{"id":{"repo_id":"ncsu","oai_identifier":"oai:repository.lib.ncsu.edu:1840.16/4982"},"canonical_url":"https://search.dev.ndltd.org/etd/ncsu/oai:repository.lib.ncsu.edu:1840.16/4982","repository":{"repo_id":"ncsu","name":"North Carolina State University","base_url":"https://repository.lib.ncsu.edu/server/oai/request"},"display":{"title":"Novel Chiral Diamines and (S)-6-Chloronicotine Derivatives as Catalysts for Asymmetric Synthesis","abstract":"Many enantiomerically pure products with biological activities are commonly used in the pharmaceutical industry due to their effectiveness. As such, procedures that produce stereochemically pure compounds are highly desirable. Asymmetric synthesis using chiral compounds has become the preferred way to make enantiopure material. For example, selectively synthesizing secondary alcohols that are ubiquitous in natural products and pharmaceuticals can be achieved through the catalytic asymmetric addition of an alkylzinc to an aldehyde. In the Comins group, we have developed new chiral diamines, amino alcohols, and amino phosphines to test in asymmetric reactions, such as the catalytic addition of diethylzinc to benzaldehyde, and palladium-catalyzed allylic alkylation. Each of these catalysts has a nitrogen containing heterocycle and is synthesized in a few steps from commercially available materials, such as ephedrine and (S)-nicotine. Overall, the amino alcohol derivatives provided the best results in the catalytic asymmetric addition of diethylzinc to various aldehydes, while the amino phosphines showed promise in the palladium-catalyzed allylic alkylation of racemic 1,3-diphenylpropen-2-yl acetate with dimethyl malonate. However, these nicotine–based catalysts did not show great selectivity or usefulness in other metal–catalyzed reactions, such as zinc alkynylations to aldehydes, copper–catalyzed 1,4–additions, the Henry reaction, and allylic oxidations.","abstract_html":"Many enantiomerically pure products with biological activities are commonly used in the pharmaceutical industry due to their effectiveness. As such, procedures that produce stereochemically pure compounds are highly desirable. Asymmetric synthesis using chiral compounds has become the preferred way to make enantiopure material. For example, selectively synthesizing secondary alcohols that are ubiquitous in natural products and pharmaceuticals can be achieved through the catalytic asymmetric addition of an alkylzinc to an aldehyde. In the Comins group, we have developed new chiral diamines, amino alcohols, and amino phosphines to test in asymmetric reactions, such as the catalytic addition of diethylzinc to benzaldehyde, and palladium-catalyzed allylic alkylation. Each of these catalysts has a nitrogen containing heterocycle and is synthesized in a few steps from commercially available materials, such as ephedrine and (S)-nicotine. Overall, the amino alcohol derivatives provided the best results in the catalytic asymmetric addition of diethylzinc to various aldehydes, while the amino phosphines showed promise in the palladium-catalyzed allylic alkylation of racemic 1,3-diphenylpropen-2-yl acetate with dimethyl malonate. However, these nicotine–based catalysts did not show great selectivity or usefulness in other metal–catalyzed reactions, such as zinc alkynylations to aldehydes, copper–catalyzed 1,4–additions, the Henry reaction, and allylic oxidations.","abstract_has_math":false,"creators":["Capracotta, Sonja Siefert"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Dr. Elon Ison, Committee Member","Dr. Suzanne T. Purrington, Committee Member","Dr. Daniel L. Comins, Committee Chair","Dr. Christian Melander, Committee Member"],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-08-26","date_published":"2009-08-26","updated_at":"2026-08-21T22:21:56Z","subjects":["asymmetric synthesis","chiral amino alcohols","chiral catalyst","amino phosphines","nicotine","allylic alkylation","addition of diethylzinc to aldehydes","chiral diamines"],"languages":[],"rights":["I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dis sertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to NC State University or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-08222008-144938"],"render_values":[{"text":"etd-08222008-144938","href":null,"code":true}]}]},"links":{"outbound_url":"http://www.lib.ncsu.edu/resolver/1840.16/4982","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"source_record":{"url":"https://repository.lib.ncsu.edu/server/oai/request?verb=GetRecord&metadataPrefix=dim&identifier=oai%3Arepository.lib.ncsu.edu%3A1840.16%2F4982","prefix":"dim"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Dr. Elon Ison, Committee Member","Dr. Suzanne T. Purrington, Committee Member","Dr. Daniel L. 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I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to NC State University or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-08222008-144938"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://www.lib.ncsu.edu/resolver/1840.16/4982"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Many enantiomerically pure products with biological activities are commonly used in the pharmaceutical industry due to their effectiveness. As such, procedures that produce stereochemically pure compounds are highly desirable. Asymmetric synthesis using chiral compounds has become the preferred way to make enantiopure material. For example, selectively synthesizing secondary alcohols that are ubiquitous in natural products and pharmaceuticals can be achieved through the catalytic asymmetric addition of an alkylzinc to an aldehyde. In the Comins group, we have developed new chiral diamines, amino alcohols, and amino phosphines to test in asymmetric reactions, such as the catalytic addition of diethylzinc to benzaldehyde, and palladium-catalyzed allylic alkylation. Each of these catalysts has a nitrogen containing heterocycle and is synthesized in a few steps from commercially available materials, such as ephedrine and (S)-nicotine. Overall, the amino alcohol derivatives provided the best results in the catalytic asymmetric addition of diethylzinc to various aldehydes, while the amino phosphines showed promise in the palladium-catalyzed allylic alkylation of racemic 1,3-diphenylpropen-2-yl acetate with dimethyl malonate. However, these nicotine–based catalysts did not show great selectivity or usefulness in other metal–catalyzed reactions, such as zinc alkynylations to aldehydes, copper–catalyzed 1,4–additions, the Henry reaction, and allylic oxidations."]},{"key":"dc:format","label":"Dc Format","values":["Thesis (Ph.D.)--North Carolina State University."]},{"key":"dc:title","label":"Title","values":["Novel Chiral Diamines and (S)-6-Chloronicotine Derivatives as Catalysts for Asymmetric Synthesis"]}]}],"canonical_facts":{"dc:contributor.advisor":["Dr. Elon Ison, Committee Member","Dr. Suzanne T. Purrington, Committee Member","Dr. Daniel L. Comins, Committee Chair","Dr. Christian Melander, Committee Member"],"dc:creator":["Capracotta, Sonja Siefert"],"dc:date.accessioned":["2010-04-02T19:05:30Z"],"dc:date.available":["2010-04-02T19:05:30Z"],"dc:date.issued":["2009-08-26"],"dc:description.abstract":["Many enantiomerically pure products with biological activities are commonly used in the pharmaceutical industry due to their effectiveness. As such, procedures that produce stereochemically pure compounds are highly desirable. Asymmetric synthesis using chiral compounds has become the preferred way to make enantiopure material. For example, selectively synthesizing secondary alcohols that are ubiquitous in natural products and pharmaceuticals can be achieved through the catalytic asymmetric addition of an alkylzinc to an aldehyde. In the Comins group, we have developed new chiral diamines, amino alcohols, and amino phosphines to test in asymmetric reactions, such as the catalytic addition of diethylzinc to benzaldehyde, and palladium-catalyzed allylic alkylation. Each of these catalysts has a nitrogen containing heterocycle and is synthesized in a few steps from commercially available materials, such as ephedrine and (S)-nicotine. Overall, the amino alcohol derivatives provided the best results in the catalytic asymmetric addition of diethylzinc to various aldehydes, while the amino phosphines showed promise in the palladium-catalyzed allylic alkylation of racemic 1,3-diphenylpropen-2-yl acetate with dimethyl malonate. However, these nicotine–based catalysts did not show great selectivity or usefulness in other metal–catalyzed reactions, such as zinc alkynylations to aldehydes, copper–catalyzed 1,4–additions, the Henry reaction, and allylic oxidations."],"dc:format":["Thesis (Ph.D.)--North Carolina State University."],"dc:identifier.other":["etd-08222008-144938"],"dc:identifier.uri":["http://www.lib.ncsu.edu/resolver/1840.16/4982"],"dc:rights":["I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dis sertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to NC State University or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report."],"dc:subject":["asymmetric synthesis","chiral amino alcohols","chiral catalyst","amino phosphines","nicotine","allylic alkylation","addition of diethylzinc to aldehydes","chiral diamines"],"dc:title":["Novel Chiral Diamines and (S)-6-Chloronicotine Derivatives as Catalysts for Asymmetric Synthesis"]},"updated_at":"2026-08-21T22:21:56Z"}