
[C43H48O7 (M+Na+)]. Anal. Calcd for C43H48O7: C,
76.31; H, 7.15. Found: C, 76.20; H 7.24. This compound
Osmylation of the double bond was conducted under stan-
dard catalytic conditions.21 To a solution of olefin 1211
(350 mg, 0.62 mmol) in THF (10 mL), tert-butanol
(1 mL) and water (0.1 mL), N-methyl morpholine N-oxide
(100 mg) and osmium tetraoxide (3.1 mL of ca 2% solution
in toluene) were added. The mixture was stirred for 24 h at
room temperature, and partitioned between brine (15 mL)
and ethyl acetate (20 mL). The organic layer was separated
and the aqueous one extracted with ethyl acetate
(2 · 20 mL), and the combined organic solutions were
dried and concentrated. Purification of the crude product
by column chromatography (hexane–ethyl acetate, 2:1)
afforded the title diol 13 as an oil (267 mg, 72%). This com-
1
was further characterized as acetate 22a: [a]D = +19.9; H
NMR d: 6.07 (m, H-6), 5.29 (m, H-7), 4.25, 4.11, 3.80
(4H, H-1, H-2, H-3, H-4), 3.94 (m, H-20), 3.89 (m, H-10),
3.50 (t, J1 2 = J2 a,2 b 8.1, H-20), 2.50 (m, H-10), 2.21 (m,
H-9), 2.00 [s, 3H, C(O)CH3], 1.84 (m, H-8a), 1.45 (m, H-
8b); 13C NMR d: 170.8 [OC(O)CH3], 140.7 (C-5), 123.2
(C-6), 108.9 [C(CH3)2], 81.7, 79.5, 78.6 and 77.1 (C-1, C-
2, C-3, C-4), 78.5 (C-10), 67.7 (C-20), 66.0 (C-7), 38.8 (C-
10), 33.5 (C-9), 29.2 (C-8), 25.8 and 25.7 [C(CH3)2], 21.3
[C(O)CH3].
0
0
0
0
pound was further characterized as
a
diacetate:
[a]D = +17.7; HRMS [ESI] m/z: 709.2990 [C36H44O8Na
(M+Na+) requires 709.2983]. Anal. Calcd for C40H46O10:
1
C, 69.95; H, 6.75. Found: C, 69.62, H, 6.90%. H NMR
d: 5.71 (ꢁt, J5,6 = J6,7 2.7, H-6), 4.98 (m, H-7), 4.62 (d,
J2,3 10.0, H-2), 4.00 (m, H-20a, H-4), 3.89 (m, H-10), 3.66
(dd, J3,4 8.8, H-3), 3.55 (m, H-20b), 2.70 (dd, J9,10 = J5,10
5.0, H-10), 2.28 (m, H-9), 2.10 (m, H-5), 2.08 and 1.99
[2 · s, 2 · C(O)CH3], 1.58 (m, H-8); 13C NMR d: 205.4
(C-1), 169.9 and 169.4 [2 · OC(O)CH3], 109.6 (C-30), 86.7
(C-3), 84.9 (C-2), 78.6 (C-10), 77.1 (C-4), 76.1, 75.6 and
72.8 (3 · OCH2Ph), 68.0 (C-7), 67.6 (C-20), 66.8 (C-6),
51.3 (C-10), 43.6 (C-5), 40.0 (C-9), 27.0 (C-8), 26.7 and
25.9 [C(CH3)2], 20.9 and 20.8 [2 · C(O)CH3].
4.5. Mitsunobu reaction of alcohol 21
A solution of 21 (64 mg, 0.09 mmol), triphenylphosphine
(52.5 mg,
0.2 mmol),
diisopropylazadicarboxylate
(40.5 mg, 0.2 mmol) and 4-nitrobenzoic acid (33.4 mg,
0.2 mmol) in anhydrous THF (10 mL) was stirred for 3
days at room temperature, and then boiled at reflux for
5 h. The reaction mixture was partitioned between satu-
rated sodium bicarbonate (5 mL) and ethyl acetate
(10 mL). The organic phase was separated and the aqueous
one extracted with EtOAc (3 · 10 mL). The combined
organic fractions were washed with brine (2 · 10 mL),
dried, concentrated and the products were isolated by
column chromatography (hexane–ethyl acetate, 3:1) to
afford 23 as an oil (33 mg; 42%) and 24 (23 mg; 29%).
4.3. (2S,3S,4R,5R,6S,7R,9S,10R)-{2,3,4-Tri-O-benzyl-6,7-
dihydroxy-1-keto-9-[(10R)-5,5-dimethyl-2,4-dioxolane-10-
yl]}bicyclo[4.5.0]-2-oxa-undecane 14
Diol 13 (75 mg 0.12 mmol) was dissolved in CH2Cl2
(10 mL) to which NaHCO3 (16 mg) and m-chloroperbenz-
oic acid (89 mg, 55% purity) were added and the mixture
stirred for 16 days at room temperature. The organic layer
was washed with saturated NaHCO3 solution, water, dried,
concentrated and the product was isolated by column chro-
matography (hexane–ethyl acetate, 4:1) to yield lactone 14
(48 mg, 65%) as an oil; [a]D = ꢀ5.1; HRMS m/z: 641.2743
4.6. (1R,2R,3S,4R,5R,8S,9S,10R)-{1,2,3,4-Tetra-O-benzyl-
8-(4-O-p-nitrobenzoyl)-9-[(10R)-5,5-dimethyl-2,4-dioxolane-
10-yl]}bicyclo[4.4.0]dec-6,7-ene 23
1
[C36H42O9Na (M+Na+) requires: 641.2721]. H NMR d:
[a]D = ꢀ1.0; HRMS m/z: 848.3381 [C50H41NO10Na
1
5.31 (d, J3,4 3.8, H-2), 4.52 (m, H-10), 4.14 (m, H-20a),
4.05 (dd, J4,5 3.8, H-3), 3.88 (m, H-4, H-7), 3.64 (m, H-6,
H-10, H-20b), 2.44 (m, H-5), 2.30 (m, H-8a), 2.05 (m, H-
9), 1.61 (m, H-8b), 1.30 and 1.26 [C(CH3)2]; 13C NMR d:
172.6 (C-1), 109.1 (C-30), 104.6 (C-2), 84.4 (C-3), 80.2 (C-
4), 75.9 (C-10), 75.2, 74.3, 71.3 (3 · OCH2Ph), 73.8 (C-6),
68.5 (C-20), 38.8 (C-10), 37.8 (C-9), 37.0 (C-5), 30.0 (C-8),
27.7 and 27.1 [C(CH3)2].
(M+Na+) requires 848.3405]. H NMR d: 6.24 (dd, J5,6
5.5, J6,7 9.9, H-6), 5.86 (dd, J7.8 3.9, H-7), 5.59 (m, H-8),
4.78 (m, H-10), 3.98 (t, J1,2 = J2,3 9.2, H-2), 3.88 (t,
J1 2 = J2 a,2 b 8.8, H-20a), 3.83 (t, J 9.2 , H-4), 3.67 (m,
H-20b, H-3), 3.60 (dd, J1,10 4.4, H-1), 2.78 (m, H-9), 2.36
(m, H-5), 2.12 (m, H-10), 1.18 (m, 6H, [CH3)2C]; 13C
NMR d: 164.3 [Ar-C(O)O-], 134.9 (C-6), 125.7 (C-7),
108.6 [(CH3)2C], 86.6 (C-3), 83.4 (C-4), 81.96 (C-2), 81.90
(C-1), 75.48 (C-10), 70.4 (C-8), 65.7 (C-20), 39.5 (C-9),
38.8 (C-5), 38.0 (C-10), 26.0 and 24.2 [(CH3)2C].
0
0
0
0
4.4. (1R,2R,3S,4R,7S,9S,10R)-{1,2,3,4-Tetra-O-benzyl-7-
hydroxy-9-[(10R)-5,5-dimethyl-2,4-dioxolane-10-yl]}bicyclo-
[4.4.0]dec-5, 6-ene 22
4.7. (1R,2R,3S,4R,5R,6S,9S,10R)-{1,2,3,4-Tetra-O-benzyl-
6-(4-O-p-nitrobenzoyl)-9-[(10R)-5,5-dimethyl-2,4-dioxolane-
10-yl]}bicyclo[4.4.0]dec-7,8-ene 24a
To a solution of diphenyldiselenide (58 mg, 0.19 mmol) in
anhydrous ethanol (5 mL), sodium borohydride was added
in portions (31 mg, 0.82 mmol) and the mixture was stirred
for 15 min until the yellow colour disappeared. Then a
[a]D = ꢀ4.5; HRMS m/z: 848.3442 [C50H41NO10Na
1
(M+Na+) requires 848.3405]. H NMR d: 6.14 (dd, J8,9

S. Jarosz et al. / Tetrahedron: Asymmetry 18 (2007) 2674–2679
2679
2.3, J7,8 10.1, H-8), 5.88 (ddd, J7,9 1.0, J6,7 5.5, H-7), 5.65
(dd, J5,6 1.3, H-6), 5.08 (m, H-10), 3.86 (m, H-2), 3.78 (t,
References
J1 ,2 a = J2 a,2 b = 7.2, H-20a), 3.59 (m, H-1, H-3), 3.52 (t,
H-20b), 3.42 (m, H-4), 2.80 (m, H-9), 2.00 (m, H-5, H-
10), 1.40 and 1.25 (6H, [CH3)2C]; 13C NMR d: 163.6
[CH3C(O)], 132.6 (C-8), 124.0 (C-7),108.6 [(CH3)2C], 86.3
and 83.3 (C-1, C-3), 82.5 (C-2), 77.8 (C-4), 75.5 (C-10),
68.1 (C-6), 64.6 (C-20), 41.4 and 33.1 (C-5, C-10), 37.1
(C-9), 32.6 (C-10), 25.9 and 24.5 [(CH3)2C].
1. Microreview: Jarosz, S.; Gaweł, A. l. Eur. J. Org. Chem. 2005,
3415.
0
0
0
0
2. Selected recent reviews and papers: Arjona, A.; Gomez, A.
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try 2003, 14, 1715.
4.8. Synthesis of the ‘inverted’ alcohol 24 by SN2 reaction of
the corresponding mesylate
To a vigorously stirred solution of alcohol 21 (53.4 mg,
0.079 mmol) in dichloromethane/triethylamine (3:1 v/v,
4 mL) containing catalytic amounts of DMAP (3 mg),
mesyl chloride (90 mg, 0.79 mmol) was added and the
mixture was stirred for 4 h. It was then concentrated and
the crude mesylate was purified by column chromato-
graphy (hexane–diethyl acetate, 3:1) to afford the mesyl-
ation product (40 mg). This was dissolved in DMF
(5 mL) to which sodium acetate (82 mg, 1 mmol) was
added and the reaction mixture was kept at 110 ꢁC until
disappearance of the starting material (3 days). The
mixture was partitioned between water (10 mL) and ether
(20 mL), the organic fractions were collected, washed with
brine, dried, concentrated and the product was isolated by
column chromatography (hexane–ethyl acetate, 3:1) to
afford the desired compound 24b (21 mg; 37%) as an oil.
7. Herczegh, P.; Zsely, M.; Szilagy, L.; Bajza, I.; Kovacs, A.;
Batta, G.; Bognar, R. In Cycloaddition Reactions in Carbo-
hydrate Chemistry; Guliano, R. M., Ed.; ACS Symposium
Series; OUP: Oxford, 1992; Vol. 494, p 112.
´
8. Jarosz, S.; Skora, S. Tetrahedron: Asymmetry 2001, 12,
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9. Crandall, J. K.; Apparu, M. Org. React. 1983, 29, 345.
10. Jarosz, S.; Boryczko, B.; Cmoch, P.; Gomez, A. M.; Lopez,
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´
11. Jarosz, S.; Skora, S. Tetrahedron: Asymmetry 2000, 11,
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M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 7, p 671.
13. Baeyer, A.; Villiger, V. Ber. Dtsch. Chem. Ges. 1899, 32, 3625;
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4.9. (1R,2R,3S,4R,5R,6S,9S,10R)-{1,2,3,4-Tetra-O-benzyl-
6-(O-acetyl)-9-[(10R)-5,5-dimethyl-2,4-dioxolane-10-
yl]}bicyclo[4.4.0]dec-7,8-ene 24b
[a]D = ꢀ13.0; m/z: 741.3 [C45H50O8Na (M+Na+)]. 1H
NMR d: 6.07 (dd, J8,9 2.8, J7,8 10.2, H-8), 5.86 (ddd, J7,9
1.7, J6,7 5.4, H-7), 5.39 (dd, J5,6 = 2.2, H-6), 5.03 (m, H-
10), 3.85-3.78 (m, H-2, H-20), 3.60-3.52 (m, H-4, H-3, H-
20), 3.37 (dd, J 9.1, J 11.5, H-1), 2.75 (m, H-9), 2.06 (m,
H-10), 2.01 [s, CH3C(O)O], 1.85 (m, H-5), 1.41 and 1.21
[6H, (CH3)2C]; 13C NMR d: 169.9 [CH3C(O)], 131.4 (C-
8), 124.7 (C-7), 108.6 [(CH3)2C], 86.3, 83.7 (C-4, C-3),
82.6 (C-2), 78.1 (C-1), 75.6 (C-10), 66.3 (C-6), 64.7 (C-20),
41.4 (C-5), 36.9 (C-9), 32.6 (C-10), 26.0 and 24.5
[(CH3)2C], 21.1 [CH3C(O)].
´
16. Jarosz, S.; Nowogrodzki, M. J. Carbohydr. Chem. 2006, 25,
139.
17. Mitsunobu, O. Synthesis 1981, 1.
18. First observation of the SN20 Mitsunobu rearrangement see:
´
Grynkiewicz, G.; Burzynska, H. Tetrahedron 1976, 32, 2109;
Other examples up to 1996 see: Jarosz, S.; Kozłowska, E.
Carbohydr. Lett. 1996, 2, 213–216, and references cited
therein.
19. Kwon, Y.-U.; Chung, S.-K. Org. Lett. 2001, 3, 3013.
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Chem., Int. Ed. 2007, 46, 2325; O’Brien, P.; Pilgrim, Ch. D.
Org. Biomol. Chem. 2003, 1, 523.
Acknowledgement
This work was financed by the Grant No. PBZ-KBN-126/
T09/07 from the Ministry of Science and Higher Education.
21. VanRheenen, V.; Kelly, R. C.; Cha, D. Y. Tetrahedron Lett.
1976, 1973; Jarosz, S. Carbohydr. Res. 1992, 224, 73.