A new and direct access to glycono-1,4-lactones from glycopyranoses by regioselective oxidation and subsequent ring restriction

Isaac, I.; Staslk, Imane; Beaupère, D.; Uzan, R.

doi:10.1016/0040-4039(94)02262-a

Cited by 63 publications

(29 citation statements)

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“…1 H and 13 C NMR spectra of δ-galactonolactone (6a) isolated in Ͼ 95% isomeric purity (Table 1) were recorded in [D 6 ]DMSO at 400 and 100 MHz, respectively. A combination of COSY, HSQC, and APT techniques allowed us to assignment all the resonances unambiguously.…”

Section: Nmr Spectroscopic and Conformational Analysesmentioning

confidence: 99%

“…NMR-scale reactions of -glucopyranose in [D 7 ]DMF have established that the initial oxidation products are in fact the δ-lactones, but control experiments with the readily accessible δ--gluconolactone (see above) showed that, under the same reaction conditions, the rhodium catalyst isomerizes them rapidly to the thermodynamically more stable γ-form (Scheme 2). [13,14] We have now discovered that Shvo's catalyst system, which is based on the dimeric ruthenium complex [(C 4 Ph 4 CO)(CO) 2 Ru] 2 (7), [15,16] also efficiently catalyzes the dehydrogenation of -gluco-, -manno-, and -galactopyranoses to the corresponding δ-lactones, but, with the exclusion of water, it does not effect the δ Ǟ γ isomerization of the kinetic to thermodynamic products.…”

Section: Introductionmentioning

confidence: 99%

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δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

Bierenstiel

Schlaf

2004

Eur J Org Chem

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δ‐D‐Gluconolactone, δ‐D‐mannonolactone, and — for the first time — the thermodynamically unstable δ‐D‐galactonolactone have been prepared and isolated from DMF solution by oxidizing the corresponding sugars with Shvo’s catalyst [(C4Ph4CO)(CO)2Ru]2 and a hydrogen acceptor. The preferred conformation of δ‐D‐galactonolactone in [D6]DMSO solution has been determined by 1H NMR spectroscopy experiments and DFT calculations to be 4H3 and is compared to those of the previously established conformations of δ‐D‐gluconolactone (4H3) and δ‐D‐mannonolactone (B2,5). The conformations of the lactones suggest an explanation for their relative rates of isomerization to their respective γ‐D‐lactones by an intramolecular mechanism. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Nmr Spectroscopic and Conformational Analysesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

Bierenstiel

Schlaf

2004

Eur J Org Chem

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“…The Oppenauer oxidation is not used for carbohydrate alcohols, [10,11] and judging by earlier reports in the literature, secondary carbohydrate alcohols appear to be very unreactive towards oxidation by transition-metal complex-catalysed hydrogen transfer: it has been shown that the anomeric hemiacetal of carbohydrates may be oxidised to the lactone by rhodium or ruthenium complexes operating by a hydrogen-transfer mechanism, without affecting unprotected secondary hydroxy groups, confirming their low reactivity. [14][15][16][17][18][19] One paper does describe low-yielding oxidation of OH-5 in a glucofuranose derivative by dehydrogenation with a RuH 2 (PPh 3 ) 4 catalyst. [19] Also, with heterogeneous catalysts some reactivity has been reported.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium‐Catalysed Epimerisation of Carbohydrate Alcohols as a Method to Determine the Equilibria for Epimer Interconversion in Hexopyranosides

et al. 2011

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“…7 We report here the use of this system for the oxidation of unprotected itols to prepare glycono-1,4-lactones.…”

mentioning

confidence: 99%

“…In a previous paper we described the oxidation of protected or unprotected lactols to glycono-1,4-lactones, in mild conditions, by C.H.T with benzalacetone as hydrogen acceptor and RhH(PPh 3 ) 4 (hydridotetrakis triphenylphosphine rhodium I) as catalyst. 7 We report here the use of this system for the oxidation of unprotected itols to prepare glycono-1,4-lactones.…”

mentioning

confidence: 99%

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh₃)₄-Benzalacetone System

Isaac¹,

Aizel²,

Stasik³

et al. 1998

Synlett

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Treatment of unprotected pentitols and hexitols with RhH(PPh 3 ) 4 -benzalacetone system leads exclusively to glycono-1,4-lactones in 60-96% yield.The literature records a number of methods for the conversion of diols to lactones in yields varying from good to poor. These include: silver carbonate on Celite, 1 stoichiometric RuCl 2 (PPh 3 ) 3 in benzene, 2 CuSO 4 -KMnO 4 , 3 tetrapropylammonium perruthenate-4-methylmorpholine Noxide, 4 and catalytic hydrogen transfer (C.H.T) [benzalacetophenoneRuH 2 (PPh 3 ) 4 ] at 140°C. 5 To our knowledge, the latter is the only method which has been described to oxidize protected pentitols to afford the corresponding pentonolactones 6 and no method was applicable for the oxidation of unprotected itols to glyconolactones.In a previous paper we described the oxidation of protected or unprotected lactols to glycono-1,4-lactones, in mild conditions, by C.H.T with benzalacetone as hydrogen acceptor and RhH(PPh 3 ) 4 (hydridotetrakis triphenylphosphine rhodium I) as catalyst. 7 We report here the use of this system for the oxidation of unprotected itols to prepare glycono-1,4-lactones.As a matter of fact, we observed that treatment of meso erythritol 1 with RhH(PPh 3 ) 4 (0.2 eq) and benzalacetone (4 eq) in DMF for 3 hours at 60°C led to the racemic mixture of D,L-erythrono-1,4-lactone 2 in 95% isolated yield (Scheme 1). This method was also applied to other unprotected itols (tetritols, pentitols and hexitols) and efficiently yielded the glycono-1,4-lactones as shown in the Table. Scheme 1Pentitols and hexitols which have a plane of symmetry, for example meso erythritol 1, D-xylitol 8, D-galactitol 18 or a C-2 symmetry axis, such as D-threitol 3 or D-mannitol 13 led, with good yields, to the corresponding lactone obtained in a racemic mixture.Only one exception was observed when D-ribitol 5, having a plane of symmetry, was oxidized with 0.2 eq of catalyst and 4 eq of benzalacetone at 60°C for 5 hours. D,L-Ribono-1,4-lactone 6 and D,Larabinono-1,4-lactones 7 were isolated in 47% and 18% yield respectively. Similar epimerisation at C-2 was already observed in the oxidation of 2-acetamido-2-deoxy-D-mannopyranose with the same oxidizing system. 8When the oxidation of D-ribitol was performed at 80°C with 0.4 eq of RhH(PPh 3 ) 4 the overall yield increased to 94% but the ratio 6/7 remained equal to 2.5:1.The oxidation of L-arabinitol which has no symmetry led to the two expected L-arabinono-1,4-lactone 11 and L-lyxono-1,4-lactone 12 in 72% overall yield and in ratio 11/12=1.25:1.As explained in Scheme 2, after an oxidation at C-1 of L-arabinitol, the L-arabinopyranose or furanose formed was oxidized to give the Larabinono-1,4-lactone 11. The rare L-lyxono-1,4-lactone 12 is obtained via the L-lyxose resulting from the oxidation at the C-5 of the starting itol.Downloaded by: University of Illinois. Copyrighted material.

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A new and direct access to glycono-1,4-lactones from glycopyranoses by regioselective oxidation and subsequent ring restriction

Cited by 63 publications

References 32 publications

δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

Ruthenium‐Catalysed Epimerisation of Carbohydrate Alcohols as a Method to Determine the Equilibria for Epimer Interconversion in Hexopyranosides

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh₃)₄-Benzalacetone System

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A new and direct access to glycono-1,4-lactones from glycopyranoses by regioselective oxidation and subsequent ring restriction

Cited by 63 publications

References 32 publications

δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

Ruthenium‐Catalysed Epimerisation of Carbohydrate Alcohols as a Method to Determine the Equilibria for Epimer Interconversion in Hexopyranosides

A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh3)4-Benzalacetone System

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A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by Catalytic Hydrogen Transfer with RhH(PPh₃)₄-Benzalacetone System