{"id":{"repo_id":"queens","oai_identifier":"oai:queensu.scholaris.ca:1974/34222"},"canonical_url":"https://search.dev.ndltd.org/etd/queens/oai:queensu.scholaris.ca:1974/34222","repository":{"repo_id":"queens","name":"Queens University","base_url":"https://qspace.library.queensu.ca/server/oai/request"},"display":{"title":"Sequential Enantioselective Iridium-Catalyzed Allylic Alkylation/Cope Rearrangement for the Construction of Acyclic γ-Tertiary or Quaternary Stereocenters","abstract":"Functionalized carbonyl compounds with extended chiral carbon chains are commonly found in natural and synthetic bioactive molecules. However, catalytic asymmetric γ-functionalization of carbonyl derivates is challenging because of the issues with ontrolling chemo- (O vs. C), regio- (α vs. γ), and enantioselectivity. In this way, enantioselective transition metal-catalyzed γ-allylic alkylation reactions have attracted increasing attention, albeit they are typically restricted to cyclic nucleophiles. A direct strategy to construct acyclic γ-allylated carbonyl derivates is underdeveloped due to the challenging regio- and enantiocontrol, especially for constructing quaternary stereocenters. In this regard, an innovative strategy that sequential enantioselective iridium-catalyzed allylic alkylation/Cope rearrangement to provide an efficient method approach to acyclic γ-tertiary and quaternary stereocenters. The following thesis is divided into four chapters, which encompass a comprehensive literature review followed by two research chapters, further divided based on the type of transformation discussed. Chapter 1 commences with a brief introduction to the enantioselective catalytic γ-functionalization of carbonyl derivates, which is followed by a comprehensive review divided into two major subsections based on the type of pronucleophiles, namely homoenolate and dienolate equivalents, which are further subdivided into cyclic and acyclic nucleophiles. Chapter 2 highlights the development of enantioselective iridium-catalyzed γ-allylic alkylation of acyclic pronucleophiles. This chapter begins with a review of the iridium-catalyzed allylic substitution reactions, which includes seminal examples. While direct enantioselective iridiumγcatalyzed allylic alkylation at γ-position remains a significant challenge. Hence, we developed an indirect enantioselective iridium-catalyzed γ-allylic alkylation with a broad range of acyclic α,β-iii unsaturated cyanoacetates, and allylic carbonates, which can efficiently construct acyclic γ-tertiary stereocenters at mild conditions. Chapter 3 illustrates the development of a sequential enantioselective iridium-catalyzed allylic alkylation/Cope rearrangement for the construction of acyclic γ-quaternary stereocenters. This chapter opens with a review of the historical development of the construction of acyclic quaternary stereocenters, which are limited to adjacent positions of carbonyl groups. Then, our approach involves iridium-catalyzed γ-allylic alkylation of a series of acyclic disubstituted α,β-unsaturated malononitrile for the construction of quaternary stereocenters via a sequential α-allylic alkylation and in situ Cope rearrangement. Chapter 4 highlights some future works.","abstract_html":"Functionalized carbonyl compounds with extended chiral carbon chains are commonly found in natural and synthetic bioactive molecules. However, catalytic asymmetric γ-functionalization of carbonyl derivates is challenging because of the issues with ontrolling chemo- (O vs. C), regio- (α vs. γ), and enantioselectivity. In this way, enantioselective transition metal-catalyzed γ-allylic alkylation reactions have attracted increasing attention, albeit they are typically restricted to cyclic nucleophiles. A direct strategy to construct acyclic γ-allylated carbonyl derivates is underdeveloped due to the challenging regio- and enantiocontrol, especially for constructing quaternary stereocenters. In this regard, an innovative strategy that sequential enantioselective iridium-catalyzed allylic alkylation/Cope rearrangement to provide an efficient method approach to acyclic γ-tertiary and quaternary stereocenters. The following thesis is divided into four chapters, which encompass a comprehensive literature review followed by two research chapters, further divided based on the type of transformation discussed. Chapter 1 commences with a brief introduction to the enantioselective catalytic γ-functionalization of carbonyl derivates, which is followed by a comprehensive review divided into two major subsections based on the type of pronucleophiles, namely homoenolate and dienolate equivalents, which are further subdivided into cyclic and acyclic nucleophiles. Chapter 2 highlights the development of enantioselective iridium-catalyzed γ-allylic alkylation of acyclic pronucleophiles. This chapter begins with a review of the iridium-catalyzed allylic substitution reactions, which includes seminal examples. While direct enantioselective iridiumγcatalyzed allylic alkylation at γ-position remains a significant challenge. Hence, we developed an indirect enantioselective iridium-catalyzed γ-allylic alkylation with a broad range of acyclic α,β-iii unsaturated cyanoacetates, and allylic carbonates, which can efficiently construct acyclic γ-tertiary stereocenters at mild conditions. Chapter 3 illustrates the development of a sequential enantioselective iridium-catalyzed allylic alkylation/Cope rearrangement for the construction of acyclic γ-quaternary stereocenters. This chapter opens with a review of the historical development of the construction of acyclic quaternary stereocenters, which are limited to adjacent positions of carbonyl groups. Then, our approach involves iridium-catalyzed γ-allylic alkylation of a series of acyclic disubstituted α,β-unsaturated malononitrile for the construction of quaternary stereocenters via a sequential α-allylic alkylation and in situ Cope rearrangement. Chapter 4 highlights some future works.","abstract_has_math":false,"creators":["Xie, Hengmu"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Chemistry","school":null,"contributors":[],"advisors":["Evans, P. Andrew"],"committee_chairs":[],"committee_members":[],"year":2024,"date_issued":"2024-12-16","date_published":"2024-12-16","updated_at":"2026-07-27T20:35:39Z","subjects":["Allylic alkylation","Cope rearrangement"],"languages":["eng"],"rights":["Attribution-NonCommercial-NoDerivatives 4.0 International"],"rights_urls":["http://creativecommons.org/licenses/by-nc-nd/4.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1974/34222","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:contributor.supervisor","label":"Supervisor","values":["Evans, P. 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However, catalytic asymmetric γ-functionalization of carbonyl derivates is challenging because of the issues with ontrolling chemo- (O vs. C), regio- (α vs. γ), and enantioselectivity. In this way, enantioselective transition metal-catalyzed γ-allylic alkylation reactions have attracted increasing attention, albeit they are typically restricted to cyclic nucleophiles. A direct strategy to construct acyclic γ-allylated carbonyl derivates is underdeveloped due to the challenging regio- and enantiocontrol, especially for constructing quaternary stereocenters. In this regard, an innovative strategy that sequential enantioselective iridium-catalyzed allylic alkylation/Cope rearrangement to provide an efficient method approach to acyclic γ-tertiary and quaternary stereocenters. The following thesis is divided into four chapters, which encompass a comprehensive literature review followed by two research chapters, further divided based on the type of transformation discussed. Chapter 1 commences with a brief introduction to the enantioselective catalytic γ-functionalization of carbonyl derivates, which is followed by a comprehensive review divided into two major subsections based on the type of pronucleophiles, namely homoenolate and dienolate equivalents, which are further subdivided into cyclic and acyclic nucleophiles. Chapter 2 highlights the development of enantioselective iridium-catalyzed γ-allylic alkylation of acyclic pronucleophiles. This chapter begins with a review of the iridium-catalyzed allylic substitution reactions, which includes seminal examples. While direct enantioselective iridiumγcatalyzed allylic alkylation at γ-position remains a significant challenge. Hence, we developed an indirect enantioselective iridium-catalyzed γ-allylic alkylation with a broad range of acyclic α,β-iii unsaturated cyanoacetates, and allylic carbonates, which can efficiently construct acyclic γ-tertiary stereocenters at mild conditions. Chapter 3 illustrates the development of a sequential enantioselective iridium-catalyzed allylic alkylation/Cope rearrangement for the construction of acyclic γ-quaternary stereocenters. This chapter opens with a review of the historical development of the construction of acyclic quaternary stereocenters, which are limited to adjacent positions of carbonyl groups. Then, our approach involves iridium-catalyzed γ-allylic alkylation of a series of acyclic disubstituted α,β-unsaturated malononitrile for the construction of quaternary stereocenters via a sequential α-allylic alkylation and in situ Cope rearrangement. Chapter 4 highlights some future works."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["PhD"]},{"key":"dc:title","label":"Title","values":["Sequential Enantioselective Iridium-Catalyzed Allylic Alkylation/Cope Rearrangement for the Construction of Acyclic γ-Tertiary or Quaternary Stereocenters"]}]}],"canonical_facts":{"dc:contributor.department":["Chemistry"],"dc:contributor.supervisor":["Evans, P. Andrew"],"dc:creator":["Xie, Hengmu"],"dc:date.accessioned":["2024-12-16T14:02:55Z"],"dc:date.available":["2024-12-16T14:02:55Z"],"dc:date.issued":["2024-12-16"],"dc:description.abstract":["Functionalized carbonyl compounds with extended chiral carbon chains are commonly found in natural and synthetic bioactive molecules. However, catalytic asymmetric γ-functionalization of carbonyl derivates is challenging because of the issues with ontrolling chemo- (O vs. C), regio- (α vs. γ), and enantioselectivity. In this way, enantioselective transition metal-catalyzed γ-allylic alkylation reactions have attracted increasing attention, albeit they are typically restricted to cyclic nucleophiles. A direct strategy to construct acyclic γ-allylated carbonyl derivates is underdeveloped due to the challenging regio- and enantiocontrol, especially for constructing quaternary stereocenters. In this regard, an innovative strategy that sequential enantioselective iridium-catalyzed allylic alkylation/Cope rearrangement to provide an efficient method approach to acyclic γ-tertiary and quaternary stereocenters. The following thesis is divided into four chapters, which encompass a comprehensive literature review followed by two research chapters, further divided based on the type of transformation discussed. Chapter 1 commences with a brief introduction to the enantioselective catalytic γ-functionalization of carbonyl derivates, which is followed by a comprehensive review divided into two major subsections based on the type of pronucleophiles, namely homoenolate and dienolate equivalents, which are further subdivided into cyclic and acyclic nucleophiles. Chapter 2 highlights the development of enantioselective iridium-catalyzed γ-allylic alkylation of acyclic pronucleophiles. This chapter begins with a review of the iridium-catalyzed allylic substitution reactions, which includes seminal examples. While direct enantioselective iridiumγcatalyzed allylic alkylation at γ-position remains a significant challenge. Hence, we developed an indirect enantioselective iridium-catalyzed γ-allylic alkylation with a broad range of acyclic α,β-iii unsaturated cyanoacetates, and allylic carbonates, which can efficiently construct acyclic γ-tertiary stereocenters at mild conditions. Chapter 3 illustrates the development of a sequential enantioselective iridium-catalyzed allylic alkylation/Cope rearrangement for the construction of acyclic γ-quaternary stereocenters. This chapter opens with a review of the historical development of the construction of acyclic quaternary stereocenters, which are limited to adjacent positions of carbonyl groups. Then, our approach involves iridium-catalyzed γ-allylic alkylation of a series of acyclic disubstituted α,β-unsaturated malononitrile for the construction of quaternary stereocenters via a sequential α-allylic alkylation and in situ Cope rearrangement. Chapter 4 highlights some future works."],"dc:description.degree":["PhD"],"dc:identifier.uri":["https://hdl.handle.net/1974/34222"],"dc:language.iso":["eng"],"dc:rights":["Attribution-NonCommercial-NoDerivatives 4.0 International"],"dc:rights.uri":["http://creativecommons.org/licenses/by-nc-nd/4.0/"],"dc:subject":["Allylic alkylation","Cope rearrangement"],"dc:title":["Sequential Enantioselective Iridium-Catalyzed Allylic Alkylation/Cope Rearrangement for the Construction of Acyclic γ-Tertiary or Quaternary Stereocenters"],"dc:type":["thesis"]},"updated_at":"2026-07-27T20:35:39Z"}