# US 9,751,906 B2 · Selective oxidation of carbohydrates > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,751,906 B2 - Document ID: US9751906B2 - Status: Granted - Kind: B2 - Application number: 14/409,604 - Filed: 2013-06-20 - Published: 2015-08-06 - Granted: 2017-09-05 - Earliest claimed: 2012-06-20 - Assignees: Rijksuniversiteit Groningen - Applicants: Rijksuniversiteit Groningen - Inventors: Adriaan Jacobus Minnaard; Manuel Jäger; Aditya Lakshmi Narasimha Raju Gottumukkala; Johannes Gerardus de Vries; Andreas Alexander Bastian; Andreas Herrmann - Web page: https://patentgrep.com/patent/US9751906B2 ## CPC - C07H 15/222: Cyclohexane rings substituted by at least two nitrogen atoms - C07H 1/00: Processes for the preparation of sugar derivatives - C07H 3/02: Monosaccharides - C07H 3/04: Disaccharides - C07H 3/06: Oligosaccharides, i.e. having three to five saccharide radicals attached to each other by glycosidic linkages - C07H 5/06: Aminosugars - C07H 15/04: attached to an oxygen atom of the saccharide radical - C07H 15/18: Acyclic radicals, substituted by carbocyclic rings - C07H 15/22: Cyclohexane rings, substituted by nitrogen atoms - C07H 15/224: with only one saccharide radical directly attached to the cyclohexyl radical, e.g. destomycin, fortimicin, neamine - C07H 15/226: with at least two saccharide radicals directly attached to the cyclohexane rings - C07H 15/228: attached to adjacent ring-carbon atoms of the cyclohexane rings - C07H 15/23: with only two saccharide radicals in the molecule, e.g. ambutyrosin, butyrosin, xylostatin, ribostamycin - C07H 15/232: with at least three saccharide radicals in the molecule, e.g. lividomycin, neomycin, paromomycin - C07H 15/234: attached to non-adjacent ring carbon atoms of the cyclohexane rings, e.g. kanamycins, tobramycin, nebramycin, gentamicin A2 - C07H 17/04: Heterocyclic radicals containing only oxygen as ring hetero atoms - C07H 23/00: Compounds containing boron, silicon or a metal, e.g. chelates or vitamin B12 (esters with inorganic acids C07H11/00) - C07H: SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS (derivatives of aldonic or saccharic acids C07C, C07D; aldonic acids, saccharic acids C07C59/105, C07C59/285; cyanohydrins C07C255/16; glycals C07D; compounds of unknown constitution C07G; polysaccharides, derivatives thereof C08B; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; sugar industry C13) ## Abstract The invention relates to the field of carbohydrate chemistry. Provided is a process for the regioselective oxidation of a single secondary hydroxy function of a carbohydrate substrate comprising two or more secondary hydroxy functions, comprising contacting the carbohydrate substrate in a solvent in the presence of a transition metal catalyst complex with an oxidizing agent to yield a mono-oxidized carbohydrate. ## Claims ### Claim 1 A process for the regioselective oxidation of a single secondary hydroxy function of a carbohydrate substrate comprising two or more secondary hydroxy functions, wherein the carbohydrate substrate is a neamine-based aminoglycoside antibiotic selected from the group consisting of neomycin, neamin, amikacin, paromomycin, ribostamycin, kanamycin, framycetin, isepamicin, and derivatives thereof, and wherein the single secondary hydroxyl function is the C3 hydroxyl of ring I of the neamine-backbone, comprising contacting the carbohydrate substrate in a solvent in the presence of a transition metal catalyst complex with an oxidizing agent to yield a mono-oxidized carbohydrate, and wherein the catalyst complex comprises at least one transition metal atom selected from palladium, ruthenium, copper, manganese and iron and one or more ligands comprising at least one nitrogen atom. ### Claim 2 (depends on 1) A process according to claim 1, wherein the transition metal catalyst complex comprises palladium. ### Claim 3 (depends on 2) A process according to claim 2, wherein the transition metal catalyst complex comprises at least one palladium atom and one or more ligands comprising at least one nitrogen atom. ### Claim 4 (depends on 3) A process according to claim 3, wherein the transition metal catalyst complex is a palladium phenanthroline or a palladium bis(aryl)acenapthenequinonediimine (BIAN) complex in which the phenanthroline or the BIAN ligand is optionally substituted. ### Claim 5 (depends on 1) A process according to claim 1, wherein the transition metal catalyst complex is used in a molar ratio of 0.01-10 mol % with respect to the carbohydrate substrate. ### Claim 6 (depends on 1) A process according to claim 1, wherein the oxidizing agent is selected from the group consisting of a quinone, oxygen, air, peroxide and hydroperoxide. ### Claim 7 (depends on 1) A process according to claim 1, wherein the process is performed at a temperature between 0-100° C. ### Claim 8 (depends on 1) A process according to claim 1, wherein the oxidation reaction is performed in solvent containing water, DMSO, DMF, THF, dioxane, acetonitril, HMPA, NMP, or any mixture thereof. ### Claim 9 (depends on 8) Process according to claim 8, wherein the reaction is performed in a mixture of acetonitrile/water in a ratio of 4:1 to 20:1 (v/v), in DMSO, in a mixture of dioxane/water in a ratio of 4:1 to 20:1 (v/v), or dioxane/DMSO in a ratio of 4:1 to 20:1 (v/v). ### Claim 10 (depends on 1) Process according to claim 1, wherein the carbohydrate substrate does not carry any protecting groups on the secondary hydroxyl groups. ### Claim 11 (depends on 1) Process according to claim 1, wherein the mono-oxidized carbohydrate is subjected to a further derivatization reaction. ### Claim 12 (depends on 11) Process according to claim 11, wherein said further derivatization reaction comprises reduction, reductive amination, acetalisation, diazotation, hydrocyanation, imination, oximation, hydrazination, de-oxygenation, alkylation, or any combination thereof.