Catalytic Regioselective Oxidation of Glycosides

Jäger, Manuel; Hartmann, Marcel; Vries, Johannes G. de; Minnaard, Adriaan J.

doi:10.1002/ange.201301662

Cited by 18 publications

(16 citation statements)

References 26 publications

(18 reference statements)

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“…The cationic Pd II catalyst 2 2 (OTf) 2 catalyzes the selective oxidation of primary and secondary aliphatic alcohols,20–23 vicinal diols,21 polyols,22 and carbohydrates 24. For vicinal diols and polyols, room temperature oxidation with 2 2 (OTf) 2 is chemoselective to afford the α‐hydroxyketones 21.…”

Section: Methodsmentioning

confidence: 99%

Trinuclear Pd₃O₂ Intermediate in Aerobic Oxidation Catalysis

Ingram¹,

Solis‐Ibarra²,

Zare³

et al. 2014

Angewandte Chemie

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The activation of O2 is a key step in selective catalytic aerobic oxidation reactions mediated by transition metals. The bridging trinuclear palladium species, [(LPdII)3(μ3‐O)2]2+ (L=2,9‐dimethylphenanthroline), was identified during the [LPd(OAc)]2(OTf)2‐catalyzed aerobic oxidation of 1,2‐propanediol. Independent synthesis, structural characterization, and catalytic studies of the trinuclear compound show that it is a product of oxygen activation by reduced palladium species and is a competent intermediate in the catalytic aerobic oxidation of alcohols. The formation and catalytic activity of the trinuclear Pd3O2 species illuminates a multinuclear pathway for aerobic oxidation reactions catalyzed by Pd complexes.

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Section: Methodsmentioning

confidence: 99%

Trinuclear Pd₃O₂ Intermediate in Aerobic Oxidation Catalysis

Ingram¹,

Solis‐Ibarra²,

Zare³

et al. 2014

Angewandte Chemie

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“…Although the basis for site-selectivity is not yet fully understood, the C3 selectivity observed here is congruent with the substrate-controlled selectivity previously noted by both Minnaard, Waymouth, and Wendlandt in oxidation reactions. 13,17,18,37 Nuclear magnetic resonance (NMR) titration experiments reveal an equilibrium interaction between 1a and tetrabutylammonium phosphate (TBAP)…”

Section: Mechanistic Investigationsmentioning

confidence: 99%

“…[7][8][9][10][11][12] Especially, Minnaard group realized regioselective oxidation of several types of glycosides via palladium system with benzoquinone as an oxidant without using protecting groups. 13 As the development of photoredox catalysis in recent years. [14][15][16] the Wendlandt group recently reported the preparation of rare sugar isomers directly from biomass carbohydrates through the site-selective epimerization reactions.…”

Section: Introductionmentioning

confidence: 99%

Enzyme-like C–H Oxidation of Glucosides Promoted by Visible Light

Jiang

Tian

et al. 2022

CCS Chem

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To match nature's prowess at using enzymes to make desired motifs in a regioselective fashion, we explore the use of visible light for the selective oxidation of the hydroxyl group to the corresponding ketosaccharide. This highly admirable approach offers several advantages over the enzymatic approach in terms of yields, the scope of substrates. Herein we report the development of a simple visible-light-promoted selective oxidation of unprotected glucosides that allows for inexpensive access to valuable ketosaccharides building blocks. The method is employed on a variety of different natural and artificial glucosides, is operationally simple and scalable, and is applied to access ketosaccharides rapidly and inexpensively.

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“…A mixture of the tosylhydrazine 14 (405 mg, 0.94 mmol) and sodium acetate trihydrate (511 mg, 3.75 mmol) in 11 mL of ethanol was refluxed for 3 h. Ethanol was removed in vacuo, and the residue was purified by flash chromatography on a 15 g silica cartridge with DCM/MeOH, increasing ratio of MeOH from 0 to 10% in 20 min, the product eluted at 5% MeOH to provide a white solid (154 mg, 66%), m.p. : 164−166 °C; 1 H NMR (400 MHz, methanol-d 4 ) δ 4.83 (d, J = 3.6 Hz, 1H), 4.02−3.88 (m, 2H), 3.79 (dd, J = 11.7, 2.0 Hz, 1H), 3.65 (dd, J = 11.7, 5.0 Hz, 1H), 3.60−3.49 (m, 2H), 1.94 (s, 3H), 1.93−1.88 (m, 1H), 1.78 (dt, J = 12.7, 10.8 Hz, 1H), 1.25 (d, J = 6.3 Hz, 3H), 1.13 (d, J = 6.1 Hz, 3H); 13 (16). Isopropyl 2-acetamido-2,3-dideoxy-α-D-ribohexopyranoside 15 (143 mg, 0.58 mmol) was dissolved in HCl (aq) (2 M, 0.7 mL) and heated at 100 °C for 2 h. Subsequent evaporation of the volatiles provided the product (107 mg, 92%) as a brown syrup.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…We had shown earlier in the glucose series that reductive amination of the C3 carbonyl provides an efficient route to 3amino glucose. 16 Here, we used this strategy on 3-keto GlcNAc 7 as well. Synthesis of the methyl oxime 17 (formed as a 1:1 mixture of E and Z isomers) was followed by hydrogenolysis/ hydrogenation with Adams' catalyst and hydrogen (Scheme 5).…”

Section: ■ Introductionmentioning

confidence: 99%