Synthesis of 3-deoxy-d-manno-2-octulosonic acid (Kdo) and d-glycero-d-talo-2-octulosonic acid (Ko) and their α-glycosides

Reiner, Martin; Schmidt, Richard R.

doi:10.1016/s0957-4166(99)00557-1

Cited by 39 publications

(15 citation statements)

References 25 publications

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“…its superior reactivity, the indium-mediated allylation has been applied in numerous natural product syntheses by us and others, e.g. N-acetylneuraminic acid (Neu5Ac, 1) [10,11], 3-deoxy-d-glycero-d-galacto-nonulosonic acid (Kdn, 2) [12], 3-deoxy-d-manno-2-octulosonic acid (Kdo, 3) [13] or legionaminic acid (Leg, 4) [14,15] (Fig. 1).…”

Section: Electronic Supplementary Materialsmentioning

confidence: 99%

“…The mixture was concentrated and purified by column chromatography with dichloromethane/methanol (4:1 v/v) as eluent to give 126 mg compound 22 (0.777 mmol, 86%) as colorless oil. 1 J 4,3b = 3.4 Hz, 3 J 4,5 = 3.1 Hz, 3 J 4,6b = 0.9 Hz, 1H, H-4), 3.937 (dd, 2 J 6a,6b = 11.5 Hz, 3 J 6a,5 = 9.6 Hz, 1H, H-6a), 3.814 (ddd, 3 J 5,6a = 9.6 Hz, 3 J 5,6b = 4.9 Hz, 3 J 5,4 = 3.1 Hz, 1H, H-5), 3.662 (ddd, 2 J 6b,6a = 11.5 Hz, 3 J 6b,5 = 4.9 Hz, 3 J 6b,4 = 0.9 Hz, 1H, H-6b), 3.500 (d, 2 J 1a,1b = 11.8 Hz, 1H, H-1a), 3.470 (d, 2 J 1b,1a = 11.8 Hz, 1H, H-1b), 1.995 (dd, 2 J 3a,3b = 14.5 Hz, 3 J 3a,4 = 5.1 Hz, 1H, H-3a), 1.940 (dd, 2 J 3b,3a = 14.5 Hz, 3 J 3b,4 = 3.4 Hz, 1H, H-3b) ppm; 13…”

Section: 3-dideoxy-2-c-methylidene-d-erythro-hexitol (22 C 7 H 14 mentioning

confidence: 99%

“…Separation of the resulting epimers was achieved via column chromatography using heptane/ethyl acetate (1:1 v/v) as eluent to give 779 mg compound syn-23 (1.64 mmol) as colorless oil and 250 mg compound anti-23 (0.527 mmol) as colorless oil (80%, 51% de). syn-23: 1 H NMR (600.25 MHz, CDCl 3 , 25 °C): δ = 5.422 (dd, 3 J 6,7 = 7.3 Hz, 3 J 6,5 = 3.9 Hz, 1H, 6-H), 5.278 (dd, 3 J 5,4 = 6.9 Hz, 3 J 5,6 = 3.9 Hz, 1H, 5-H), 5.186 (ddd, 3 J 4,3b = 9.2 Hz, 3 J 4,5 = 6.9 Hz, 3 J 4,3a = 3.6 Hz, 1H, 4-H), 5.141 (d, 2 J 1′a,1′b = 0.9 Hz, 1H, 1′-Ha), 5.059 (ddd, 3 J 7,6 = 7.3 Hz, 3 J 7,8b = 5.4 Hz, 3 J 7,8a = 3.1 Hz, 1H, 7-H), 5.028 (d, 2 J 1′b,1′a = 0.9 Hz, 1H, 1′-Hb), 4 13…”

Section: 45678-hexa-o-acetyl-23-dideoxy-2-c-methylidene-d-glucmentioning

confidence: 99%

“…The aqueous layer was concentrated and the resulting oil was purified by column chromatography using dichloromethane/methanol (4:1 v/v) as eluent to give 40 mg compound 15 (0.18 mmol, 78%) as a colorless oil. 1 H NMR (600.25 MHz, D 2 O, 25 °C): β-pyranose:keto isomer:α-furanose:β-furanose: = 1.00:0.19:0.18:0.09; δ (β-pyranose) = 4.120 (dd, 3 J 6,7 = 9.0 Hz, 3 J 6,5 = 1.4 Hz, 1H, 6-H), 4.111 (ddd, 3 J 4,3a = 3.7 Hz, 3 J 4,5 = 3.6 Hz, 3 J 4,3b = 2.8 Hz, 1H, 4-H), 3.862 (ddd, 3 J 5,4 = 3.6 Hz, 3 J 5,6 = 1.4 Hz, 4 J 5,3b = 1.0 Hz, 1H, 5-H), 3.855 (ddd, 3 J 7,6 = 9.0 Hz, 3 J 7,8b = 6.0 Hz, 3 J 7,8a = 2.9 Hz, 1H, 7-H), 3.835 (dd, 2 J 8a,8b = 12.0 Hz, 3 J 8a,7 = 2.9 Hz, 1H, 8-Ha), 3.664 (dd, 2 J 8b,8a = 12.0 Hz, 3 J 8b,7 = 6.0 Hz, 1H, 8-Hb), 3.456 (s, 2H, 1-Ha, 1-Hb), 2.024 (dd, 2 J 3a,3b = 14.9 Hz, 3 J 3a,4 = 3.7 Hz, 1H, 3-Ha), 1.782 (ddd, 2 J 3b,3a = 14.9 Hz, 3 J 3b,4 = 2.8 Hz, 4 J 3b,5 = 1.0 Hz, 1H, 3-Hb) ppm; δ (keto isomer) = 4.435 (dd, 2 J 1a,1b = 19.2 Hz, 4 J 1a,3b = 0.6 Hz, 1H, 1-Ha), 4.380 (dd, 2 J 1b,1a = 19.2 Hz, 4 J 1b,3b = 0.6 Hz, 1H, 1-Hb), 4.257 (ddd, 3 J 4,3a = 9.4 Hz, 3 J 4,5 = 5.7 Hz, 3 J 4,3b = 3.5 Hz, 1H, 4-H), 3.827 (dd, 2 J 8a,8b = 12.0 Hz, 3 J 8a,7 = 3.0 Hz, 1H, 8a-H), 3.773 (ddd, 3 J 7,6 = 8.2 Hz, 3 J 7,8b = 6.3 Hz, 3 J 7,8a = 3.0 Hz, 1H, 7-H), 3.740 (dd, 3 J 5,4 = 5.7 Hz, 3 J 5,6 = 2.4 Hz, 1H, 5-H), 3.655 (dd, 2 J 8b,8a = 12.0 Hz, 3 J 8b,7 = 6.3 Hz, 1H, 8-Hb), 3.627 (dd, 3 J 6,7 = 8.2 Hz, 3 J 6,5 = 2.4 Hz, 1H, 6-H), 2.750 (dd, 2 J 3a,3b = 16.3 Hz, 3 J 3a,4 = 9.4 Hz, 1H, 3-Ha), 2.713 (dddd, 2 J 3b,3a = 16.3 Hz, 3 J 3b,4 = 3.5 Hz, 4 J 3b,1a = 0.6 Hz, 4 J 3b,1b = 0.6 Hz, 1H, 3-Hb) ppm; δ (α-furanose) = 4.614 (ddd, 3 J 4,3a = 6.3 Hz, 3 J 4,5 = 4.4 Hz, 3 J 4,3b = 3.3 Hz, 1H, 4-H), 4.294 (dd, 3 J 5,6 = 5.0 Hz, 3 J 5,4 = 4.4 Hz, 1H, 5-H), 3.921 (dd, 3 J 6,7 = 6.8 Hz, 3 J 6,5 = 5.0 Hz, 1H, 6-H), 3.814 (dd, 2 J 8a,8b = 12.0 Hz, 3 J 8a,7 = 3.3 Hz, 1H, 8-Ha), 3.785 (ddd, 3 J 7,8b = 6.9 Hz, 3 J 7,6 = 6.8 Hz, 3 J 7,8a = 3.3 Hz, 1H, 7-H), 3.678 (dd, 2 J 8b,8a = 12.0 Hz, 3 J 8b,7 = 6.9 Hz, 1H, 8-Hb), 3.653 (s, 2H, 1-Ha, 1-Hb), 2.305 (dd, 2 J 3a,3b = 14.5 Hz, 3 J 3a,4 = 6.3 Hz, 1H, 3-Ha), 2.241 (dd, 2 J 3b,3a = 14.5 Hz, 3 J 3b,4 = 3.3 Hz, 1H, 3-Hb) ppm; δ (β-furanose) = 4.538 (ddd, 3 J 4,3a = 5.6 Hz, 3 J 4,5 = 4.1 Hz, 3 J 4,3b = 1.9 Hz, 1H, 4-H), 4.122 (dd, 3 J 5,6 = 5.3 Hz, 3 J 5,4 = 4.1 Hz, 1H, 5-H), 3.979 (dd, 3 J 6,7 = 6.9 Hz, 3 J 6,5 = 5.3 Hz, 1H, 6-H), 3.814 (dd, 2 J 8a,8b = 11.6 Hz, 3 J 8a,7 = 3.3 Hz, 1H, 8-Ha), 3.789 (ddd, 3 J 7,6 = 6.9 Hz, 3 J 7,8b = 6.9 Hz, 3 J 7,8a = 3.3 Hz, 1H, 7-H), 3.677 (dd, 2 J 8b,8a = 11.6 Hz, 3 J 8b,7 = 6.9 Hz, 1H, 8-Hb), 3.597 (d, 2 J 1a,1b = 11.8 Hz, 1H, 1-Ha), 3.589 (d, 2 J 1b,1a = 11.8 Hz, 1H, 1-Hb), 2.417 (dd, 2 J 3a,3b = 14.3 Hz, 3 J 3a,4 = 5.6 Hz, 1H, 3-Ha), 2.055 (dd, 2 J 3b,3a = 14.3 Hz, 3 J 3b,4 = 1.9 Hz, 1H, 3-Hb) ppm; 13 1,4,5,6,7,8,9-Hepta-O-acetyl-2,3-dideoxy-2-C-methylidene-d-glycero-d-galacto-nonitol (syn-25, C 24 H 34 O 14 ) d-Mannose (200 mg, 19, 1.11 mmol) and 251 mg 2-(bromomethyl)prop-2-en-1-ol (14, 1.67 mmol, 1.5 equiv.) were dissolved in 8 cm 3 ethanol and 2 cm 3 water.…”

Section: -Deoxy-d-gluco-octulose (15 C 8 H 16 O 7 )mentioning

confidence: 99%

“…The residue was purified by column chromatography using heptane/ethyl acetate (19/1 14/1 v/v) as eluent to give 3.70 g ethyl 2-(benzyloxymethyl)acrylate (29,16.8 mmol, 87%) as a yellowish liquid. 1 H NMR (600.25 MHz, CDCl 3 , 25 °C): δ = 7.407-7.326 (m, 4H, H-7, H-8), 7.326-7.270 (m, 1H, H-9), 6.324 (dd, 3 J 4a,3 = 1.5 Hz, 2 J 4a,4b = 1.4 Hz, 1H, H-4a), 5.927 (dd, 3 J 4b,3 = 1.9 Hz, 2 J 4b,4a = 1.4 Hz, 1H, H-4a), 4.594 (s, 2H, H-5), 4.248 (dd, 3 J 3,4b = 1.9 Hz, 3 J 3,4a = 1.5 Hz, 2H, H-3), 4.226 (q, 3 J 1′,2′ = 7.2 Hz, 2H, H-1′), 1.304 (t, 3 J 2′,1′ = 7.2 Hz, 3H, H-2′) ppm; 13…”

Section: Ethyl 2-(benzyloxymethyl)acrylate (29 C 13 H 16 O 3 )mentioning

confidence: 99%

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Synthesis of 3-deoxy-2-uloses via the indium-mediated allylation reaction

et al. 2019

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We utilized the indium-mediated allylation reaction for the synthesis of carbohydrate structures containing the 3-deoxy-2-ulose motif, a barely investigated compound class. The stereoselective outcome can be controlled by the presence or absence of a chelating group in α-position to the carbonyl function. By introduction of an UV-active allyl building block, we enabled epimer separation by HPLC towards the synthesis of 3-deoxy-d-glycero-d-galacto-2-nonulose, the carboxylreduced analogue of widely distributed 3-deoxy-d-glycero-d-galacto-nonulosonic acid (Kdn). Ozonolysis of the introduced 2-C-methylidenepropan-1-ol motif provided the desired 3-deoxy-2-uloses.

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Section: Electronic Supplementary Materialsmentioning

confidence: 99%

Section: 3-dideoxy-2-c-methylidene-d-erythro-hexitol (22 C 7 H 14 mentioning

confidence: 99%

Section: 45678-hexa-o-acetyl-23-dideoxy-2-c-methylidene-d-glucmentioning

confidence: 99%

Section: -Deoxy-d-gluco-octulose (15 C 8 H 16 O 7 )mentioning

confidence: 99%

Section: Ethyl 2-(benzyloxymethyl)acrylate (29 C 13 H 16 O 3 )mentioning

confidence: 99%

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Synthesis of 3-deoxy-2-uloses via the indium-mediated allylation reaction

et al. 2019

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The Barton‐McCombie Reaction

2012

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Deoxygenations of alcohols, i.e., processes that replace a hydroxyl group with hydrogen at a saturated carbon, find applications in both total synthesis and the systematic modifications of natural products. They may also be employed to introduce deuterium or tritium in a site‐specific manner. Reductive methods that involve ionic or highly polarized reagents or intermediates can be limited in their applicability: for example, competing reaction pathways including cationic rearrangements and anionic eliminations may be encountered in sterically hindered systems with substrates bearing heteroatoms close to the center undergoing reduction. As evidenced by developments over the last few decades, methods that involve the generation and direct quenching via hydrogen atom abstraction of the derived, carbon‐centered radical typically show the greatest tolerance for the presence of other functional groups and for variations in both the steric acid and the electronic environment in the vicinity of the center undergoing deoxygenation. Derivatization of the hydroxyl is a prerequisite, the determinant factors for efficient formation of the deoxygenated product lies in the ability of the combination of the substrate and reagents to induce homolysis of the C‐O bond coupled with the induction of homolysis to rapidly reduce a free radical by hydrogen donation, thereby propagating an efficient chain process. A high‐yielding way to realize this sequence was first described by Barton McCombie using the free‐radical chain reaction of O ‐thioacyl derivatives of secondary alcohols with tri‐ n ‐butylstannane. This chapter provides a detailed description and comparison of the combinations of substrates and reagents that will bring about these processes and provides a summary and evaluation of alternative deoxygenation methods. Mechanistic and stereochemical issues set out the scope and limitations of these processes with respect to both the thioacylation and reduction steps and exemplify some applications to both total synthesis and the modification of natural products.

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Efficient Synthesis of 3-Deoxy-D-arabino-2-heptulosonate (DAH) and -D-gluco-2-heptulosonate by a Two-Carbon Chain Elongation of D-Arabinose

2002

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Reaction of α‐lithiated methyl glyoxylate diethyl mercaptal (3) with 2,3,5‐tri‐O‐benzyl‐D‐arabinose (2) stereoselectively afforded the D‐gluco‐2‐heptulosonate derivative 4. Mercaptal cleavage led to the corresponding pyranose 5a which could be directly transformed into unprotected D‐gluco‐2‐heptulosonic acid (1a), one of the target molecules. Deoxygenation of 5a at C‐3 could also be readily accomplished as its 3‐hydroxy group is unprotected. Thus, the second target molecule, 1b, was obtained in just a few steps.

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Synthesis of 3-deoxy-d-manno-2-octulosonic acid (Kdo) and d-glycero-d-talo-2-octulosonic acid (Ko) and their α-glycosides

Cited by 39 publications

References 25 publications

Synthesis of 3-deoxy-2-uloses via the indium-mediated allylation reaction

Synthesis of 3-deoxy-2-uloses via the indium-mediated allylation reaction

The Barton‐McCombie Reaction

Efficient Synthesis of 3-Deoxy-D-arabino-2-heptulosonate (DAH) and -D-gluco-2-heptulosonate by a Two-Carbon Chain Elongation of D-Arabinose

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