Approach towards highly oxygenated cis-decalins from sugar allyltins

Article abstract of DOI:10.1080/07328300600732782

A convenient method for the preparation of sugar allyltin derivatives and their application in stereocontrolled synthesis of highly oxygenated, optically pure carbobicyclic derivatives is presented. Special attention is focused on stereoselective transfor

Full text of DOI:10.1080/07328300600732782

This article was downloaded by: [Colorado College]
On: 16 October 2014, At: 17:24
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office:
Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Carbohydrate Chemistry
Publication details, including instructions for authors and subscription
information:
http://www.tandfonline.com/loi/lcar20
Approach Towards Highly Oxygenated
cis‐Decalins from Sugar Allyltins
Sławomir Jarosz a & Marcin Nowogródzki a
a Institute of Organic Chemistry , Polish Academy of Sciences , Kasprzaka,
Warszawa
Published online: 17 Aug 2006.
To cite this article: Sławomir Jarosz & Marcin Nowogródzki (2006) Approach Towards Highly
Oxygenated cis‐Decalins from Sugar Allyltins, Journal of Carbohydrate Chemistry, 25:2-3, 139-149, DOI:
10.1080/07328300600732782
To link to this article: http://dx.doi.org/10.1080/07328300600732782
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”)
contained in the publications on our platform. However, Taylor & Francis, our agents, and our
licensors make no representations or warranties whatsoever as to the accuracy, completeness, or
suitability for any purpose of the Content. Any opinions and views expressed in this publication
are the opinions and views of the authors, and are not the views of or endorsed by Taylor &
Francis. The accuracy of the Content should not be relied upon and should be independently
verified with primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities
whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or
arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any substantial
or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or
distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use
can be found at http://www.tandfonline.com/page/terms-and-conditions

Journal of Carbohydrate Chemistry, 25:139–149, 2006
Copyright # Taylor & Francis Group, LLC
ISSN: 0732-8303 print 1532-2327 online
DOI: 10.1080/07328300600732782
Approach Towards Highly
Oxygenated cis-Decalins
from Sugar Allyltins
´
Sławomir Jarosz and Marcin Nowogrodzki
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka, Warszawa
A convenient method for the preparation of sugar allyltin derivatives and their appli-
cation in stereocontrolled synthesis of highly oxygenated, optically pure carbobicyclic
derivatives is presented. Special attention is focused on stereoselective transformations
of the precursors obtained directly from sugar allyltins.
Keywords Sugars, Allyltin derivatives, Carbocyclic derivatives, Rearrangement,
Mechanism
INTRODUCTION: FROM HIGHER CARBON SUGARS TO
CARBOBICYCLIC SYNTHONS
Higher carbon sugars apart from C-disaccharides are attractive targets, and
their synthesis has gained considerable attention in the past two decades. A
number of methods leading to such complicated molecules have been devel-
oped.[1,2] In the past several years, we proposed a general methodology for
the preparation of higher carbon sugars by coupling of two sugar subunits.
The precursor 5 is readily obtained from sugar phosphoranes 1, phosphonates
2, or vinyltin derivatives of monosaccharides 4 (Fig. 1).[2] Higher carbon sugars
can be, eventually, obtained also from homoallylic alcohols 6, which can be
prepared directly from sugar allyltin derivatives 3.[3–5]
However, the latter process is not trivial. In the typical reaction of the
D-gluco-configurated allyltin 7 with the aldehyde 8, the expected homoallylic
alcohol 9 was formed as a minor product; the main turned out to be dienoalde-
hyde 10, resulting from a controlled fragmentation of 7 (Sch. 1).[3]
Received November 23, 2005; accepted January 31, 2006.
Address correspondence to Sławomir Jarosz, Institute of Organic Chemistry, Polish
Academy of Sciences, Kasprzaka 44, 01-224, Warszawa. E-mail: sljar@icho.edu.pl
139

´
S. Jarosz and M. Nowogrodzki
140
Figure 1: Methods for the preparation of higher carbon sugars.
This result opened a new, very interesting possibility for stereocontrolled
synthesis of highly functionalized enantiomerically pure carbocyclic com-
pounds (see “Synthesis of carbobicylic highly oxygenated derivatives from
sugar allytins”).
SYNTHESIS OF SUGAR ALLYLTIN DERIVATIVES
Organotin derivatives are, nowadays, useful reagents in modern organic chem-
istry.[6–9] Although known for more than 150 years,[9] they became useful
synthons only since mid-1960s when Kuivila et al.[10] discovered that trialkyl-
tin hydrides react with alkyl halides according to a radical-chain mechanism
involving short-lived trialkyltin radicals. This led to elaboration of one of the
Scheme 1: i. TiCl4, CH2Cl2, 2 788C.

Approach Toward Highly Oxygenated cis-Decalins
141
most convenient methods for deoxygenation of secondary alcohols—the
Barton-McCombie reaction.[11] Special attention is directed to the preparation
and application of allyltin derivatives, useful precursors of homoallylic
alcohols.[12] Very interesting are sugar allyltins, which may be prepared most
conveniently by a C(3) þ C(0) strategy, that is, reaction of properly activated
allyl derivative (a C3 fragment) with tin electrophile, nucleophile, or radical
(a C0 fragment).[13]
The ‘Xanthate’ Method of the Preparation of Sugar Allyltins
One of the most convenient methods consists of conversion of allylic
alcohols into xanthates followed by sigmatropic thermal [3,3] rearrange-
ment into dithiocarbonates and reaction with Bu3SnH, leading finally
to allyltins usually as a mixture of geometrical isomers.[14] This method
is most suitable for the preparation of sugar allyltin derivatives.
First such derivative was prepared by Mortlock and Thomas from
D-glyceraldehyde.[15]
Soon after this we reported on the synthesis of the more complicated
derivative 7 using the same methodology[3] (Sch. 2). By this method a
number of sugar organometallics, derivatives of pyranoses and furanoses,
were prepared in good yields.[16,17] The important feature of this methodology
was formation of a mixture of sugar allyltins with the E-isomer highly predo-
minating regardless of the geometry across the double bond in starting
allylic alcohol. As we proved, a mixture of the same composition of the E/Z
isomers was obtained either from the pure E or pure Z or a 1:1 mixture of
both isomers.[18]
Scheme 2: i. 1. Ph3P55CHCO2Me; 2. DIBAL-H; 3. NaH/CS2/Mel; ii. 808C (ref. 15) or 1108C (ref. 3);
iii. Bu3SnH.

´
S. Jarosz and M. Nowogrodzki
142
Tin Nucleophiles in the Preparation of Sugar Allyltins
Although the ‘xanthate’ method is highly reproducible and provides sugar
allyltins in good yields, it has one main limitation. The allyltin derivatives
obtained by this method are always mixtures of geometrical isomers with the
E isomers strongly predominating; availability of the Z-isomers is very
limited by this method. However, for many synthetic purposes (e.g., for
reaction with aldehydes under high pressure or at high temperature directed
to homoallylic alcohols[12]) such pure isomers are needed. Pure geometrical
isomers of sugar allyltins may be, eventually, prepared by reaction of the
properly activated allylic derivatives with tin nucleophiles, particularly with
soft tributyltin cuprate (‘Bu3SnCu’).[19]
It was found that reaction of sterically hindered D-galacto-configurated
primary allylic bromides with Bu3SnCu indeed proceeded with the retention
of the configuration across the double bond.[18,20] However, less sterically
hindered sugar electrophiles (derived from D-glucose, or D-mannose) reacted
preferentially in an SN20 mode leading to secondary sugar allyltins in reason-
able yields[21] (Fig. 2). We observed that only one secondary isomer was
formed regardless of the configuration across the double bond in starting
allylic derivative 11.[21]
CONTROLLED FRAGMENTATION OF SUGAR ALLYLTINS
Upon treatment with a Lewis acid (preferably ZnCl2), both the primary[16] and
the secondary[21] sugar allyltin derivatives undergo facile fragmentation to the
dienoaldehydes 12 with the E-geometry across the internal double bond.
Thermal stability of both isomers, however, is different. Primary sugar allyltins
are stable up to 2148C (boiling trichlorobenzene), while the secondary isomers
decompose already at 1408C (boiling benzene). From the S-isomers, the main or
exclusive products of the reaction of Bu3SnCu with allylic sugar electrophiles,
the Z-dienoaldehydes 13 are formed (Fig. 3).[21]
Figure 2: Regioselectivity of formation of sugar allyltins.

Approach Toward Highly Oxygenated cis-Decalins
143
Figure 3: Fragmentation of sugar allyltins.
This fact opened a convenient route to carbobicyclic derivatives with the
desired geometry of the ring junction.
SYNTHESIS OF CARBOBICYLIC HIGHLY OXYGENATED
DERIVATIVES FROM SUGAR ALLYLTINS
The idea of the stereoselective preparation of enantiomerically pure bicy-
clo[4.3.0]nonene (14) derivative is shown in Figure 4. Reaction of the E-diene
12 with the simplest stabilized Wittig reagent afforded the corresponding
triene, cyclization of which under high pressure (10kbar) led to the trans deriva-
tive 14-trans. Alternatively, the same sequence performed for the Z-diene 13
provided the cis bicycle 14-cis. Such stereochemistry resulted from the endo-
transition state of this intramolecular Diels-Alder reaction (IMDA).[13]
Compounds 14 prepared above from sugar allyltins (via dienoaldehydes 12
and 13) can, eventually, serve as precursors in the stereoselective synthesis of
highly oxygenated, optically pure derivatives of perhydroindane 15, which
might possess interesting biological properties.[22]
Also, more highly oxygenated decalins might be prepared from the same
dienoaldehydes as shown in Scheme 3.
Conversion of the aldehyde 10 into the methyl ester 16 followed by reaction
with dimethyl methylphosphonate anion afforded the phosphonate 17 in good
yield. Further reaction with 2,3-isopropylidene-D-glyceraldehyde (18) under
mild phase transfer conditions furnished the triene 19, which cyclized spon-
taneously to the bicyclic synthon 20.[23] The cis-configuration at the ring
junction was secured by the endo-transition state of this IMDA reaction.

´
S. Jarosz and M. Nowogrodzki
144
Figure 4: Preparation of highly oxygenated bicyclo[4.3.0]nonanes from dienoaldehydes
derived from sugar allyltins.
Functionalization of the double bond in 20 was performed using standard
methodology: cis- or trans-dihydroxylation; the results are shown in Figure 5.
First, reduction of the carbonyl group at the C-5 position was performed
highly stereoselectively with sodium borohydride, and the resulting alcohol
Scheme 3: i. Jones’ oxidation, then CH2N2; ii. MeP(O)(OMe)2, BuLi THF, 15 min, 86%, iii. K2CO3,
toluene, rt, 18-crown-6, 75%.

Approach Toward Highly Oxygenated cis-Decalins
145
Figure 5: Partial functionalization of decalin precursor 20.
21a was osmylated with very high selectivity to compound 22 (Fig. 5).[24] Epox-
idation of the double bond in 21b, the benzyl protected form of alcohol 21a, was
done conveniently with MCPBA, although selectivity of this process was low;
oxiranes 23a and 23b were formed in comparable amounts.[24] Opening,
however, of the three-membered ring with nucleophiles (AcO2, or N32) was
highly regioselective and occurred at the C2 position in 23a and at the C1
position in 23b.[24]
To finish the synthesis of fully oxygenated decalin (e.g., 21) two important
problems had to be solved: oxidation of the allylic position (in 20) and the
cleavage of the C4–C40 bond with insertion of the heteroatom. Functionalization
of the C8 position can be done eventually on two routes: direct allylic oxi-
dation[25] or isomerization of the C1-C2 epoxide under basic conditions.[26]
However, as we observed, both these convenient methods could not be
applied for functionalization of the allylic position in our bicyclic systems.[27]
We decided, therefore, to take advantage of this highly regioselective opening
of the oxirane ring and use the selenium chemistry[28] for functionalization of
the C3 position. For the model study, epoxide 23a[24] was selected, which
should be opened by a nucleophile at the desired C2 position (Sch. 4).
The reaction proceeded as expected. Indeed, the opening of the three-
membered ring occurred at the C2 position to give selenium intermediate 27,
which decomposed under oxidative conditions to the allylic alcohol 26. No for-
mation of the alternative isomer 28 resulting from the opening of the oxirane
ring at the C1 position was noted. Its eventual presence was excluded on the
basis of the 13C NMR data, in which no signal of the aliphatic CH2 group (at
the C3 position of 28) was seen.

´
S. Jarosz and M. Nowogrodzki
146
Scheme 4: i. 1.NaBH4, EtOH, (PhSe)2, 5 min, then 23a reflux 2 h; ii. THF, H2O2, 08C to rt,
overnight; 93% overall.
Compound 26 is a powerful synthon for the stereoselective preparation of
different analogs of highly oxygenated decalins. Inversion of the configuration
at the C1 position can be performed with either oxygen or other nucleophile.
Functionalization of the C255C3 double bond can be achieved either by cis-
or trans-dihydroxylation, aminohydroxylation, etc. Also, various heteroatoms
such as N, P, or S can be placed at either position from C1 to C3 of the
skeleton of 26. This will be a subject of further studies.
CONCLUSION
The efficient method for the preparation of highly oxygenated, optically pure
bicyclo[4.3.0]nonenes (e.g., 14) and bicyclo[4.4.0]decenes (e.g., 20) from sugar
allyltin derivatives were reviewed. The allylic fragment in 20 was conveniently
functionalized by epoxidation of the double bond followed by highly regioselec-
tive opening of the oxirane ring and subsequent elimination of selenoxide. The
resulting allylic alcohol 26 will be extremely useful in the preparation of
various stereoisomeric, highly oxygenated decalins.
EXPERIMENTAL
General: NMR spectra were recorded with a Bruker AM 500 spectrometer for
solutions in CDCl3 (internal Me4Si). All resonances were assigned by COSY
(1H-1H), HETCOR, and DEPT correlations. The 1H and 13C aromatic

Approach Toward Highly Oxygenated cis-Decalins
147
resonances occurring at the typical d values were omitted for simplicity. Mass
spectra were recorded with an ESI/MS Mariner (PerSeptive Biosystem) mass
spectrometer. Optical rotations were measured with a Jasco P-1020 polari-
meter at rt. IR spectra (film) were recorded with a Perkin Elmer Spectrum
2000 apparatus. THF was distilled from potassium prior to use. Column chrom-
atography was performed on silica gel (Merck, 70-230). For chromatography
purposes a fraction of mineral oil with a boiling point in the range of 70 to
908C was used as mixture of hexanes. Acetylation reaction was performed
under standard conditions: acetic anhydride, triethylamine, and DMAP as a
catalyst in dry methylene chloride.
Synthesis
of
1(R),4(S),4a(R),5(R),6(S),7(S),8(R),8a(R),40(S)-4-(20,
20-Dimethyl-[10,30]dioxolan-40-yl)-5,6,7,8-tetrabenzyloxy-1,4,4a,5,6,7,8,8a-
octa-hydro-naphthalen-1-ol (26): To a solution of diphenyl diselenide
(32 mg, 0.1 mmol) in anhydrous ethanol (5 mL), sodium borohydride (15 mg,
0.4 mmol) was added in portions under an argon atmosphere until disappear-
ance of the yellow color of the solution. After 5 min, a solution of epoxide
23a[24] (101.2 mg, 0.15 mmol) in a mixture of anhydrous ethanol and THF
(6 mL; 1:1 v/v) was added, and the mixture was boiled under reflux for 2 h. It
was then diluted with THF (10 mL) and cooled to 08C on an ice bath.
Hydrogen peroxide (0.5 mL of a 30% solution in water, 4.4 mmol) was added
dropwise, and the mixture was allowed to warm to rt and then kept at this
temperature overnight. A saturated aqueous solution of sodium carbonate in
water (100 mL) was added, and the aqueous phase extracted with diethyl
ether (4 ꢀ 20 mL) and ethyl acetate (15 mL). The combined organic layers
were washed with concentrated aqueous sodium carbonate in water (50 mL),
dried over anhyd Na2SO4, and concentrated, and the crude product was
isolated by column chromatography on silica gel (Merck, 70-230 mesh) with
4:1 to 3:1 hexane/ethyl acetate to give 26 (94.7 mg, 0.14 mmol, 93%); ESI
HRMS: Calcd [C43H48O7Na]: 669.3292. Found: 669.3260. This compound was
characterized as its acetate 26-Ac. Data for the acetate: [a]2D4 ¼ 28.7
(c ¼ 0.5, CHCl3); IR (CH2Cl2, cm21) 3031, 2916, 1737, 1454, 1368, 1239,
1
1070, 799, 736, 698. H NMR d 6.08 (dd, J3,2 ¼ 10.1, J3,4 ¼ 2.7 Hz, 1H, H-3),
5.88–5.84 (m, 1H, H-2), 5.40 (dd, J ¼ 5.5, 1.9 Hz, 1H, H-1), 5.06–5.00
(m, 1H, H-10), 4.96–4.90 (m, 2H, CH2OPh), 4.83–4.77 (m, 4H, CH2OPh), 4.62
(d, J ¼ 11.3 Hz, 1H, part of AB), 4.50 (d, J ¼ 10.9 Hz, 1H, part of AB), 3.85–
3.78 (m, 2H, H-6, H-50), 3.59–3.53 (m, 3H, H-1, H-50, H-7), 3.36 (dd, J ¼ 11.4,
9.2, 1H, H-8), 2.77–2.72 (m, 1H, H-4), 2.06–2.01 (m, 1H, H-4a), 2.01 (s, 3H,
OAc), 1.88–1.82 (m, 1H, H-8a), 1.41 and 1.21 (2 ꢀ s, 6H, CMe2). 13C NMR d
169.9 (C55O), 138.6, 138.5, 138.1, and 137.8 (4xCIV in Bn), 131.4 (C-4), 124.7
(C-2), 108.6 (CMe2), 86.3 (C-7 or C-5), 83.6 (C-5 or C-7), 82.6 (C-6), 78.1 (C-8),
76.0, 75.8, 75.2 and 73.9 (4xOCCH2Ph), 75.6 (C-40), 66.3 (C-1), 64.7 (C-50),
41.4 (C-8a), 36.9 (C-4), 32.6 (C-4a), 26.0 and 24.5 (CMe2), 21.1 (MeCO).

´
S. Jarosz and M. Nowogrodzki
148
REFERENCES
[1] See, for example: (a) Danishefsky, S.J.; DeNinno, M.P. Totally synthetic routes to
the higher monosac-charides. Angew. Chem. Int. Ed. Engl. 1987, 26, 15–23;
(b) Marshall, J.A. Chiral allylic and allenic stannanes as reagents for asymmetric
synthesis. Chem. Rev. 1996, 96, 31–47; (c) Gyorgydeak, Z.; Pelyvas, I. Monosac-
charide Sugars: Chemical Synthesis by Chain Elongation, Degradation and
Epimerization; (Academic Press), 1998; (d) Liu, H.-M.; Zou, D.-P.; Zhang, F.;
Zhu, W.-G.; Peng, T. Stereo-selective synthesis of new higher carbon sugars from
D-xylose. Eur. J. Org. Chem. 2004, 2103–2106.
[2] For a review see: Jarosz, S. Synthesis of higher carbon sugars via coupling of simple
monosac-charides—Wittig, Horner–Emmons and related methods. J. Carbohydr.
Chem. 2001, 20, 93–107, and references therein.
[3] Jarosz, S.; Fraser-Reid, B. Synthesis of higher sugars via allyltin derivatives of
simple monosaccharides. J. Org. Chem. 1989, 54, 4011–4013.
´
[4] Jarosz, S.; Skora, S.; Szewczyk, K.; Ciunik, Z. Reaction of sugar allyltins with alde-
hydes. A remarkable difference in reactivity between furanose and pyranose orga-
nometallic derivatives. Tetrahedron: Asymm. 2001, 12, 1895–1905.
[5] Jarosz, S.; Szewczyk, K.; Gaweł, A.; Luboradzki, R. Reaction of sugar allyltins with
aldehydes under high pressure. Tetrahedron: Asymm. 2004, 15, 1719–1727.
[6] Sato, T. Anionic organotin compounds in organic synthesis—trialkylstannyl-
lithium and trialkylstannylmethyllithium. Synthesis 1990, 259–270.
[7] (a) Jarosz, S.; Kozłowska, E. Synthesis and application of allyltin derivatives in
organic chemistry. Polish J. Chem. 1998, 72, 815–831; (b) Jarosz, S.;
Zamojski, A. Carbohydrate derivatives containing the carbon-lithium and
carbon-tin bonds. Curr. Org. Chem. 2003, 7, 13–33.
[8] Neumann, W.P. Tri-n-butyltin hydride as reagent in organic synthesis. Synthesis
1987, 655.
[9] Davies, A.L. Organotin Chemistry; Wiley-VCH: Weinheim, New York, 1997
[Second, Completely Revised and Updated Edition, 2004].
[10] Kuivila, H.G.; Menapace, L.W.; Warner, C.R. Reduction of alkyl halides by organo-
tin hydrides. Evidence for a free radical mechanism. J. Am. Chem. Soc. 1962, 84,
3584–3586.
[11] Barton, D.H.R.; McCombie, S.W. A new method for the deoxygenation of secondary
alcohols. J. Chem. Soc. Perkin Trans. 1, 1975, 16, 1574.
[12] (a) Yamamoto, Y.; Yatagai, H.; Ishihara, Y.; Maeda, N.; Maruyama, K. Stereo- and
regiocontrol of acyclic systems via the lewis acid mediated reaction of allylic stan-
nanes with aldehydes. Tetrahedron 1984, 40, 2239–2246; (b) Yamamoto, Y. Acyclic
stereocontrol via allylic organometallic compounds. Acc. Chem. Res. 1987, 20,
243–249; (c) Yamamoto, Y.; Asao, N. Selective reactions using allylic metals.
Chem. Rev. 1993, 93, 2207–2293; (d) Marshall, J.A. Chiral allylic and allenic stan-
nanes as reagents for asymmetric synthesis. Chem. Rev. 1996, 96, 31–48;
(e) Sumida, S.-I.; Ohga, M.; Mitani, J.; Nokami, J. New and stereoselective
synthesis of 1,4-disubstituted buten-4-ols (homoallylic alcohol a-adducts) from the
corresponding -isomers (3,4-disubstituted buten-4-ols) via an acid-catalyzed allyl-
transfer reaction with aldehydes. J. Am. Chem. Soc. 2000, 122, 1310–1313, and
references therein; (f) Fliegel, F.; Beaudet, I.; Watrelot-Bourdeau, S.; Cornet, N.;
Quintard, J.-P. Preparation of a-substituted g-alkoxyallylstannanes from b-tribu-
tylstannyl acrolein acetals: scope of the method and primary rationalization of the
obtained results. J. Organomet. Chem. 2005, 690, 659–673, and references therein.

Approach Toward Highly Oxygenated cis-Decalins
149
[13] For a review, see: Jarosz, S.; Gaweł, A. Sugar allyltin derivatives. Preparation and
application in organic synthesis. Eur. J. Org. Chem. 2005, 3415–3432.
[14] (a) Ueno, Y.; Okawara, M. Desulfurizative stannylation of propargylic or allylic
sulfides via an SH0 process. J. Am. Chem. Soc. 1979, 101, 1893–1894;
(b) Ueno, Y.; Sano, H.; Okawara, M. A new method for the 1,3-hydroxy-transposi-
tion in allylic alcohols via allylic stannanes. Synthesis 1980, 1011–1012.
[15] Mortlock, S.V.; Thomas, E.J. An observation of diastereoface selectivity in thermal
reactions between d-alkoxyallylstannanes and aldehydes. Tetrahedron Lett. 1988,
28, 5343–5346.
[16] Kozłowska, E.; Jarosz, S. From sugar allyltin derivatives to chiral dienoaldehydes
and trienoates. J. Carbohydr. Chem. 1994, 13, 889–898.
´
[17] Jarosz, S.; Skora, S.; Szewczyk, K. A convenient route to enantiomerically pure,
conjugated dienes from sugar allyltin derivatives. Tetrahedron: Asymm. 2000,
11, 1997–2006.
[18] Jarosz, S. Tri-n-butyltin cuprate as a tool for the preparation of stannyl derivatives
of carbohydrates. Tetrahedron 1997, 53, 10765–10774.
[19] Lipshutz, B.H.; Ellsworth, E.L.; Dimock, S.H.; Reuter, D.C. Transmetalation reac-
tions of higher order cyanocuprates: direct formation of trialkyltin cuprates from
tin hydrides which bypasses organolithium intermediates. Tetrahedron Lett.
1989, 30, 2065–2068.
[20] Jarosz, S.; Szewczyk, K.; Zawisza, A. Synthesis and reactivity of sugar allyltin
derivatives. Polish J. Chem. 2003, 77, 985–994.
[21] Jarosz, S.; Szewczyk, K.; Zawisza, A. Synthesis and thermal stability of secondary
sugar allyltin derivatives. Tetrahedron: Asymm. 2003, 14, 1715–1723.
[22] Mehta, G.; Ramesh, S.S. Polycyclitols: synthesis of novel carbasugar and conduritol
analogues as potential glycosidase inhibitors. Tetrahedron Lett. 2001, 42,
1987–1990.
´
[23] Jarosz, S.; Skora, S. A convenient route to enantiomerically pure highly oxyge-
nated decalines from sugar allyltin derivatives. Tetrahedron: Asymm. 2000, 11,
1433–1438.
´
[24] Jarosz, S.; Skora, S. Sugar allyltins in the synthesis of carbobicycles. Preparation of
highly oxygenated enantiomerically pure decalins. Tetrahedron: Asymm. 2001, 12,
1651–1656.
[25] Andrus, M.B.; Lashley, J.C. Copper catalyzed allylic oxidation with peresters. Tet-
rahedron 2002, 58, 845–866.
[26] Magnus, A.; Bertilsson, S.K.; Andersson, P.G. Asymmetric base-mediated epoxide
isomerisation. Chem. Soc. Rev. 2002, 31, 223–229.
[27] Jarosz, S.; Boryczko, B.; Cmoch, P.; Gomez, A.M.; Lopez, C. Synthesis of complex
carbobicyclic compounds from sugar allyltins; functionalization of the allylic
position in bicyclo[4.3.0]nonene derivatives. Tetrahedron: Asymm. 2005, 16,
513–518.
[28] Sharpless, K.B.; Lauer, R.F. Mild procedure for the conversion of epoxides to allylic
alcohols. First organoselenium reagent. J. Am. Chem. Soc. 1973, 95, 2697–2699.