A convenient route to enantiomerically pure highly oxygenated decalins from sugar allyltin derivatives

Article abstract of DOI:10.1016/S0957-4166(00)00084-7

Preparation of enantiomerically pure, highly oxygenated decalins via tandem Wittig-type Diels-Alder reactions from the corresponding sugar-derived dieno-phosphoranes and/or -phosphonates and sugar aldehydes is described. Application of the phosphonates is more convenient than phosphoranes since the former can be prepared in much higher yields and react with aldehydes under milder conditions. The intermediate trienes resulting from the Wittig-type process undergo spontaneous and highly stereoselective cyclization to the cis-decalins under the reaction conditions.

Full text of DOI:10.1016/S0957-4166(00)00084-7

Tetrahedron: Asymmetry 11 (2000) 1433±1448
A convenient route to enantiomerically pure highly
oxygenated decalins from sugar allyltin derivatives1
S•awomir Jarosz* and Stanis•aw Skora
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warszawa, Poland
Received 14 February 2000; accepted 28 February 2000
Abstract
Preparation of enantiomerically pure, highly oxygenated decalins via tandem Wittig-type Diels±Alder
reactions from the corresponding sugar-derived dieno-phosphoranes and/or -phosphonates and sugar
aldehydes is described. Application of the phosphonates is more convenient than phosphoranes since the
former can be prepared in much higher yields and react with aldehydes under milder conditions. The
intermediate trienes resulting from the Wittig-type process undergo spontaneous and highly stereoselective
cyclization to the cis-decalins under the reaction conditions. # 2000 Elsevier Science Ltd. All rights
reserved.
1. Introduction
Transformation of simple monosaccharides into enantiomerically pure carbocyclic compounds
(the `chiron' approach2) is now one of the most convenient methods for the preparation of highly
oxygenated cyclopentane3 and cyclohexane4 derivatives. Synthesis of more complex enantio-
merically pure carbobicyclic derivatives can be achieved also by this methodology.5,6
The main task in such an approach to enantiomerically pure carbocyclic system from carbo-
hydrates (probably one of the most useful and simplest methodologies) is the preparation of
appropriate sugar-derived reagents±chirons.
Recently, we elaborated a convenient method of the synthesis of chiral dienoaldehydes 1 from
sugar allyltins 2.7 Such aldehydes were used for the preparation of chiral cyclopentane deriva-
tives8 3 and Ð after conversion into trienes 4 (by reaction with appropriate Wittig or Wittig±
Horner reagents) Ð into enantiomerically pure highly oxygenated bicyclo[4.3.0]nonane deriva-
tives9 5 (Fig. 1).
The readily available dienoaldehydes 1 may serve also as synthons for chiral decalin derivatives
such as 6. This carbocyclic backbone may be found in the molecules of several macrolide antibiotics
* Corresponding author. E-mail: sljar@icho.edu.pl
0957-4166/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0957-4166(00)00084-7

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1434
Figure 1. Preparation of enantiomerically pure carbocyclic derivatives from sugar allyltins
such as nodusmicin (R=H; isolated from Saccharopolyspora hirsuta10) or structurally related
nargenicins (R=2-pyrrolyl-CO-)11 which are active against Gram-positive and drug resistant
bacteria. The elegant and ecient synthesis of nargenicin A1 via intramolecular Diels±Alder
methodology has been recently accomplished by Roush.6a
Application of dienoaldehyde 1 for the preparation of enantiomerically pure, highly oxygenated
decalin system 6 requires a conversion of 1 into 7 (isomeric to 4) followed by an intramolecular
[4+2] cyclization of the latter. In this paper the model study on the stereoselective preparation of
the bicyclo[4.4.0]decane system is presented.
2. Results and discussion
In order to convert the dienoaldehydes 1 into trienes 7 the hydrogen atom of the carbonyl
group should be replaced with the ole®nic moiety (^CHˆCHR grouping). The Wittig-type
methodology (i.e. conversion of simple monosaccharides into sugar phoshoranes12 or phos-
phonates13 and further reaction of such intermediates with sugar aldehydes) applied by us for the
preparation of higher carbon sugars (having up to 21 carbon atoms in the chain14) opens a
convenient route for such a transformation.

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1435
2.1. Preparation of Wittig-type reagents
The synthesis of unsaturated sugar-derived phosphoranes and phosphonates is outlined in
Scheme 1 (exempli®ed by conversion of aldehyde 1a with the d-xylo-con®guration at the three
secondary carbinol centers into 11a and 12a).
Scheme 1. (i) Jones oxidation; (ii) N,N-carbonyl diimidazole, benzene, rt, 15 min; (iii) Ph3PˆCH2 (3 equiv.), benzene,
rt, 2 h, 55% from 8a; (iv) CH2N2; (v) MeP(O)(OMe)2, BuLi, THF, 15 min, 86%
Preparation of the d-xylo-phosphorane 11a (a precursor of ole®n 7, cf. Fig. 1) essentially
followed our method which works satisfactorily in higher sugar chemistry.12 Thus, aldehyde 1a
was oxidized to acid 8a with the Jones reagent and further treated with N,N-carbonyl diimidazole
to a€ord reactive (and unstable) imidazolide 10a. This compound was reacted with an excess of
methylenetriphenylphosphorane (Ph3PˆCH2) yielding the corresponding ylide 11a with the d-xylo-
con®guration. Similarly, ylide 11b (d-lyxo) was prepared from the appropriate aldehyde 1b. Both
ylides 11a and 11b were obtained in ca. 50%; all attempts to optimize the reaction conditions and
to improve the yield of phosphoranes failed.
Sugar phosphonates represent an alternative to the ylides; we have observed, that they are
usually more reactive towards sugar aldehydes and can be prepared in much higher yields than
the corresponding phosphoranes.14 The standard methodology14 was applied for the preparation
of phosphonates 12a±c. Thus, aldonic acids 8a±c were converted into methyl esters 9a±c and

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1436
Scheme 2. (i) Xylene, re¯ux; (ii) toluene, 10 kbar; (iii) K2CO3, 18-crown-6, toluene, rt
treated with dimethyl methylphoshonate anion to a€ord phosphonates 12a±c in ca. 80±85%
yield (Scheme 1).
2.2. Reaction of unsaturated Wittig-type intermediates with sugar aldehydes
Ecient synthesis of a decalin system from carbohydrates requires the solution of at least two
problems. The ®rst one is the elaboration of an ecient method for the preparation of intermediate
trienes, and the second one is concerned with the stereoselective cyclization of these reactive
intermediates. For optimization of the conditions of the process, the reaction of phosphorane 11a
and phosphonate 12a (with the d-xylo-con®guration at the three consecutive stereogenic centers)
with the simplest sugar aldehyde, O-isopropylidene-d-glyceraldehyde 13, was studied (Scheme 2).
We observed, that phosphonate 11a (which can be prepared in only 55% yield) did not react
with aldehyde 13 under the standard conditions12 applied in the preparation of higher carbon
sugars, i.e. at room or slightly elevated temperature. The Wittig reaction took place at a much
higher temperature (boiling xylene, ca. 140ꢀC) and Ð under these conditions Ð the intermediate
triene 7a underwent spontaneous cyclization a€ording decalin 6a-I as a single stereoisomer in
35% isolated yield; this was the only cyclic product formed.y We observed also signi®cant
decomposition of both substrates at this temperature.
Reaction of 11a with 13 under high pressure (10 kbar) was more ecient and provided the
same stereoisomer in 55% yield, again as the only cyclic product. Much better results were
obtained by using the corresponding phosphonate 12a; reaction of this material with 13 under
y
Numbering of decalins 6: letters a, b, and c refer to the con®guration of the starting phosphonate (d-xylo-, d-lyxo-
and l-arabino-, respectively); numbers: I, II, III refer to the aldehyde partner (13, 14, and 15; see also Scheme 2). The
con®gurations of all decalins 6 were determined by NMR spectroscopy: COSY, HETCOR, NOE and/or NOESY. For
details see Experimental and Schemes 3±5.

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very mild phase transfer conditions (anhydrous toluene, 18-crown-6 at room temperature for 5 h)
a€orded the same cyclic product 6a-I in 75% yield. It must be noted that even under these mild
conditions (rt) cyclization of the intermediate triene occurred spontaneously. This was rather
unexpected, since similar trienes 70 are reported to be stable at room temperature and their
cyclization to a decalin system is induced by high temperature or high pressure or a Lewis acid
catalyst15 (Fig. 2).
Figure 2. (i) 10 kbar, or PhCl re¯ux, or Et2AlCl, 0ꢀC
Only one stereosiomeric decalin was formed in all these reactions; the other important infor-
mation from this model study is that the synthesis of chiral, highly oxygenated decalins can be
performed much more conveniently using unsaturated phosphonates 12 instead of phosphoranes
11. The yields are much higher in the case of 12 (preparation of 12 Ð 80%, reaction with alde-
hyde Ð 75%=60% overall) than for 11 [preparation of 11 Ð 50%, reaction with aldehyde Ð
35% (thermal process) or 50% (high pressure)=18% or 25% overall].
The stereochemical outcome of the reaction of 11a or 12a with the aldehyde having the oppo-
site con®guration at the C-a to the carbonyl group [methyl 2,3,4-tri-O-benzyl-a-d-glucopyranosid-
6-ulose 14] signi®cantly di€ered from that described above (with 13). The reaction was not
selective and a mixture of isomeric decalins 6a-II was formed in this process (Scheme 3).
Scheme 3. (i) Xylene, re¯ux; (ii) toluene, 10 kbar; (iii) K2CO3, 18-crown-6, toluene, rt

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1438
On the basis of these results it might be postulated that the phosphonate 12a or phosphorane
11a having the d-xylo-con®guration form the `matched pair' with the R aldehyde (13) and the
`mismatched pair' with the S aldehyde 14. The results obtained in the reactions of the Wittig-type
reagents having the di€erent con®gurations (d-lyxo-11b and 12b, and l-arabino-12c) raised, however,
the question if this simple statement (`matched mismatched pairs') is correct. The stereochemical
outcome of the condensation of the d-lyxo-phosphorane 11b or phosphonate 12b with 13 and 14
was the same. Decalins 6b-I and 6b-II formed in this reaction had the same con®guration at the
three newly created stereogenic centers (at C5, C9 and C10) in both cases regardless of the con-
®guration of the aldehyde used (R-13 and S-14). The same trend was observed in reaction of
phosphonate 12c with both 13 and 14. Again, the products: decalins 6c-I and 6c-II had the same
con®gurations at C5,9,10 regardless of the con®guration of the aldehyde used (Scheme 3).
The con®gurations at the newly created stereogenic centers in the latter products (6c-I and 6c-
II) were opposite to those formed in the reaction of the d-lyxo-ylides with aldehydes, namely
decalins 6b-I and 6b-II. It is clear, therefore, that the con®guration of the phosphorane or phos-
phonate itself is responsible for the stereochemical outcome of the formation of decalins 6. To
prove this hypothesis reaction of phosphonates 12a±c with achiral aldehyde was studied.
2.3. Stereochemistry of the reaction of unsaturated phosphonates with achiral aldehyde
The simplest non-chiral sugar-like aldehyde, O-tbutyldiphenylsilyl glycoladehyde16 (15) was
chosen as the carbonyl substrate in the study of this asymmetric tandem Wittig-type Diels±Alder
reaction leading to the [4.4.0]bicyclic system. Aldehyde 15 reacted readily with phosphonates 12
under very mild phase transfer conditions to a€ord the corresponding trienes (cf. Scheme 2)
which underwent spontaneous cyclization under the reaction conditions yielding decalins 6-III.
The results are presented in Scheme 4.
Scheme 4. (i) K2CO3, 18-crown-6, toluene, rt
Reaction of 12a (d-xylo-con®guration) with 15 a€orded decalin 6a-III as a mixture of stereo-
isomers, while the condensation of the two other remaining phosphonates was highly stereo-
selective and led to decalins 6b-III (from 12b) and 6c-III (from 12c) with the same con®guration
at the newly created stereogenic centers as the corresponding products obtained in reactions of

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1439
12b and 12c with chiral aldehydes. It is, therefore, clear that the stereochemistry of the cyclization
process is governed by the con®guration of the pre-existing stereogenic centers in the Wittig-type
reagents and not those in the aldehyde partner.
2.4. Stereochemical aspects of the formation of decalins 6
In all reactions studied in this paper only the cis-decalin system was formed. This is consistent
with the literature data on the excellent cis selectivity in the intramolecular [4+2] cyclization of
1,7,9-decatrien-3-ones.6,17 The transition state shown in Fig. 3 may explain this cis selectivity.
Such arrangement of the reacting parts of the molecule (with the carbonyl group directed inside
the diene system) allows for better overlapping of orbitals and, therefore, should lower the energy
of the transition state of the intramolecular cyclization. Although the intermediate trienes 7 were
not isolated (they underwent spontaneous cyclization under the reaction conditions) the trans
geometry of the conjugated double bond could be expected on the basis of previous results.18
Indeed, the trans relation between H<1> and H<2> protons in the ®nal product 6 proved this
assumption.
Figure 3. The model of the cyclization of decatrienes with the `internal' activation of dienophile
The absolute stereochemistry of the tandem Wittig-type Diels±Alder reaction between unsaturated
phosphonates and aldehydes is explained in Fig. 4. Triene 7a (I or II or III) is formed in the
condensation of the d-xylo-phosphonate 12a with aldehydes 13, 14 (both chiral, but having the
opposite con®guration at the C-a to the carbonyl group) or 15 (achiral), respectively. Similarly,
trienes 7b (I, II, III) and 7c (I, II, III) were formed from phosphonates 12b (d-lyxo) and 12c
(l-arabino). The transition states A and A0 leading to the cis-decalin system are presented in Fig. 4.
Neither transition state in cyclization of 7a is preferred; there are severe steric as well as
Coulombic interactions in both A and A0. So, we should not expect the good selectivity unless the
di€erentiation between both transition states would be possible by a (quite distant) chiral substituent
at the dienophile part. Indeed, no, selectivity was observed in the reaction of 12a with the achiral
reagent (RˆCH2OSiR3), but very high selectivity in the reaction with chiral aldehyde having the
R-con®guration at Ca (13; the opposite aldehyde S-14, however, also did not di€erentiate
between A and A0).
The cyclization process of trienes 7b (d-lyxo) and 7c (l-arabino) is independent of the con®g-
uration of the substituent at the dienophile moiety (which is quite distant). The transition state A0
is preferred over A in the cyclization of 7b and A over A0 in the cyclization of 7c (see Fig. 2).
2.5. Model reaction of unsaturated phosphorus compounds with ꢀ-hydroxyaldehyde
Reaction of phosphorane 11a with 3,4:5,6-di-O-isopropylidene-d-glucose (16, conveniently
prepared from d-gluconolactone in three simple steps19) was studied. The phosphorane reacted more
easily with such a-hydroxyaldehydes than with aldehydes without a free hydroxy group in the

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molecule; at 80ꢀC (boiling benzene) 53% of the cyclic product 6a-V0 was isolated after 20 h (140ꢀC
was required for reaction of 11a with 13, 14, and 15). Moreover, the yield of 6a-V0 was higher
than 6a-I (53% versus 35%). This is connected probably with the subsequent formation of the
additional ®ve-membered ring, i.e. cyclization of the ketoalcohol 6a-IV to lactol 6a-V0 (Scheme 5).
Figure 4. Transition states for cyclization of intermediate trienes 7

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1441
Scheme 5. (i) 16, benzene, re¯ux, 20 h; (ii) 16, K2CO3, 18-crown-6, toluene, rt
Although the hydroxyaldehyde 16 is very unstable even under mild basic conditions,19 it sur-
vived the phase transfer conditions used in the preparation of chiral decalins. Its toluene solution
reacted with phosphonate 12a in the presence of potassium carbonate and 18-crown-6 to a€ord
product 6a-V0 in 75% yield, much better than in the reaction of 16 with phosphorane 11a. Since
in reactions of the d-xylo-phosphorus intermediates with the R-aldehyde only one isomer is
formed (cf. 11a or 12a+13!6a-I), we expected the same selectivity in this reaction. Indeed,
compound 6a-V0 was isolated as the only isomer from the reaction mixture and its con®guration
at the C5, C9 and C10 centers was the same as in 6a-I.
The con®guration of decalin 6a-V0 was also assigned from the high-resolution NMR spectra.
Since the appropriate diagnostic signals overlapped in 6a-V0, the compound was converted into
p-nitrobenzoyl ester 6a-V00 in the spectrum of which the corresponding NOEs between H5±H10
(6%) and H10±H10 (4.5%) were seen. The resonance of the C1 atom was also observed at
d=109.0, which indicated the presence of the ®ve-membered heterocyclic ring in the molecule.
3. Conclusion
The highly oxygenated decalin derivatives 6 could be obtained by reaction of sugar-derived
unsaturated phosphoranes 11a,b or phosphonates 12a±c with aldehydes. The latter process is
more convenient and allows preparing the carbobicyclic products 6 in much higher yields and
under milder conditions. There is no di€erence in the stereochemical outcome of the process

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1442
conducted with either phosphorane or phosphonate (with the same con®guration at the three
carbinol centers). Preparation of decalins 6 from phosphonates or phosphoranes and aldehydes
consists of two steps: (i) formation of a triene intermediate in the Wittig-type reaction and (ii)
cyclization of the latter. The second step (cyclization) occurs spontaneously under the conditions
of the Wittig-type reaction and the intermediate triene cannot be isolated.
The stereochemistry of this tandem Wittig-type Diels±Alder reaction depends solely on the
geometry of the starting phosphoranes or phosphonates having the d-lyxo- and l-arabino-
con®gurations 11b, 12b, and 12c and does not depend on the con®guration of the aldehyde used,
R-13, S-14 or achiral 15. However, for the d-xylo-phosphorus substrates 11a and 12a the situa-
tion is di€erent; the con®guration of the product depends on the con®guration of the aldehyde
used 13 and does not depend on the chirality of the phosphorus substrates.
4. Experimental
4.1. General
NMR spectra were recorded with a Bruker AM 500 spectrometer for solutions in CDCl3 (internal
Me4Si) unless otherwise stated. All resonances were assigned by COSY (1H±1H and 1H±13C) and
DEPT correlations. The relative con®gurations of the protons were determined by NOE or NOESY
experiments. Mass spectra [LSIMS (m-nitrobenzyl alcohol was used as a matrix to which sodium
acetate was added) or EI] were recorded with an AMD-604 (AMD Intectra GmbH, Germany)
mass spectrometer. Speci®c rotations were measured with a JASCO DIP Digital Polarimeter for
chloroform solution (cꢁ1.5) at room temperature. Column chromatography was performed on
silica gel (Merck, 70±230 and 230±400 mesh). Organic solutions were dried over anhydrous magnesium
sulfate. All reactions with BuLi were performed under an argon atmosphere. 2,3,4-Tri-O-benzyl-
oct-5(E),7-dieno-d-xylose 1a, 2,3,4-tri-O-benzyl-oct-5(E),7-dieno-d-lyxose 1b, and 2,3,4-tri-O-benzyl-
oct-5(E),7-dieno-l-arabinose 1c were prepared according to Ref. 7. Aldehydes 13, 14, 15, and 16
were prepared directly before use; 2,3-O-isopropylidene-d-glyceraldehyde 13 by a cleavage of
diacetono-mannitol with NaIO4,20 methyl 2,3,4-tri-O-benzyl-a-d-glucopyranosid-6-ulose 14 by a
Swern oxidation21 of the parent alcohol, O-tbutyldiphenylsilyl glycoladehyde16,22 15 from the
protected allyl alcohol by a cleavage of the double bond with ozone followed by reduction with
Me2S, and 3,4:5,6-di-O-isopropylidene-d-glucose 16 from d-gluconolactone according to Ref. 19.
4.2. Preparation of unsaturated aldonic acids
To a solution of appropriate dienoaldehyde7 1a, 1b, or 1c (1 mmol) in acetone (10 mL) a
solution of Jones reagent23 in water was added until TLC (hexane:ethyl acetate, 3:1) indicated
the disappearance of a starting material and formation of a new very polar product, acid 8a±c.
The mixture was partitioned between ethyl acetate and brine, the organic layer was separated,
washed with water, dried and the crude acid (obtained in ca. 90% yield) was characterized as
methyl ester 9a±c (obtained by reaction of the crude product with diazomethane).
4.2.1. Methyl 2,3,4-tri-O-benzyl-oct-5(E),7-dieno-d-xylonate 9a
1
85%; [ꢀ]D +50. H NMR (200 MHz) ꢁ 6.22 (m, H-6,7), 5.49 (dd, J4,5 7.7, J5,6 14.5, H-5), 5.13
(m, both H-8), 4.22 (dd, J3,4 7.5, H-4), 4.08 (d, J2,3 3.3, H-2), 3.91 (dd, H-3), 3.55 (OMe). 13C

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1443
NMR ꢁ 171.0 (C-1), 136.0, 134.9, 129.9 (C-5,6,7), 118.2 (C-8), 82.0, 80.8, 78.6 (C-2,3,4), 74.9, 73.1,
71.0 (3ÂCH2Ph), 51.7 (OMe). HRMS m/z: 495.2153 [C30H32O5Na (M+Na+) requires 495.2147].
4.2.2. Methyl 2,3,4-tri-O-benzyl-oct-5(E),7-dieno-d-lyxonate 9b
1
79%; [ꢀ]D ^51.9. H NMR (200 MHz) inter alia ꢁ 6.30 (m, H-6,7), 5.67 (dd, J4,5 7.8, J5,6 14.7,
H-5), 5.19 (m, both H-8), 3.62 (OMe). 13C NMR ꢁ 171.5 (C-1), 136.1, 134.6, 130.6 (C-5,6,7),
118.0 (C-8), 82.8, 79.3, 78.4 (C-2,3,4), 74.8, 72.6, 70.6 (3ÂCH2Ph), 51.8 (OMe). HRMS m/z:
495.2124 [C30H32O5Na (M+Na+) requires 495.2147].
4.2.3. Methyl 2,3,4-tri-O-benzyl-oct-5(E),7-dieno-l-arabinate 9c
1
81%; [ꢀ]D +16.9. H NMR (200 MHz) inter alia ꢁ 6.39 (m, H-6,7), 5.68 (dd, J4,5 7.9, J5,6 14.7,
H-5), 5.13 (m, both H-8), 3.9 (dd, J3,4 3.3, H-4), 3.59 (OMe). 13C NMR ꢁ 171.7 (C-1), 136.1,
135.6, 131.3 (C-5,6,7), 118.1 (C-8), 81.7, 78.5, 78.3 (C-2,3,4), 74.3, 73.2, 70.2 (3ÂCH2Ph), 51.7
(OMe). HRMS m/z: 495.2140 [C30H32O5Na (M+Na+) requires 495.2147].
4.3. Preparation of unsaturated phosphoranes
To a solution of the aldonic acid 8a or 8b (1 mmol) in benzene (10 mL) under an argon
atmosphere, N,N0-carbonyldiimidazole (195 mg, 1.2 equiv.) was added in one portion and the
mixture was stirred at room temperature until evolution of the gaseous products ceased (ca. 15
min). This solution of crude imidazolide 10a or 10b was then added to a solution of Ph3PˆCH2 (3
equiv., generated from 1.22 g of Ph3PCH3I and 1.2 mL of 2.5 M BuLi in benzene at rt for 2 h),
the mixture was stirred for 2 h at rt, partitioned between ethyl acetate and brine, the organic layer
was separated, washed with water, dried and concentrated and the product was puri®ed by
column chromatography (hexane:ethyl acetate, 2:1!1:4) to a€ord ylides 11a (55%) or 11b (50%),
respectively. These compounds were characterized only by HRMS: 11a m/z: 717.3131; 11b m/z:
717.3130 [C48H46O4P (M+H+) requires 717.3134].
All attempts to optimize the yield (changing the solvent for THF, lowering the temperature
etc.) failed.
4.4. Preparation of unsaturated phosphonates
To a cooled ^78ꢀC solution of dimethyl methylphosphonate (0.313 mL, 2.93 mmol) in dry THF
(20 mL), a 2.5 M solution of butyllithium in hexane (1.14 mL, 2.85 mmol) was added and the
mixture was stirred at ^78ꢀC for 30 min. Appropriate methyl ester 9a±c (0.6 mmol) was added in
ca. 5 min by a syringe, the mixture was stirred at ^78ꢀC for 30 min, partitioned between ethyl acetate
and brine, the organic layer was separated, washed with water, dried, and concentrated and the
crude phosphonate was isolated by column chromatography (hexane:ethyl acetate, 4:1!1:2).
4.4.1. Dimethyl [2-keto-(3R,4S,5R)-tri-O-benzyl-6(E),8-dienonon-1-yl]phosphonate 12a
1
86%; H NMR (200 MHz) ꢁ 6.24 (m, H-6,7), 5.59 (dd, J4,5 7.8, J5,6 14.5, H-5), 5.15 (m, both
H-8), 4.03 (dd, J3,4 4.4, H-4), 3.70 and 3.64 (2d, JP,H 4.2 and 4.6, 2ÂOMe), 3.36 and 2.91 [both
CH2P(O)(OMe)2 (dd, JH,H 14.5, JH,P 22.0) and (dd, JH,P 20.9)]. 13C NMR ꢁ 200.8 (d, JC,P 6.2, C-
1), 135.9, 134.6, 130.0 (C-5,6,7), 118.2 (C-8), 82.5, 82.1, 79.0 (C-2,3,4), 73.8, 72.8, 71.0
(3ÂCH2Ph), 52.7 and 51.9 (2d, both JC,P 6.3, 2ÂOMe), 38.4 [d, JC,P 128, CH2P(O)(OMe)2].
HRMS m/z: 587.2162 [C32H37O7PNa (M+Na+) requires 587.2175].

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4.4.2. Dimethyl [2-keto-(3S,4S,5R)-tri-O-benzyl-6(E),8-dienonon-1-yl]phosphonate 12b
1
81%; H NMR (200 MHz) ꢁ 6.24 (m, H-6,7), 5.59 (dd, J4,5 8.0, J5,6 14.3, H-5), 5.15 (m, both
H-8), 4.11 (dd, J3,4 6.0, H-4), 3.89 (dd, J2,3 4.0, H-3), 3.71 and 3.69 (2d, JP,H 4.0 and 4.8,
2ÂOMe), 3.46 and 3.02 [both CH2P(O)(OMe)2 (dd, JH,H 14.6, JH,P 20.7) and (dd, JH,P 22.2)].
13C NMR ꢁ 202.8 (d, JC,P 7.0, C-1), 135.8, 135.1, 130.3 (C-5,6,7), 118.3 (C8), 83.7, 83.5, 80.0
(C-2,3,4), 74.5, 72.8, 70.6 (3ÂCH2Ph), 52.7 and 52.6 (2d, both JC,P 6.3, 2ÂOMe), 37.9 [d, JC,P
130, CH2P(O)(OMe)2]. HRMS m/z: 587.21801 [C32H37O7PNa (M+Na+) requires 587.2175].
4.4.3. Dimethyl [2-keto-(3R,4S,5S)-tri-O-benzyl-6(E),8-dienonon-1-yl]phosphonate 12c
1
82%; H NMR (200 MHz) ꢁ 6.37 (m, H-6,7), 5.69 (dd, J4,5 8.1, J5,6 14.1, H-5), 5.20 (m, both
H-8), 4.10 (dd, J3,4 7.1, H-4), 3.85 (dd, J2,3 3.5, H-3), 3.71 and 3.65 (2d, JP,H 7.7 and 7.6,
2ÂOMe), 3.15 [center of multiplet of both CH2P(O)(OMe)2]. 13C NMR ꢁ 203.3 (d, JC,P 6.1, C1),
136.1, 135.9, 130.6 (C-5,6,7), 118.5 (C-8), 84.6, 81.9, 78.9 (C-2,3,4), 74.3, 73.5, 70.1 (3ÂCH2Ph),
52.7 and 52.6 (2d, JC,P 5.8 and 5.9, 2ÂOMe) [d, JC,P 132, CH2P(O)(OMe)2]. HRMS m/z: 587.2207
[C32H37O7PNa (M+Na+) requires 587.2175].
4.5. Reaction of unsaturated phosphoranes with aldehydes
4.5.1. Under atmospheric pressure
To a solution of phosphorane 11a or 11b (0.5 mmol) in xylene (15 mL), appropriate aldehyde
13 or 14 was added (0.5 mmol) and the reaction mixture was boiled under re¯ux for 30 h. After
that time TLC (hexane:ethyl acetate, 1:1) indicated disappearance of the very polar ylide and
formation of a less polar product (under these harsh conditions both, the aldehyde and dieno-
phosphorane underwent considerable decomposition). The solvent was evaporated and the residue
was puri®ed by column chromatography (hexane:ethyl acetate, 5:1!3:1) to a€ord:
. 6a-I (from 11a and 13) in 35% yield as the only cyclic product (for characterization of all
pure isomers see Section 4.7).
. 6a-II (from 11a and 14) in 40% yield as an inseparable mixture of decalins; MS m/z:
923.4149 [C58H60O9Na (M+Na+) requires 923.4135]. Two major products were seen (ratio
ca. 1:1) in the NMR spectra [1H- 3.49, 3.34 (OMe) and 13C- 98.2, 97.7 ppm (C1 of glucose
moiety)]. Signals at 3.10, 2.89 (H5 of both isomers), 34.4, 31.2 ppm (C5), 2.64, 2.46 (H10),
49.9, 43.6 (C10), and 5.85±5.6 (H6,7), 129.8, 127.4, 126.2, 123.0 (C7,8) proved the decalin
structure of both isomers 6a-II.
. 6b-II (from 11b and 14) in 45% yield as the only cyclic product.
4.5.2. Under high pressure
A solution of 11a or 11b (ca. 0.5 mmol) and aldehyde 13 or 14 in a toluene:benzene mixture
(4:1 v/v, 11 mL) was placed in a piston-cylinder type apparatus24 under 10 kbar for 2 days at
room temperature. Products were isolated by column chromatography as described above to
a€ord:
. 6a-I (from 11a and 13) in 55% yield as the only cyclic product.
. 6a-II (from 11a and 14) in 50% yield (ca. 1:1 mixture of isomers, the same as in thermal
reaction).
. 6b-II (from 11b and 14) in 60% yield as the only cyclic product.

Â
S. Jarosz, S. Skora / Tetrahedron: Asymmetry 11 (2000) 1433±1448
1445
4.6. Reaction of unsaturated phosphonates with aldehydes
To a solution of phosphonate 12a, or 12b, or 12c (1 mmol) and aldehyde 13, or 14, or 15 in
anhydrous toluene (20 mL) anhydrous potassium carbonate (ca. 0.5 g) was added followed by a
catalytic amount (ca. 30 mg) of 18-crown-6. The mixture was stirred at room temperature until
TLC (hexane:ethyl acetate, 3:1) indicated disappearance of both starting materials and formation
of a new product (2±6 h). The mixture was diluted with ethyl acetate (30 mL), washed with water,
dried and concentrated and the products were isolated by column chromatography (hexane:ethyl
acetate, 6:1) to a€ord:
. 6a-I (from 12a and 13); 75%.
. 6b-I (from 12b and 13); 75%.
. 6c-I (from 12c and 13); 72%.
. 6a-II (from 12a and 14); 80%; ca. 1:1 mixture of (the same as in 11a+13).
. 6b-II (from 12b and 14); 72%.
. 6c-II (from 12c and 14); 76%.
. 6a-III (from 12a and 15); 63% (inseparable mixture of at least three stereoisomers as
detected by HPLC (hexane:ethyl acetate, 10:1); HRMS for the mixture m/z: 759.3512
[C48H52O5NaSi (M+Na+) requires 759.3481].
. 6b-III (from 12b and 15); 71%.
. 6c-III (from 12c and 15); 60%.
4.7. Characterization of enantiomerically pure decalins 6
4.7.1. (2R,3S,4R,5S,9S,10R)-{1-Keto-2,3,4-tri-O-benzyl-6,7-ene-9-[10(R)-5,5-dimethyl-2,4-di-
oxolane-10-yl]}decalin 6a-I
1
0
0
[ꢀ]D +123.1. H NMR ꢁ 6.01 (m, H-7), 5.75 (m, H-6), 4.65 (d, J2,3 10.2, H-2), 4.03 (dd, J1 ,2
5.5, J2 ,2 8.1, H-20a), 3.90 (m, H-10), 3.82 (dd, J3,4 9.1, J4,5 10.5, H-4), 3.68 (dd, H-3), 3.53 (dd,
0
0
J1 ,2 8.8, H-20b), 2.56 (dd, J9,10 11.8, J5,10 5.6, H-10), 2.42 (m, H-5), 2.19 (m, H-9), 1.78 and 2.01
(2m, both H-8), 1.30 (6H, CMe2). 13C NMR ꢁ 207.0 (C1), 127.8 and 126.0 (C6,7), 109.4 (CMe2),
85.6 (C2), 85.5 (C3), 83.3 (C4), 78.7 (C10), 76.0, 75.7 and 72.8 (3ÂOBn), 67.8 (C20), 53.5 (C10),
38.6 (C5), 37.5 (C9), 27.2 (C8), 26.9 and 26.1 (CMe2) ppm. NOEs: H5±H10 (7%), H5±H3 (4%),
H4±H9 (7%), H2±H9 (7%). HRMS m/z: 591.2762 [C36H40O6Na (M+Na+) requires 591.2723].
0
0
4.7.2. (2S,3S,4R,5R,9R,10S)-{1-Keto-2,3,4-tri-O-benzyl-6,7-ene-9-[10(R)-5,5-dimethyl-2,4-di-
oxolane-10-yl]}decalin 6b-I
[ꢀ]D ^96.6. 1H NMR ꢁ 5.84 and 5.65 (2m, H-6,7), ꢁ4.5 (H-2), 3.96 (dd, J2,3 2.8, J3,4 5.5, H-3), 3.91
(m, H-10), 3.84 (m, H-20a), 3.81 (dd, J4,5 4.2, H-4), 3.50 (m, H-20b), 2.94 (m, H-5), 2.64 (m, H-10), 2.60
(m, H-9), 2.25 and 1.94 (2m, both H-8), 1.37 and 1.32 (CMe2). 13C NMR ꢁ 208.1 (C-1), 128.0 and
124.9 (C-6,7), 108.7 (CMe2), 80.6 (C-2), 79.9 (C-3), 78.1 (C-10), 77.5 (C-4), 73.1, 73.0 and 72.3
(3ÂOBn), 66.6 (C-20), 50.0 (C-10), 37.2 (C-5), 35.1 (C-9), 26.3 (C-8), 26.2 and 25.6 (CMe2). NOESY:
H5±H10, H5±H4, H9±H2. HRMS m/z: 591.2732 [C36H40O6Na (M+Na+) requires 591.2723].
4.7.3. (2R,3S,4S,5S,9S,10R)-{1-Keto-2,3,4-tri-O-benzyl-6,7-ene-9-[10(R)-5,5-dimethyl-2,4-di-
oxolane-20-yl]}decalin 6c-I
[ꢀ]D +31.4. 1H NMR ꢁ 5.65 (m, H-7), 5.15 (dd, J6,7 10.1, J5,6 1.5, H-6), 4.54 (d, J2,3 10.4, H-2),
3.92 (m, H-10,20a), 3.87 (dd, J3,4 2.6, J4,5 3.0, H-4), 3.62 (dd, H-3), 3.50 (m, H-2b0), 2.82 (m, H-5),

Â
S. Jarosz, S. Skora / Tetrahedron: Asymmetry 11 (2000) 1433±1448
1446
2.59 (m, H-10), 2.48 (m, H-9), 2.35 and 2.17 (2m, both H-8), 1.37 and 1.33 (CMe2). 13C NMR ꢁ
206.0 (C-1), 129.8 (C-7), 123.8 (C-6), 108.7 (CMe2), 84.5 (C-2), 80.4 (C-3), 78.9 (C-2), 77.0 (C-10),
74.2, 73.7 and 72.0 (3ÂOBn), 68.0 (C-20), 43.9 (C-10), 35.2 (C-5), 33.8 (C-9), 26.7 and 25.8
(CMe2), 23.5 (C8). NOESY: H5±H10, H5±H4, H9±H2. HRMS m/z: 591.2728 [C36H40O6Na
(M+Na+) requires 591.2723].
4.7.4. (2S,3S,4R,5R,9R,10S)-[1-Keto-2,3,4-tri-O-benzyl-6,7-ene-9-(methyl 2,3,4-tri-O-benzyl-ꢀ-d-
glucopyranosid-5-yl)]decalin 6b-II
1H NMR ꢁ 5.75 (m, H-6,7), 4.52 (d, J1 ,2 3.5, H-10), 4.40 (d, J2,3 2.3, H-2), 4.00 (dd, J2 ,3 9.3,
0
0
0
0
J3 ,4 9.0, H-30), 3.94 (dd, J3,4 6.6, J4,5 4.3, H-4), 3.85 (dd, H-3), 3.62 (dd, J4 ,5 9.6, J5 ,9 5.9, H-50),
3.44 (dd, H-20), 3.38 (OMe), 3.33 (dd, H-40), 3.03 (m, H-5), 2.98 (dd, J9,10 7.0, J5,10 6.4, H-10),
2.91 (m, H-9), 2.39 and 2.06 (2m, both H8). 13C NMR ꢁ 128.9 and 124.5 (C-6,7), 97.6 (C-10), 82.1
(C-30), 81.4 (C-40), 81.1 (C-2), 80.1 (C-20), 79.9 (C-3), 78.1 (C-4), 72.6 (C-50), 56.3 (OMe), 48.5 (C-
10), 37.0 (C-5), 34.5 (C-9), 28.0 (C-8). NOEs: H4±H5 (6%), H4±H10 (3%); NOESY: H5±H10,
H9±H2. HRMS m/z: 923.4146 [C58H60O9Na (M+Na+) requires 923.4135].
0
0
0
0
0
4.7.5. (2R,3S,4S,5S,9S,10R)-[1-Keto-2,3,4-tri-O-benzyl-6,7-ene-9-(methyl 2,3,4-tri-O-benzyl-ꢀ-d-
glucopyranosid-5-yl)]decalin 6c-II
0
[ꢀ]D +40.8. 1H NMR ꢁ 5.56 and 5.08 (2m, H-6,7), 4.48 (d, J1 ,2 3.5, H-1 ), 4.42 (d, J2,3 10.4, H-2),
0
0
3.97 (dd, J2 ,3 9.5, J3 ,4 9.1, H-3 ), 3.80 (dd, J3,4 2.4, J4,5 2.7, H-4), 3.68 (dd, J4 ,5 9.6, J5 ,9 5.6, H-50),
3.58 (dd, H-3), 3.43 (dd, H-20), 3.35 (dd, H-40), 3.31 (OMe), 3.08 (m, H-5), 2.92 (m, H-10), 2.89
(m, H-9), 2.49 and 2.05 (2m, both H-8). 13C NMR ꢁ 206.1 (C-1), 129.8 and 124.2 (C-6,7), 97.8
(C-10), 84.7 (C-2), 82.5 (C-30), 80.6 (C-3), 80.1 (C-20), 80.0 (C-40), 78.6 (C-4), 72.4 (C-50), 55.6
(OMe), 42.2 (C-10), 35.7 (C-5), 30.5 (C-9), 26.0 (C-8). NOESY: H5±H4, H5±H10. Anal. calcd for
C58H60O9: C, 77.31; H, 6.71. Found: C, 77.20; H, 6.61.
0
0
0
0
0
0
0
0
4.7.6. (2S,3S,4R,5R,9R,10S)-[1-Keto-2,3,4-tri-O-benzyl-6,7-ene-9-(t-butyldiphenyl sililoxymethyl-
ene)]decalin 6b-III
1
[ꢀ]D ^63.0. H NMR ꢁ 5.83 (m, H-7), 5.67 (m, H-6), 4.32 (d, J2,3 2.6, H-2), 3.96 (dd, J3,4 5.7,
H-3), 3.89 (dd, J4,5 4.2, H-4), 3.49 (d, J 6.8, both H-10), 2.96 (m, H-5), 2.82 (dd, J9,10 8.8, J5.10 6.2,
H-10), 2.62 (m, H-9), 2.45 and 1.88 (both H-8). 13C NMR ꢁ 208.9 (C-1), 129.6 (C-7), 124.7 (C-6),
81.0 (C-2), 80.3 (C-3), 78.2 (C-4), 73.2, 73.0 and 72.1 (3ÂOBn), 65.8 (C-10), 49.1 (C-10), 36.6
(C-5), 34.9 (C-9), 27.6 (C8) ppm. NOESY: H5±H10, H5±H4, H2±H9, H5±H10, H10±H10. HRMS
m/z: 759.3508 [C48H52O5SiNa (M+Na+) requires 759.3482].
4.7.7. (2R,3S,4S,5S,9S,10R)-[1-Keto-2,3,4-tri-O-benzyl-6,7-ene-9-(t-butyldiphenyl sililoxymethyl-
ene)]decalin 6c-III
[ꢀ]D +12.2. 1H NMR ꢁ 5.52 (m, H-7), 5.09 (dd, J6,7 10.1, J5,6 ꢁ1, H-6), 4.63 (d, J2,3 10.3, H-2),
3.91 (dd, J3,4 2.5, J4,5 3.0, H-4), 3.62 (dd, H-3), 3.54 (dd, J1 ,1 10.0, J1 ,9 10.0, H-10a), 3.46 (dd, J1 ,9
9.9, H-10b), 3.19 (H-10), 2.92 (m, H-5), 2.71 (m, H-9), 2.36 and 1.61 (both H-8). 13C NMR ꢁ 207.8
(C-1), 129.2, (C-7), 124.2 (C-6), 84.9 (C-2), 80.7 (C-3), 78.5 (C-4), 74.3, 73.7 and 72.5 (3ÂOBn),
64.8 (C-10), 42.5 (C-10), 34.0 (C-5), 32.49 (C-9), 24.0 (C-8) ppm. NOESY: H5±H10, H5±H4, H10±
H10a10b; there is also the NOE between H9±H10, but although these protons are in the trans
relation, they are close because of the preferred conformation of the bicyclic system (H9±H10 are
gauche-arranged). HRMS m/z: 759.3546 [C48H52O5SiNa (M+Na+) requires 759.3482]. Anal.
0
0
0
0
.
calcd for C48H52O5Si 1/2H2O: C, 77.28; H, 7.03. Found: C, 77.36; H, 6.88.

Â
S. Jarosz, S. Skora / Tetrahedron: Asymmetry 11 (2000) 1433±1448
1447
4.8. Preparation of decalin 6a-V0
4.8.1. Reaction of ꢀ-hydroxyaldehyde 16 with phosphorane 11a
Under atmospheric pressure: Phosphorane 11a (0.35 g, 0.49 mmol) and aldehyde 16 (0.15 g, 0.58
mmol) in dry benzene (10 mL) were heated under re¯ux until TLC (hexane:ethyl acetate, 1:1)
indicated disappearance of ylide 11a (20 h). Solvent was evaporated under reduced pressure and
the product was isolated by column chromatography (hexane:ethyl acetate, 6:1!3:1) to a€ord
decalin 6-V0 as a single isomer (180 mg, 0.26 mmol, 53%); MS m/z: 721.3349 [C42H50O9Na
(M+Na+) requires 721.3352]. No carbonyl absorption in the IR spectrum of 6a-V0 was observed.
1
In the 500 MHz H NMR spectrum most of the diagnostic signals overlapped, however the
13C NMR data proved the bicyclic structure: 13C NMR inter alia ꢁ 109.8 and 109.0 (2ÂCMe2),
104.2 (C-1), 47.8 (C-10), 37.8 and 37.2 (C-5,9), 27.9 (C-8). For better characterization this
compound was converted into the p-nitrobenzoyl derivative 6-V00 by action of p-nitrobenzoyl
chloride on a solution of 6-V0 in CH2Cl2 in the presence of triethylamine and DMAP.
4.8.1.1. (1R,20R,03S,4R,5S,9S,10R)-{1-O-p-Methoxybenzoyl-2,3,4-tri-O-benzyl-6,7-ene-9-[(1,10-
0
0
0
00
{
anhydro)-(2 ,3 :4 ,5 -di-O-isopropylidene-d-gluco-1 -yl)]}decalin 6-V . 1H NMR ꢁ 6.01 (m, H-7),
5.81 (m, H-6), 4.62 (d, J 10.9, H-10), ꢁ4.1 (H-2), 3.91 (dd, J3,4 9.7, J2,3 10.0, H-3), 3.54 (dd, J4,5
10.8, H-4), 3.19 (dd, J5,10 6.8, J9.10 13.5, H-10), 2.80 (m, H-5), 2.34 (m, H-9), 2.28 and 2.07 (both
H-8), 1.44, 1.42, 1.39 and 1.36 (2ÂCMe2). 13C NMR ꢁ 162.5 (COAr), 128.3 (C-7), 126.7 (C-6),
111.6 and 109.8 (2ÂCMe2), 109.0 (C-1), 86.0 (C-2), 83.5 (C-3), 84.0 (C-4), 82.9 (C-10), 78.0, 77.3
and 76.5 (C-20,30,40), 76.1, 75.6 and 74.7 (3ÂOBn), 67.5 (C-50), 47.1 (C-10), 38.6 (C-9), 38.1 (C-5),
27.2 (C-8), 27.1, 27.0, 26.7 and 25.2 (2ÂCMe2). NOEs: H5±H10 (6%), H10±H11 (4.5%), H10±
H11 (4.2%).
Under high pressure: High pressure reaction of 11a with aldehyde 16 was unsuccessful; only
traces of decalin 6a-V0 was isolated after 24 h under 10 kbar pressure.
4.8.2. Reaction of ꢀ-hydroxyaldehyde 16 with phosphonate 12a
Aldehyde 16 (260 mg, 1 mmol) and phosphonate 12a (680 mg, 1.2 mmol) were dissolved in
anhydrous toluene (15 mL) to which potassium carbonate (0.5 g) and 18-crown-6 (ca. 30 mg)
were added. The heterogeneous mixture was stirred at room temperature for 2 h, partitioned
between ethyl acetate and brine, the organic layer was separated, washed with water, dried and
concentrated and the product was puri®ed as desribed above yielding decalin 6a-V0 (630 mg,
75%), which was converted into 6a-V00 (as in Section 4.8.1).
Acknowledgements
This work was supported by a grant 3T09A 07015 from the State Committee for Scienti®c
Research, which is gratefully acknowledged.
{
Although the systematic name of this compound coined by the C.A. service (not including stereochemistry) is: 4-
nitro-benzoic acid 6,7,8-tris-benzyloxy-2-(2,2,20,20-tetramethyl-4,40-bi-1,3-dioxolanyl-5-yl)-2a,5a,6,7,8,8b-hexahydro-
2H,3H-naphtho-1,8-bc-furan-8a-yl ester, we named 6b-V00 by analogy to other decalins.

Â
S. Jarosz, S. Skora / Tetrahedron: Asymmetry 11 (2000) 1433±1448
1448
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