{"id":{"repo_id":"wvu","oai_identifier":"oai:researchrepository.wvu.edu:etd-1359"},"canonical_url":"https://search.dev.ndltd.org/etd/wvu/oai:researchrepository.wvu.edu:etd-1359","repository":{"repo_id":"wvu","name":"West Virginia University","base_url":"https://researchrepository.wvu.edu/do/oai/"},"display":{"title":"Amine Nucleophilic Addition to Nitro-alkene as a New Reaction Mode for the Synthesis of N-heterocycles","abstract":"Amine Nucleophilic Addition to Nitro-alkene as a New Reaction Mode for the Synthesis of N-heterocycles: An efficient stereoselective synthesis of polycyclic lactams has been developed using Michael addition of conjugated amino-esters to nitro-alkenes. Using acyclic and cyclic aminoesters, this method provided a promising approach to the synthesis of bicyclic and tricyclic lactam core (5,5; 6,5; 5,5,5; 5,6,5; 6,5,5; 6,6,5 etc) in moderate to excellent yield (up to 95%) and excellent diastereoselectivities (up to 99:1 dr). The key steps in this asymmetric synthesis include a heteroatom Michael-Michael addition followed by reductive amidation to gamma-lactams. Lactam cores are biologically active broad spectrum antibiotics.;Enantioselective Synthesis of Piperidines by Exocyclic Chirality Transfer: Piperidines are very important structural moieties contained in a wide range of biologically active and medicinally significant compounds. An efficient route to chiral piperidines was developed which involved diastereoselective synthesis of substituted piperidines (yields up to 75% with dr up to 10:1 of single isomer) followed by removal of one chiral fragment also called N-deprotection to enantiopure piperidine (yields up to 92%) with 100% chirality retention.;Unique Reactivity of Triazole Gold towards Alkyne Activation to Enones and Chiral Allenes: 1,2,3-Triazole coordinated gold(I) complexes were found as the effective catalysts in promoting propargylic ester/ether rearrangement and sequential allene hydration giving enones with excellent yields (up to 97% yields, 0.2% catalyst loading). This catalyst also catalyzed the more challenging Meyer-Schuster rearrangement (0.5% catalyst loading, up to 98% yields). Unlike other reported Au catalysts, the TA-Au complexes provided effective chirality transfer without racemization over a long period of time, giving enantioriched allenes with excellent stereoselectivity (1% catalyst loading, up to 99% ee).","abstract_html":"Amine Nucleophilic Addition to Nitro-alkene as a New Reaction Mode for the Synthesis of N-heterocycles: An efficient stereoselective synthesis of polycyclic lactams has been developed using Michael addition of conjugated amino-esters to nitro-alkenes. Using acyclic and cyclic aminoesters, this method provided a promising approach to the synthesis of bicyclic and tricyclic lactam core (5,5; 6,5; 5,5,5; 5,6,5; 6,5,5; 6,6,5 etc) in moderate to excellent yield (up to 95%) and excellent diastereoselectivities (up to 99:1 dr). The key steps in this asymmetric synthesis include a heteroatom Michael-Michael addition followed by reductive amidation to gamma-lactams. Lactam cores are biologically active broad spectrum antibiotics.;Enantioselective Synthesis of Piperidines by Exocyclic Chirality Transfer: Piperidines are very important structural moieties contained in a wide range of biologically active and medicinally significant compounds. An efficient route to chiral piperidines was developed which involved diastereoselective synthesis of substituted piperidines (yields up to 75% with dr up to 10:1 of single isomer) followed by removal of one chiral fragment also called N-deprotection to enantiopure piperidine (yields up to 92%) with 100% chirality retention.;Unique Reactivity of Triazole Gold towards Alkyne Activation to Enones and Chiral Allenes: 1,2,3-Triazole coordinated gold(I) complexes were found as the effective catalysts in promoting propargylic ester/ether rearrangement and sequential allene hydration giving enones with excellent yields (up to 97% yields, 0.2% catalyst loading). This catalyst also catalyzed the more challenging Meyer-Schuster rearrangement (0.5% catalyst loading, up to 98% yields). Unlike other reported Au catalysts, the TA-Au complexes provided effective chirality transfer without racemization over a long period of time, giving enantioriched allenes with excellent stereoselectivity (1% catalyst loading, up to 99% ee).","abstract_has_math":false,"creators":["Gautam, Lekh Nath Sharma"],"institution":null,"degree_name":"PhD","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Xiaodong Michael Shi","Peter M. Gannett","Jeffrey L. Petersen","Bjorn C. G. Soderberg","Kung K. Wang"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2013,"date_issued":"2013-12-01T08:00:00Z","date_published":"2013-12-01T08:00:00Z","updated_at":"2026-07-24T06:14:24Z","subjects":["Organic chemistry","Pharmaceutical sciences"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["https://researchrepository.wvu.edu/etd/356"],"render_values":[{"text":"https://researchrepository.wvu.edu/etd/356","href":"https://researchrepository.wvu.edu/etd/356","code":true}]}]},"links":{"outbound_url":"https://doi.org/10.33915/etd.356","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Xiaodong Michael Shi","Peter M. Gannett","Jeffrey L. Petersen","Bjorn C. G. Soderberg","Kung K. 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Using acyclic and cyclic aminoesters, this method provided a promising approach to the synthesis of bicyclic and tricyclic lactam core (5,5; 6,5; 5,5,5; 5,6,5; 6,5,5; 6,6,5 etc) in moderate to excellent yield (up to 95%) and excellent diastereoselectivities (up to 99:1 dr). The key steps in this asymmetric synthesis include a heteroatom Michael-Michael addition followed by reductive amidation to gamma-lactams. Lactam cores are biologically active broad spectrum antibiotics.;Enantioselective Synthesis of Piperidines by Exocyclic Chirality Transfer: Piperidines are very important structural moieties contained in a wide range of biologically active and medicinally significant compounds. An efficient route to chiral piperidines was developed which involved diastereoselective synthesis of substituted piperidines (yields up to 75% with dr up to 10:1 of single isomer) followed by removal of one chiral fragment also called N-deprotection to enantiopure piperidine (yields up to 92%) with 100% chirality retention.;Unique Reactivity of Triazole Gold towards Alkyne Activation to Enones and Chiral Allenes: 1,2,3-Triazole coordinated gold(I) complexes were found as the effective catalysts in promoting propargylic ester/ether rearrangement and sequential allene hydration giving enones with excellent yields (up to 97% yields, 0.2% catalyst loading). This catalyst also catalyzed the more challenging Meyer-Schuster rearrangement (0.5% catalyst loading, up to 98% yields). Unlike other reported Au catalysts, the TA-Au complexes provided effective chirality transfer without racemization over a long period of time, giving enantioriched allenes with excellent stereoselectivity (1% catalyst loading, up to 99% ee)."]},{"key":"dc:title","label":"Title","values":["Amine Nucleophilic Addition to Nitro-alkene as a New Reaction Mode for the Synthesis of N-heterocycles"]}]}],"canonical_facts":{"dc:contributor":["Xiaodong Michael Shi","Peter M. Gannett","Jeffrey L. Petersen","Bjorn C. G. Soderberg","Kung K. Wang"],"dc:creator":["Gautam, Lekh Nath Sharma"],"dc:date.available":["2019-01-17T08:00:00Z"],"dc:description.abstract":["Amine Nucleophilic Addition to Nitro-alkene as a New Reaction Mode for the Synthesis of N-heterocycles: An efficient stereoselective synthesis of polycyclic lactams has been developed using Michael addition of conjugated amino-esters to nitro-alkenes. Using acyclic and cyclic aminoesters, this method provided a promising approach to the synthesis of bicyclic and tricyclic lactam core (5,5; 6,5; 5,5,5; 5,6,5; 6,5,5; 6,6,5 etc) in moderate to excellent yield (up to 95%) and excellent diastereoselectivities (up to 99:1 dr). The key steps in this asymmetric synthesis include a heteroatom Michael-Michael addition followed by reductive amidation to gamma-lactams. Lactam cores are biologically active broad spectrum antibiotics.;Enantioselective Synthesis of Piperidines by Exocyclic Chirality Transfer: Piperidines are very important structural moieties contained in a wide range of biologically active and medicinally significant compounds. An efficient route to chiral piperidines was developed which involved diastereoselective synthesis of substituted piperidines (yields up to 75% with dr up to 10:1 of single isomer) followed by removal of one chiral fragment also called N-deprotection to enantiopure piperidine (yields up to 92%) with 100% chirality retention.;Unique Reactivity of Triazole Gold towards Alkyne Activation to Enones and Chiral Allenes: 1,2,3-Triazole coordinated gold(I) complexes were found as the effective catalysts in promoting propargylic ester/ether rearrangement and sequential allene hydration giving enones with excellent yields (up to 97% yields, 0.2% catalyst loading). This catalyst also catalyzed the more challenging Meyer-Schuster rearrangement (0.5% catalyst loading, up to 98% yields). Unlike other reported Au catalysts, the TA-Au complexes provided effective chirality transfer without racemization over a long period of time, giving enantioriched allenes with excellent stereoselectivity (1% catalyst loading, up to 99% ee)."],"dc:identifier":["https://doi.org/10.33915/etd.356","https://researchrepository.wvu.edu/etd/356"],"dc:subject":["Organic chemistry","Pharmaceutical sciences"],"dc:title":["Amine Nucleophilic Addition to Nitro-alkene as a New Reaction Mode for the Synthesis of N-heterocycles"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["PhD"]},"updated_at":"2026-07-24T06:14:24Z"}