{"id":{"repo_id":"ottawa-retro","oai_identifier":"oai:ruor.uottawa.ca:10393/10949"},"canonical_url":"https://search.dev.ndltd.org/etd/ottawa-retro/oai:ruor.uottawa.ca:10393/10949","repository":{"repo_id":"ottawa-retro","name":"University of Ottawa","base_url":"https://ruor.uottawa.ca/server/oai/request"},"display":{"title":"Studies in synthetic carbohydrate chemistry: Part 1. Nitromethane cyclization of sugar polyaldehydes with a view to the synthesis of nitrocyclodextrins. Part 2. Approaches to the synthesis of 2-(R)-fluoro-daunosamine, a carbohydrate moiety for an antitumor drug.","abstract":"Part I. Polyaldehydes derived by periodate oxidation from methyl 4,6-O-benzylidene-alpha-D-glucopyranoside, phenyl 4',6'-O-benzylidene-alpha-maltoside, and 6-deoxy-beta-cyclodextrin incorporate nitromethine functionalities by base-catalyzed reaction with nitromethane according to the general principle of nitroalkane cyclization of sugar dialdehydes, leading to 3-deoxy-3-nitro heptoseptanosides, 3,3'-dideoxy-3,3'-dinitro-disaccharides, and "nitro 6-deoxy-beta-cyclodextrin", respectively. Chapter 1. Methyl 5,7-O-benzylidene-3-deoxy-3-nitro-alpha-D- glycero-D-ido-heptoseptanoside was debenzylidenated, and the resulting nitrotetrol was acetylated. A twofold reductive dehydroacetoxylation of the nitro tetraacetate at C-2 and C-4, and concomitant deacetylation at O-5 and O-7 then resulted in a crystalline mixture of methyl 2,3,4-trideoxy-3-nitro-alpha-D- ribo- and alpha-D-arabino-heptoseptanosides, further characterized as the corresponding 5,7-diacetates. Acetylation of methyl 5,7- O-benzylidene-3-deoxy-3-nitro-alpha-D-glycero-D- ido-heptoseptanoside with acetic anhydride and sodium acetate gave a methyl 2-O-acetyl-5,7-O-benzylidene-3,4-dideoxy-3-nitro-hept-3-enoseptanoside, reduction of which afforded a methyl 2,3,4-trideoxy-3-nitro heptoseptanoside. Chapter 2. Reductive cleavage of the benzylidene acetal ring of phenyl 4',6'-O-benzylidene-alpha-maltoside derivatives was attempted by several methods. One approach led to a low yield of 4'-benzyl ether of phenyl alpha-maltoside. Sodium metaperiodate oxidation of phenyl 4',6'-O-benzylidene-alpha-maltoside and its 6-deoxy derivative led to di- and tetra-aldehydes. Nitromethane condensation of the aldehydes resulted in mono- and dinitro-disaccharides, respectively. The structural analysis was done by the aid of mass spectrometry. Chapter 3. Heptakis(6-deoxy)cyclomaltoheptaose (6-deoxy-beta-CD) was obtained in high yield via 6-bromo-, 6-iodo-, and 6-phenyl-6-thio-beta-CD. Periodate oxidation of the product gave 6-deoxycyclodextrin polyaldehyde, which was confirmed by sodium borohydride reduction and acetylation to give a macrocyclic polyacetal. Nitromethane condensation of the polyaldehyde resulted in "nitro 6-deoxy-beta-CD". Part II. In an attempt to synthesize of 2(R )-fluorodaunosamine, a carbohydrate moiety for an antitumor antibiotic 2'-(R)-fluorodaunorubicin, a possible precursor compound, namely methyl 3,6-dideoxy-3-trifluoroacetamido-alpha-L-galactopyranoside was synthesized via periodate oxidation of L-rhamnopyranoside, nitromethane cyclization, reduction of the nitro group, and trifluoroacetylation of the resulting amino group. Selective trifluoromethanesulfonylation at 2-OH of the product gave its 2-triflate. Reaction of the latter with tetrabutylammonium fluoride, however, did not lead to displacement by fluoride but gave an epimine. Simultaneous protection of the 3-amino and 4-hydroxyl groups of methyl 3-amino-3,6-dideoxy-alpha-L-galactopyranoside with ethyl chloroformate gave the 3-N,4-O-carbonyl derivative which was subsequently triflated at 2-OH. Reaction of this triflate with tetrabutylammonium fluoride also failed to introduce fluorine, and resulted in a tricyclic 2,3-epimino-3-N,4-O-carbonyl compound.","abstract_html":"Part I. Polyaldehydes derived by periodate oxidation from methyl 4,6-O-benzylidene-alpha-D-glucopyranoside, phenyl 4',6'-O-benzylidene-alpha-maltoside, and 6-deoxy-beta-cyclodextrin incorporate nitromethine functionalities by base-catalyzed reaction with nitromethane according to the general principle of nitroalkane cyclization of sugar dialdehydes, leading to 3-deoxy-3-nitro heptoseptanosides, 3,3'-dideoxy-3,3'-dinitro-disaccharides, and "nitro 6-deoxy-beta-cyclodextrin", respectively. Chapter 1. Methyl 5,7-O-benzylidene-3-deoxy-3-nitro-alpha-D- glycero-D-ido-heptoseptanoside was debenzylidenated, and the resulting nitrotetrol was acetylated. A twofold reductive dehydroacetoxylation of the nitro tetraacetate at C-2 and C-4, and concomitant deacetylation at O-5 and O-7 then resulted in a crystalline mixture of methyl 2,3,4-trideoxy-3-nitro-alpha-D- ribo- and alpha-D-arabino-heptoseptanosides, further characterized as the corresponding 5,7-diacetates. Acetylation of methyl 5,7- O-benzylidene-3-deoxy-3-nitro-alpha-D-glycero-D- ido-heptoseptanoside with acetic anhydride and sodium acetate gave a methyl 2-O-acetyl-5,7-O-benzylidene-3,4-dideoxy-3-nitro-hept-3-enoseptanoside, reduction of which afforded a methyl 2,3,4-trideoxy-3-nitro heptoseptanoside. Chapter 2. Reductive cleavage of the benzylidene acetal ring of phenyl 4',6'-O-benzylidene-alpha-maltoside derivatives was attempted by several methods. One approach led to a low yield of 4'-benzyl ether of phenyl alpha-maltoside. Sodium metaperiodate oxidation of phenyl 4',6'-O-benzylidene-alpha-maltoside and its 6-deoxy derivative led to di- and tetra-aldehydes. Nitromethane condensation of the aldehydes resulted in mono- and dinitro-disaccharides, respectively. The structural analysis was done by the aid of mass spectrometry. Chapter 3. Heptakis(6-deoxy)cyclomaltoheptaose (6-deoxy-beta-CD) was obtained in high yield via 6-bromo-, 6-iodo-, and 6-phenyl-6-thio-beta-CD. Periodate oxidation of the product gave 6-deoxycyclodextrin polyaldehyde, which was confirmed by sodium borohydride reduction and acetylation to give a macrocyclic polyacetal. Nitromethane condensation of the polyaldehyde resulted in "nitro 6-deoxy-beta-CD". Part II. In an attempt to synthesize of 2(R )-fluorodaunosamine, a carbohydrate moiety for an antitumor antibiotic 2'-(R)-fluorodaunorubicin, a possible precursor compound, namely methyl 3,6-dideoxy-3-trifluoroacetamido-alpha-L-galactopyranoside was synthesized via periodate oxidation of L-rhamnopyranoside, nitromethane cyclization, reduction of the nitro group, and trifluoroacetylation of the resulting amino group. Selective trifluoromethanesulfonylation at 2-OH of the product gave its 2-triflate. Reaction of the latter with tetrabutylammonium fluoride, however, did not lead to displacement by fluoride but gave an epimine. Simultaneous protection of the 3-amino and 4-hydroxyl groups of methyl 3-amino-3,6-dideoxy-alpha-L-galactopyranoside with ethyl chloroformate gave the 3-N,4-O-carbonyl derivative which was subsequently triflated at 2-OH. Reaction of this triflate with tetrabutylammonium fluoride also failed to introduce fluorine, and resulted in a tricyclic 2,3-epimino-3-N,4-O-carbonyl compound.","abstract_has_math":false,"creators":["Shu, Youn Yuen."],"institution":"University of Ottawa (Canada)","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-04-17T16:04:34Z","date_published":"2009-04-17T16:04:34Z","updated_at":"2026-07-24T03:39:29Z","subjects":["Chemistry, Organic."],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["Source: Dissertation Abstracts International, Volume: 68-07, Section: B, page: 4495.","http://dx.doi.org/10.20381/ruor-8536"],"render_values":[{"text":"Source: Dissertation Abstracts International, Volume: 68-07, Section: B, page: 4495.","href":null,"code":true},{"text":"http://dx.doi.org/10.20381/ruor-8536","href":"http://dx.doi.org/10.20381/ruor-8536","code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10393/10949","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Shu, Youn Yuen."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2009-04-17T16:04:34Z","1992"]},{"key":"dc:publisher","label":"Institution","values":["University of Ottawa (Canada)"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Organic."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["Source: Dissertation Abstracts International, Volume: 68-07, Section: B, page: 4495.","http://hdl.handle.net/10393/10949","http://dx.doi.org/10.20381/ruor-8536"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Part I. Polyaldehydes derived by periodate oxidation from methyl 4,6-O-benzylidene-alpha-D-glucopyranoside, phenyl 4',6'-O-benzylidene-alpha-maltoside, and 6-deoxy-beta-cyclodextrin incorporate nitromethine functionalities by base-catalyzed reaction with nitromethane according to the general principle of nitroalkane cyclization of sugar dialdehydes, leading to 3-deoxy-3-nitro heptoseptanosides, 3,3'-dideoxy-3,3'-dinitro-disaccharides, and "nitro 6-deoxy-beta-cyclodextrin", respectively. Chapter 1. Methyl 5,7-O-benzylidene-3-deoxy-3-nitro-alpha-D- glycero-D-ido-heptoseptanoside was debenzylidenated, and the resulting nitrotetrol was acetylated. A twofold reductive dehydroacetoxylation of the nitro tetraacetate at C-2 and C-4, and concomitant deacetylation at O-5 and O-7 then resulted in a crystalline mixture of methyl 2,3,4-trideoxy-3-nitro-alpha-D- ribo- and alpha-D-arabino-heptoseptanosides, further characterized as the corresponding 5,7-diacetates. Acetylation of methyl 5,7- O-benzylidene-3-deoxy-3-nitro-alpha-D-glycero-D- ido-heptoseptanoside with acetic anhydride and sodium acetate gave a methyl 2-O-acetyl-5,7-O-benzylidene-3,4-dideoxy-3-nitro-hept-3-enoseptanoside, reduction of which afforded a methyl 2,3,4-trideoxy-3-nitro heptoseptanoside. Chapter 2. Reductive cleavage of the benzylidene acetal ring of phenyl 4',6'-O-benzylidene-alpha-maltoside derivatives was attempted by several methods. One approach led to a low yield of 4'-benzyl ether of phenyl alpha-maltoside. Sodium metaperiodate oxidation of phenyl 4',6'-O-benzylidene-alpha-maltoside and its 6-deoxy derivative led to di- and tetra-aldehydes. Nitromethane condensation of the aldehydes resulted in mono- and dinitro-disaccharides, respectively. The structural analysis was done by the aid of mass spectrometry. Chapter 3. Heptakis(6-deoxy)cyclomaltoheptaose (6-deoxy-beta-CD) was obtained in high yield via 6-bromo-, 6-iodo-, and 6-phenyl-6-thio-beta-CD. Periodate oxidation of the product gave 6-deoxycyclodextrin polyaldehyde, which was confirmed by sodium borohydride reduction and acetylation to give a macrocyclic polyacetal. Nitromethane condensation of the polyaldehyde resulted in "nitro 6-deoxy-beta-CD". Part II. In an attempt to synthesize of 2(R )-fluorodaunosamine, a carbohydrate moiety for an antitumor antibiotic 2'-(R)-fluorodaunorubicin, a possible precursor compound, namely methyl 3,6-dideoxy-3-trifluoroacetamido-alpha-L-galactopyranoside was synthesized via periodate oxidation of L-rhamnopyranoside, nitromethane cyclization, reduction of the nitro group, and trifluoroacetylation of the resulting amino group. Selective trifluoromethanesulfonylation at 2-OH of the product gave its 2-triflate. Reaction of the latter with tetrabutylammonium fluoride, however, did not lead to displacement by fluoride but gave an epimine. Simultaneous protection of the 3-amino and 4-hydroxyl groups of methyl 3-amino-3,6-dideoxy-alpha-L-galactopyranoside with ethyl chloroformate gave the 3-N,4-O-carbonyl derivative which was subsequently triflated at 2-OH. Reaction of this triflate with tetrabutylammonium fluoride also failed to introduce fluorine, and resulted in a tricyclic 2,3-epimino-3-N,4-O-carbonyl compound."]},{"key":"dc:format","label":"Dc Format","values":["192 p.","application/pdf"]},{"key":"dc:title","label":"Title","values":["Studies in synthetic carbohydrate chemistry: Part 1. Nitromethane cyclization of sugar polyaldehydes with a view to the synthesis of nitrocyclodextrins. Part 2. Approaches to the synthesis of 2-(R)-fluoro-daunosamine, a carbohydrate moiety for an antitumor drug."]}]}],"canonical_facts":{"dc:creator":["Shu, Youn Yuen."],"dc:date":["2009-04-17T16:04:34Z","1992"],"dc:description":["Part I. Polyaldehydes derived by periodate oxidation from methyl 4,6-O-benzylidene-alpha-D-glucopyranoside, phenyl 4',6'-O-benzylidene-alpha-maltoside, and 6-deoxy-beta-cyclodextrin incorporate nitromethine functionalities by base-catalyzed reaction with nitromethane according to the general principle of nitroalkane cyclization of sugar dialdehydes, leading to 3-deoxy-3-nitro heptoseptanosides, 3,3'-dideoxy-3,3'-dinitro-disaccharides, and "nitro 6-deoxy-beta-cyclodextrin", respectively. Chapter 1. Methyl 5,7-O-benzylidene-3-deoxy-3-nitro-alpha-D- glycero-D-ido-heptoseptanoside was debenzylidenated, and the resulting nitrotetrol was acetylated. A twofold reductive dehydroacetoxylation of the nitro tetraacetate at C-2 and C-4, and concomitant deacetylation at O-5 and O-7 then resulted in a crystalline mixture of methyl 2,3,4-trideoxy-3-nitro-alpha-D- ribo- and alpha-D-arabino-heptoseptanosides, further characterized as the corresponding 5,7-diacetates. Acetylation of methyl 5,7- O-benzylidene-3-deoxy-3-nitro-alpha-D-glycero-D- ido-heptoseptanoside with acetic anhydride and sodium acetate gave a methyl 2-O-acetyl-5,7-O-benzylidene-3,4-dideoxy-3-nitro-hept-3-enoseptanoside, reduction of which afforded a methyl 2,3,4-trideoxy-3-nitro heptoseptanoside. Chapter 2. Reductive cleavage of the benzylidene acetal ring of phenyl 4',6'-O-benzylidene-alpha-maltoside derivatives was attempted by several methods. One approach led to a low yield of 4'-benzyl ether of phenyl alpha-maltoside. Sodium metaperiodate oxidation of phenyl 4',6'-O-benzylidene-alpha-maltoside and its 6-deoxy derivative led to di- and tetra-aldehydes. Nitromethane condensation of the aldehydes resulted in mono- and dinitro-disaccharides, respectively. The structural analysis was done by the aid of mass spectrometry. Chapter 3. Heptakis(6-deoxy)cyclomaltoheptaose (6-deoxy-beta-CD) was obtained in high yield via 6-bromo-, 6-iodo-, and 6-phenyl-6-thio-beta-CD. Periodate oxidation of the product gave 6-deoxycyclodextrin polyaldehyde, which was confirmed by sodium borohydride reduction and acetylation to give a macrocyclic polyacetal. Nitromethane condensation of the polyaldehyde resulted in "nitro 6-deoxy-beta-CD". Part II. In an attempt to synthesize of 2(R )-fluorodaunosamine, a carbohydrate moiety for an antitumor antibiotic 2'-(R)-fluorodaunorubicin, a possible precursor compound, namely methyl 3,6-dideoxy-3-trifluoroacetamido-alpha-L-galactopyranoside was synthesized via periodate oxidation of L-rhamnopyranoside, nitromethane cyclization, reduction of the nitro group, and trifluoroacetylation of the resulting amino group. Selective trifluoromethanesulfonylation at 2-OH of the product gave its 2-triflate. Reaction of the latter with tetrabutylammonium fluoride, however, did not lead to displacement by fluoride but gave an epimine. Simultaneous protection of the 3-amino and 4-hydroxyl groups of methyl 3-amino-3,6-dideoxy-alpha-L-galactopyranoside with ethyl chloroformate gave the 3-N,4-O-carbonyl derivative which was subsequently triflated at 2-OH. Reaction of this triflate with tetrabutylammonium fluoride also failed to introduce fluorine, and resulted in a tricyclic 2,3-epimino-3-N,4-O-carbonyl compound."],"dc:format":["192 p.","application/pdf"],"dc:identifier":["Source: Dissertation Abstracts International, Volume: 68-07, Section: B, page: 4495.","http://hdl.handle.net/10393/10949","http://dx.doi.org/10.20381/ruor-8536"],"dc:publisher":["University of Ottawa (Canada)"],"dc:subject":["Chemistry, Organic."],"dc:title":["Studies in synthetic carbohydrate chemistry: Part 1. Nitromethane cyclization of sugar polyaldehydes with a view to the synthesis of nitrocyclodextrins. Part 2. Approaches to the synthesis of 2-(R)-fluoro-daunosamine, a carbohydrate moiety for an antitumor drug."],"dc:type":["Thesis"]},"updated_at":"2026-07-24T03:39:29Z"}