Direct conversion of 1-deoxy-1-nitroalditols to methyl glycofuranosides

DOI: 10.1016/j.tetlet.2008.03.044

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Tetrahedron Letters p. 3112 - 3116 (2008)

Update date:2022-08-12

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Vojtech Vojtech

Petru?ová

Pribulová

Petru? Petru?

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Article abstract of DOI:10.1016/j.tetlet.2008.03.044

Treatment of the sodium nitronate forms of 1-deoxy-1-nitrohexitols with methanolic sulfuric or hydrochloric acid at -30 °C leads to their regiospecific conversion to the corresponding methyl glycofuranosides. The reaction exhibits more pronounced stereoselectivity for 1-deoxy-1-nitroalditols with the 2,3-erythro configuration than with the 2,3-threo substrates and cis methyl glycofuranosides are the major products. The observed stereoselectivity indicates the lysis of the protonated aci-nitro form which is a two-step process consisting of nucleophilic addition to the protonated carbon-nitrogen double bond followed by the bimolecular nucleophilic substitution of the nitrogen-containing residue.

Full text of DOI:10.1016/j.tetlet.2008.03.044

Available online at www.sciencedirect.com

Tetrahedron Letters 49 (2008) 3112–3116

Direct conversion of 1-deoxy-1-nitroalditols to methyl glycofuranosides

M. Vojtech, M. Petrusˇova, B. Pribulova, L. Petrus

ˇ ^*

Institute of Chemistry, Center for Glycomics, Slovak Academy of Sciences, SK-845 38 Bratislava, Slovakia

Received 22 January 2008; revised 22 February 2008; accepted 7 March 2008

Available online 12 March 2008

Abstract

Treatment of the sodium nitronate forms of 1-deoxy-1-nitrohexitols with methanolic sulfuric or hydrochloric acid at ꢀ30 °C leads to

their regiospeciﬁc conversion to the corresponding methyl glycofuranosides. The reaction exhibits more pronounced stereoselectivity for

1-deoxy-1-nitroalditols with the 2,3-erythro conﬁguration than with the 2,3-threo substrates and cis methyl glycofuranosides are the

major products. The observed stereoselectivity indicates the lysis of the protonated aci-nitro form which is a two-step process consisting

of nucleophilic addition to the protonated carbon–nitrogen double bond followed by the bimolecular nucleophilic substitution of the

nitrogen-containing residue.

Keywords: Nef reaction; Stereoselectivity; 1-Deoxy-1-nitroalditol; Nitronate; Ring-closure reaction; Intramolecular nucleophilic addition; Walden

inversion; Methyl glycofuranoside

Methyl glycofuranosides are important starting

compounds for the synthesis of more complex structures

containing glycofuranosyl building blocks.¹In particular,

D-galactofuranose and D-arabinofuranose-containing cell

surface oligosaccharides endemic to pathogenic micro-

organisms, such as Mycobacteria,²have attracted attention

to the development of new approaches for the treatment

and prevention of diseases caused by these pathogens.³

Two general groups of methods for the synthesis of

methyl glycofuranosides have been known for a long time.

The ﬁrst group is based on kinetically controlled Fischer

glycosidation of free aldoses in methanolic hydrogen chlo-

ride.⁴In the course of the reaction, the concentration

decrease of the starting aldose is associated with a rapid,

but temporary formation of furanosides, which slowly

isomerize to pyranosides.⁵This method is also stereoselec-

tive and preferentially provides 1,2-trans methyl glyco-

furanosides. In the presence of calcium or strontium ions,

which form tridentate complexes with the methoxy and

hydroxyl groups, 1,2-cis glycosides are the major pro-

ducts.⁶In place of the acid catalyst, especially on a

preparative scale, a strongly acidic-cation exchange resin

is used in order to avoid a troublesome removal of acid.

Mostly, however, methyl glycopyranosides are also present

in the reaction mixtures to some extent such that their

separation is necessary.⁷

The other group of methods is based on the starting

aldose dithioacetals and, in spite of the unpleasant prepara-

tion of the starting compounds, these are considered to be

the most convenient for the synthesis of glycofuranosides.⁸

The procedure involves transformation into a monothio-

acetal which is then treated with a thiophilic promoter.⁹

Due to the acyclic structure of the starting compounds

and the neutral conditions for the decomposition of their

thioacetal group they provide the desired ﬁve-membered

ring glycosides unambiguously.⁸The process has also been

extended to the synthesis of furanose-containing

disaccharides.¹⁰

The conversion of the nitronate forms of aliphatic nitro

compounds into carbonyl compounds is a very common

transformation. Although the original Nef procedure,

ﬁrst described in 1894,¹¹involves strong acid-catalyzed

hydrolysis of nitronates, many alternative, non-hydrolytic

Corresponding author. Tel.: +421 2 5941 0232; fax: +421 2 5941 0222.

E-mail address: chemlpet@savba.sk (L. Petrusˇ).

doi:10.1016/j.tetlet.2008.03.044

M. Vojtech et al. / Tetrahedron Letters 49 (2008) 3112–3116

3113

procedures have been developed since.¹²This was mostly

due to the harsh conditions of the conversion (pH<1),

but also because of the failure of the acid-catalyzed hydro-

lysis of the nitronate group alone. Hydrolysis failures were

reported for some multifunctional group compounds,

where the starting nitro derivatives were recovered.^13–15

However, a Nef-type strong acid-catalyzed methanolysis

of the nitronate forms of C-glycosylnitromethanes¹⁶as well

as of some other non-sugar nitro compounds,^12,15which

resist the Nef reaction in water, proceeds smoothly and

dimethyl acetals or ketals of the corresponding carbonyl

compounds were the products. The acid-catalyzed methano-

lysis of nitronates was ﬁrst used because of the increasing

solubility of, and consequently the yields of products from

nitronates of hydrophobic, medium and high molecular

weight nitro compounds.¹⁷Here, we report a simple and

general method for the preparation of methyl glycofuran-

osides, which is based on a strong acid-catalyzed methanoly-

sis of the nitronate forms of 1-deoxy-1-nitroalditols.¹⁸The

starting nitro compounds, the nitronates of which are inter-

mediates of the Sowden procedure for the preparation of

aldoses, can be easily obtained by decationization of the

nitronates, followed by the separation of their epimers by

fractional crystallization,¹⁹or by chromatography on

cation exchange resins in the La³⁺or Ca²⁺forms.²⁰Some

are also available commercially. Scheme 1 illustrates this

general method for preparing 1-deoxy-1-nitrohexitols from

the parent aldopentoses by the nitromethane synthesis, as

exempliﬁed by the preparation of 1-deoxy-1-nitro-^D-

ido-hexitol (1a) and 1-deoxy-1-nitro-^D-gulo-hexitol (1b)

from ^D-xylose.

to a mixture of the corresponding methyl ^D-idofuranosides

2a and 3a.²²

Under the same conditions of kinetic control, similar

behaviour was observed for other 1-deoxy-1-nitrohexitols

and the corresponding mixtures of anomeric methyl hexo-

furanosides, not containing remarkable amounts of any

other sugar compounds (by H NMR), were obtained in

combined ꢁ90% yields (Table 1). All the products were

characterized by ¹H and ¹³C NMR spectral data and

speciﬁc rotation, and by comparison with known methyl

hexofuranosides.^6,23The analysis of the composition of

the reaction mixtures revealed that in all the cases the

1,2-cis methyl hexofuranosides were the major anomers.

Moreover, the predominance of the 1,2-cis anomers was

signiﬁcantly higher in the group of 2,3-cis hexofuranosides

(entries b, d, f and h) than with the 2,3-trans hexofurano-

sides (Table 1, entries a, c, e and g). The observed stereo-

selectivities using this method, which can be considered a

modiﬁed Nef solvolysis, are opposite to the stereoselectivi-

ties obtained using the Fischer glycosidation,⁵and are very

indicative of the lysis mechanism of the protonated nitro-

nate group.

As shown in Scheme 3, for the conversion of 1-deoxy-1-

nitro-^D-manno-hexitol (1d) to methyl D-mannofuranosides

2d and 3d, the ﬁrst step involves activation of the nitro

form via deprotonated nitronate 4d. After acidiﬁcation,

the C-4-OH group intramolecularly attacks the double

bond of the protonated nitronate 5d from the least hin-

dered Si face. The same preference of the Si face attack

is apparent also for 1-deoxy-1-nitrohexitols with ^D-ido, D-

talo and ^D-altro conﬁgurations (entries a, f and g), while

preferential intramolecular addition in the nitronates with

remaining ^D-gulo, D-gluco, D-galacto and D-allo conﬁgura-

tions (Table 1, entries b, c, e and h) proceeds mainly from

the Re face. Moreover, the 2,3-erythro arrangement of the

One-pot treatment²¹of a methanolic solution of 1-

deoxy-1-nitro-D-ido-hexitol (1a, Scheme 2) with sodium

methoxide followed with methanolic sulfuric or hydro-

chloric acid at ꢀ30 °C resulted in its quantitative conversion

NO₂

1. MeNO₂, NaOMe, MeOH

2. H⁺resin, H₂O

Parent aldose

(D-xylose)

Scheme 1.

NO₂

1. NaOMe/MeOH

2. H₂SO₄/MeOH

OMe

Scheme 2.

3114

M. Vojtech et al. / Tetrahedron Letters 49 (2008) 3112–3116

Table 1

Stereoselectivities and yields observed in the H₂SO₄catalyzed methanolysis of the sodium nitronate forms of 1-deoxy-1-nitrohexitols at ꢀ30 °C

Entry

Nitrohexitol (1)

cis-Furanoside (2)

Yield (%)

trans-Furanoside (3)

Yield (%)

NO₂

OMe

NO₂

OMe

NO₂

OMe

NO₂

OMe

NO₂

OMe

NO₂

OMe

NO₂

OMe

NO₂

OMe

hydroxyl groups blocks the reaction site and thus more

discrimination between the respective Re and Si

faces occurs during the addition than with the 2,3-threo

substrate and, consequently, the respective ratios of the

resulting anomeric glycofuranosides diﬀer more clearly.

In the next step, methanol acts as the second, aglycon

nucleophile and, with a Walden inversion at the anomeric

carbon atom, substitutes the hydrated nitroxyl moiety of

6d leading to the formation of the ﬁnal methyl

hexofuranosides.

M. Vojtech et al. / Tetrahedron Letters 49 (2008) 3112–3116

3115

NO₂Na

MeOH

NaOMe

MeOH

- H , - NOH, - H₂O

NO₂

OMe

major (1,2-cis

)

minor (1,2-trans)

Scheme 3.

The stereoselectivity of the transformation, which is

controlled by the structural conﬁgurations of individual

starting compounds, may even change stereospeciﬁcally

as demonstrated by a 5 min treatment of 4d with methano-

lic H₂SO₄at ꢀ50 °C. The only product of this transforma-

tion was methyl b-^D-mannofuranoside (2d) isolated in a

30% yield; the remainder was starting 1-deoxy-1-nitro-^D-

mannitol (1d). On the other hand, if the reaction tempera-

ture was increased to 0 °C, a signiﬁcant amount of methyl

a-^D-mannopyranoside appeared in the reaction mixture.

This may result from the consecutive reactions also accom-

panying the Fischer procedure for the preparation of

glycosides.⁵

The high preference for the observed ﬁve-membered ring

closure over six-membered ring closure during the methan-

olysis of the protonated nitronic acids of 1-deoxy-1-nitro-

alditols is in good agreement with a diﬀerence in the

relative rate constants for closing ﬁve- and six-membered

lactone rings from the respective 4-bromobutanoate and

5-bromopentanoate of about two orders.²⁴However, a

much more convenient model for studying the competitive

ring-closure addition reactions, which are so common in

carbohydrate chemistry, including those occurring in this

novel preparation of methyl glycofuranosides, is strong

acid-catalyzed methanolysis of 1,2-dideoxy-1-nitro-^L-arabi-

no-hex-1-enitol to ^L-arabinofuranosylmethanal dimethyl

acetals.¹⁶This model reaction proceeds cascade-wise and

thus is able to quench reactive intermediates of the cycliza-

tion step forming stable compounds. This study, applied to

the starting compounds of diﬀerent conﬁgurations is in

progress in our laboratory.

lyzed methanolysis of their respective nitronates at ꢀ30 °C.

In addition to the regiospeciﬁcity, which results from pre-

ferential ﬁve-membered ring closure, the new reaction is

also stereoselective. The stereoselectivity of the reactions

led to the conclusion that lysis of the protonated aci-nitro

form involves a two-step process, that is nucleophilic addi-

tion to the protonated carbon–nitrogen double bond in the

ﬁrst step, followed by the bimolecular nucleophilic substitu-

tion of the nitrogen-containing residue in the second step.

Acknowledgements

This work was supported by the APVV-51-046505 and

VEGA-2/6129/26 Grants. The funds for the NMR

measurements were provided by the Slovak State

Programme Project No. 2003SP200280203.

References and notes

1. Lowary, T. L. Curr. Opin. Chem. Biol. 2003, 7, 749.

2. (a) Brennan, P. J.; Nikaido, H. Annu. Rev. Biochem. 1995, 64, 29; (b)

Lindberg, B. Adv. Carbohydr. Chem. Biochem. 1990, 48, 279; (c)

Brennan, P. J. Tuberculosis 2003, 83, 91; (d) Chatterjee, D.; Khoo, K.

H. Glycobiology 1998, 8, 113.

3. (a) Lowary, T. L. Mini-Rev. Med. Chem. 2003, 3, 694; (b) Jachak, S.

M.; Jain, R. Anti-Infect. Agents Med. Chem. 2006, 5, 123; (c) Biava,

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Rev. Microbiol. 2006, 4, 469.

4. (a) Pietruszka, J. Carbohydrate 2003, 219; (b) Magnusson, G.;

Nilsson, U. J. Glycoscience 2001, 2, 1543; (c) Igarashi, K. Adv.

Carbohydr. Chem. Biochem. 1977, 34, 243; (d) Freudenberg, K. Adv.

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5. (a) Bishop, C. T.; Cooper, F. P. Can. J. Chem. 1962, 40, 224; (b)

Bishop, C. T.; Cooper, F. P. Can. J. Chem. 1963, 41, 2743; (c)

In conclusion, we have developed a new and simple

method for the preparation of methyl glycofuranosides

from acyclic 1-deoxy-1-nitroalditols using strong acid-cata-

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Article Doi

Direct conversion of 1-deoxy-1-nitroalditols to methyl glycofuranosides

DOI: 10.1016/j.tetlet.2008.03.044

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Article abstract of DOI:10.1016/j.tetlet.2008.03.044

Full text of DOI:10.1016/j.tetlet.2008.03.044

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