{"id":{"repo_id":"ottawa-retro","oai_identifier":"oai:ruor.uottawa.ca:10393/28552"},"canonical_url":"https://search.dev.ndltd.org/etd/ottawa-retro/oai:ruor.uottawa.ca:10393/28552","repository":{"repo_id":"ottawa-retro","name":"University of Ottawa","base_url":"https://ruor.uottawa.ca/server/oai/request"},"display":{"title":"Synthesis of Single Isomer Trisubstituted Olefins from beta-chloro-alpha-iodo-alpha, beta-Unsaturated Esters and Alkynyl Esters","abstract":"A convenient method to synthesize regiospecific and stereoselective trisubstituted olefins bearing three substitutents with various functionalities is disclosed. A unique olefin template such as (E)-beta-chloro-alpha-iodo-alpha,beta-unsaturated esters cross-couple with 9-alkyl-9-BBN to produce single isomer trisubstituted olefins using palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. This methodology can be further expanded to introduce various alkyl groups at the beta-position. The mechanism is somewhat unusual as it involves two catalytic cycles with an allenoate intermediate to explain the observed stereochemistry and protonolysis of that intermediate produces the key product, (E)-beta-chloro-alpha,beta-unsaturated ester. The protonolysis is mediated by the presence of H2O in the inorganic base, K3PO4·H2O.* Similarly, another method has been developed to synthesize trisubstituted olefins using the alkynyl ester and 9-alkyl-9-BBN. This process also has a broad scope to introduce various alkyl groups at the beta-position. The mechanism currently proposed involves an oxidation of palladium to form H-[Pd]-OH species. This was confirmed based on the importance of water in the catalytic system and the isotopic experiments also confirmed the olefinic hydrogen at the alpha-position arises from the water itself. Following the formation of H-[Pd]-OH, syn carbopalladation to the alkynyl ester creates the hydroxyl palladium vinyl intermediate. However, this mechanism does not explain the observed stereochemistry. A more detailed study is required regarding this mechanism.* *Please refer to dissertation for diagrams.","abstract_html":"A convenient method to synthesize regiospecific and stereoselective trisubstituted olefins bearing three substitutents with various functionalities is disclosed. A unique olefin template such as (E)-beta-chloro-alpha-iodo-alpha,beta-unsaturated esters cross-couple with 9-alkyl-9-BBN to produce single isomer trisubstituted olefins using palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. This methodology can be further expanded to introduce various alkyl groups at the beta-position. The mechanism is somewhat unusual as it involves two catalytic cycles with an allenoate intermediate to explain the observed stereochemistry and protonolysis of that intermediate produces the key product, (E)-beta-chloro-alpha,beta-unsaturated ester. The protonolysis is mediated by the presence of H2O in the inorganic base, K3PO4·H2O.* Similarly, another method has been developed to synthesize trisubstituted olefins using the alkynyl ester and 9-alkyl-9-BBN. This process also has a broad scope to introduce various alkyl groups at the beta-position. The mechanism currently proposed involves an oxidation of palladium to form H-[Pd]-OH species. This was confirmed based on the importance of water in the catalytic system and the isotopic experiments also confirmed the olefinic hydrogen at the alpha-position arises from the water itself. Following the formation of H-[Pd]-OH, syn carbopalladation to the alkynyl ester creates the hydroxyl palladium vinyl intermediate. However, this mechanism does not explain the observed stereochemistry. A more detailed study is required regarding this mechanism.* *Please refer to dissertation for diagrams.","abstract_has_math":false,"creators":["Rajagopal, Thivisa"],"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":2013,"date_issued":"2013-11-07T19:30:21Z","date_published":"2013-11-07T19:30:21Z","updated_at":"2026-07-24T03:39:25Z","subjects":["Chemistry, Organic."],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["Source: Masters Abstracts International, Volume: 49-02, page: 1188.","http://dx.doi.org/10.20381/ruor-19328"],"render_values":[{"text":"Source: Masters Abstracts International, Volume: 49-02, page: 1188.","href":null,"code":true},{"text":"http://dx.doi.org/10.20381/ruor-19328","href":"http://dx.doi.org/10.20381/ruor-19328","code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10393/28552","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Rajagopal, Thivisa"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2013-11-07T19:30:21Z","2010"]},{"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":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["Source: Masters Abstracts International, Volume: 49-02, page: 1188.","http://hdl.handle.net/10393/28552","http://dx.doi.org/10.20381/ruor-19328"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A convenient method to synthesize regiospecific and stereoselective trisubstituted olefins bearing three substitutents with various functionalities is disclosed. A unique olefin template such as (E)-beta-chloro-alpha-iodo-alpha,beta-unsaturated esters cross-couple with 9-alkyl-9-BBN to produce single isomer trisubstituted olefins using palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. This methodology can be further expanded to introduce various alkyl groups at the beta-position. The mechanism is somewhat unusual as it involves two catalytic cycles with an allenoate intermediate to explain the observed stereochemistry and protonolysis of that intermediate produces the key product, (E)-beta-chloro-alpha,beta-unsaturated ester. The protonolysis is mediated by the presence of H2O in the inorganic base, K3PO4·H2O.* Similarly, another method has been developed to synthesize trisubstituted olefins using the alkynyl ester and 9-alkyl-9-BBN. This process also has a broad scope to introduce various alkyl groups at the beta-position. The mechanism currently proposed involves an oxidation of palladium to form H-[Pd]-OH species. This was confirmed based on the importance of water in the catalytic system and the isotopic experiments also confirmed the olefinic hydrogen at the alpha-position arises from the water itself. Following the formation of H-[Pd]-OH, syn carbopalladation to the alkynyl ester creates the hydroxyl palladium vinyl intermediate. However, this mechanism does not explain the observed stereochemistry. A more detailed study is required regarding this mechanism.* *Please refer to dissertation for diagrams."]},{"key":"dc:format","label":"Dc Format","values":["209 p.","application/pdf"]},{"key":"dc:title","label":"Title","values":["Synthesis of Single Isomer Trisubstituted Olefins from beta-chloro-alpha-iodo-alpha, beta-Unsaturated Esters and Alkynyl Esters"]}]}],"canonical_facts":{"dc:creator":["Rajagopal, Thivisa"],"dc:date":["2013-11-07T19:30:21Z","2010"],"dc:description":["A convenient method to synthesize regiospecific and stereoselective trisubstituted olefins bearing three substitutents with various functionalities is disclosed. A unique olefin template such as (E)-beta-chloro-alpha-iodo-alpha,beta-unsaturated esters cross-couple with 9-alkyl-9-BBN to produce single isomer trisubstituted olefins using palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. This methodology can be further expanded to introduce various alkyl groups at the beta-position. The mechanism is somewhat unusual as it involves two catalytic cycles with an allenoate intermediate to explain the observed stereochemistry and protonolysis of that intermediate produces the key product, (E)-beta-chloro-alpha,beta-unsaturated ester. The protonolysis is mediated by the presence of H2O in the inorganic base, K3PO4·H2O.* Similarly, another method has been developed to synthesize trisubstituted olefins using the alkynyl ester and 9-alkyl-9-BBN. This process also has a broad scope to introduce various alkyl groups at the beta-position. The mechanism currently proposed involves an oxidation of palladium to form H-[Pd]-OH species. This was confirmed based on the importance of water in the catalytic system and the isotopic experiments also confirmed the olefinic hydrogen at the alpha-position arises from the water itself. Following the formation of H-[Pd]-OH, syn carbopalladation to the alkynyl ester creates the hydroxyl palladium vinyl intermediate. However, this mechanism does not explain the observed stereochemistry. A more detailed study is required regarding this mechanism.* *Please refer to dissertation for diagrams."],"dc:format":["209 p.","application/pdf"],"dc:identifier":["Source: Masters Abstracts International, Volume: 49-02, page: 1188.","http://hdl.handle.net/10393/28552","http://dx.doi.org/10.20381/ruor-19328"],"dc:language":["en"],"dc:publisher":["University of Ottawa (Canada)"],"dc:subject":["Chemistry, Organic."],"dc:title":["Synthesis of Single Isomer Trisubstituted Olefins from beta-chloro-alpha-iodo-alpha, beta-Unsaturated Esters and Alkynyl Esters"],"dc:type":["Thesis"]},"updated_at":"2026-07-24T03:39:25Z"}