{"id":{"repo_id":"helsinki","oai_identifier":"oai:helda.helsinki.fi:10138/338521"},"canonical_url":"https://search.dev.ndltd.org/etd/helsinki/oai:helda.helsinki.fi:10138/338521","repository":{"repo_id":"helsinki","name":"University of Helsinki","base_url":"https://helda.helsinki.fi/server/oai/request"},"display":{"title":"ARYL-HETEROATOM CROSS-COUPLING WITH DUAL NICKEL/PHOTOCATALYST PROTOCOLS : THEORY, APPLICATIONS AND RECENT DEVELOPMENTS","abstract":"An overview on utilization of dual nickel/photocatalyst protocols to conduct aryl-heteroatom cross-coupling reactions is presented. Basic concepts of photocatalysis, including different relaxation pathways, the difference of singlet and triplet states, and parameters used to predict reactivity are first disclosed. The general components used in dual nickel/photocatalyst protocols are presented followed by the discussion on reactivity trends. The reactivity trends are compared with other common aryl-heteroatom cross-coupling protocols (Buchwald-Hartwig-, Ullmann- and Chan-Lam couplings) illustrating the general advantages and disadvantages of each cross-coupling method. The scope of different dual nickel/photocatalyst protocols are then explored, concentrating on cross-coupling of amines, alcohols/thiols and carboxylic acids. The developments in mechanistic understanding on the dual nickel/photocatalyst aryl-heteroatom cross-couplings in recent years are reviewed. It is concluded that photocatalytic single electron transfer-based cycles, proposed for a number of coupling protocols, are very unlikely to take place. It is made clear that, based on the current knowledge, two principle mechanism are reasonable: energy transfer or thermal Ni(I)/Ni(III) cycles. Problems concerning energy transfer mechanisms are also discussed. Finally, applicability of dual nickel/photocatalyst aryl-heteroatom cross-coupling for industrially significant transformations is briefly discussed.","abstract_html":"An overview on utilization of dual nickel/photocatalyst protocols to conduct aryl-heteroatom cross-coupling reactions is presented. Basic concepts of photocatalysis, including different relaxation pathways, the difference of singlet and triplet states, and parameters used to predict reactivity are first disclosed. The general components used in dual nickel/photocatalyst protocols are presented followed by the discussion on reactivity trends. The reactivity trends are compared with other common aryl-heteroatom cross-coupling protocols (Buchwald-Hartwig-, Ullmann- and Chan-Lam couplings) illustrating the general advantages and disadvantages of each cross-coupling method. The scope of different dual nickel/photocatalyst protocols are then explored, concentrating on cross-coupling of amines, alcohols/thiols and carboxylic acids. The developments in mechanistic understanding on the dual nickel/photocatalyst aryl-heteroatom cross-couplings in recent years are reviewed. It is concluded that photocatalytic single electron transfer-based cycles, proposed for a number of coupling protocols, are very unlikely to take place. It is made clear that, based on the current knowledge, two principle mechanism are reasonable: energy transfer or thermal Ni(I)/Ni(III) cycles. Problems concerning energy transfer mechanisms are also discussed. Finally, applicability of dual nickel/photocatalyst aryl-heteroatom cross-coupling for industrially significant transformations is briefly discussed.","abstract_has_math":false,"creators":["Puumi, Jukka"],"institution":"Helsingin yliopisto","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Helsingin yliopisto, Matemaattis-luonnontieteellinen tiedekunta","University of Helsinki, Faculty of Science","Helsingfors universitet, Matematisk-naturvetenskapliga fakulteten"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2021,"date_issued":"2021","date_published":"2021","updated_at":"2026-07-27T19:56:09Z","subjects":["Nickel","Ni","photocatalysis","photocatalyst","PC","Cross-coupling","Mechanism","EnT","SET","PET"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["URN:NBN:fi:hulib-202201121022"],"render_values":[{"text":"URN:NBN:fi:hulib-202201121022","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10138/338521","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Helsingin yliopisto, Matemaattis-luonnontieteellinen tiedekunta","University of Helsinki, Faculty of Science","Helsingfors universitet, Matematisk-naturvetenskapliga fakulteten"]},{"key":"dc:creator","label":"Author","values":["Puumi, Jukka"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2021"]},{"key":"dc:publisher","label":"Institution","values":["Helsingin yliopisto","University of Helsinki","Helsingfors universitet"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Nickel","Ni","photocatalysis","photocatalyst","PC","Cross-coupling","Mechanism","EnT","SET","PET"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["URN:NBN:fi:hulib-202201121022","http://hdl.handle.net/10138/338521"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["An overview on utilization of dual nickel/photocatalyst protocols to conduct aryl-heteroatom cross-coupling reactions is presented. Basic concepts of photocatalysis, including different relaxation pathways, the difference of singlet and triplet states, and parameters used to predict reactivity are first disclosed. The general components used in dual nickel/photocatalyst protocols are presented followed by the discussion on reactivity trends. The reactivity trends are compared with other common aryl-heteroatom cross-coupling protocols (Buchwald-Hartwig-, Ullmann- and Chan-Lam couplings) illustrating the general advantages and disadvantages of each cross-coupling method. The scope of different dual nickel/photocatalyst protocols are then explored, concentrating on cross-coupling of amines, alcohols/thiols and carboxylic acids. The developments in mechanistic understanding on the dual nickel/photocatalyst aryl-heteroatom cross-couplings in recent years are reviewed. It is concluded that photocatalytic single electron transfer-based cycles, proposed for a number of coupling protocols, are very unlikely to take place. It is made clear that, based on the current knowledge, two principle mechanism are reasonable: energy transfer or thermal Ni(I)/Ni(III) cycles. Problems concerning energy transfer mechanisms are also discussed. Finally, applicability of dual nickel/photocatalyst aryl-heteroatom cross-coupling for industrially significant transformations is briefly discussed."]},{"key":"dc:title","label":"Title","values":["ARYL-HETEROATOM CROSS-COUPLING WITH DUAL NICKEL/PHOTOCATALYST PROTOCOLS : THEORY, APPLICATIONS AND RECENT DEVELOPMENTS"]}]}],"canonical_facts":{"dc:contributor":["Helsingin yliopisto, Matemaattis-luonnontieteellinen tiedekunta","University of Helsinki, Faculty of Science","Helsingfors universitet, Matematisk-naturvetenskapliga fakulteten"],"dc:creator":["Puumi, Jukka"],"dc:date.issued":["2021"],"dc:description.abstract":["An overview on utilization of dual nickel/photocatalyst protocols to conduct aryl-heteroatom cross-coupling reactions is presented. Basic concepts of photocatalysis, including different relaxation pathways, the difference of singlet and triplet states, and parameters used to predict reactivity are first disclosed. The general components used in dual nickel/photocatalyst protocols are presented followed by the discussion on reactivity trends. The reactivity trends are compared with other common aryl-heteroatom cross-coupling protocols (Buchwald-Hartwig-, Ullmann- and Chan-Lam couplings) illustrating the general advantages and disadvantages of each cross-coupling method. The scope of different dual nickel/photocatalyst protocols are then explored, concentrating on cross-coupling of amines, alcohols/thiols and carboxylic acids. The developments in mechanistic understanding on the dual nickel/photocatalyst aryl-heteroatom cross-couplings in recent years are reviewed. It is concluded that photocatalytic single electron transfer-based cycles, proposed for a number of coupling protocols, are very unlikely to take place. It is made clear that, based on the current knowledge, two principle mechanism are reasonable: energy transfer or thermal Ni(I)/Ni(III) cycles. Problems concerning energy transfer mechanisms are also discussed. Finally, applicability of dual nickel/photocatalyst aryl-heteroatom cross-coupling for industrially significant transformations is briefly discussed."],"dc:identifier.uri":["URN:NBN:fi:hulib-202201121022","http://hdl.handle.net/10138/338521"],"dc:language.iso":["eng"],"dc:publisher":["Helsingin yliopisto","University of Helsinki","Helsingfors universitet"],"dc:subject":["Nickel","Ni","photocatalysis","photocatalyst","PC","Cross-coupling","Mechanism","EnT","SET","PET"],"dc:title":["ARYL-HETEROATOM CROSS-COUPLING WITH DUAL NICKEL/PHOTOCATALYST PROTOCOLS : THEORY, APPLICATIONS AND RECENT DEVELOPMENTS"]},"updated_at":"2026-07-27T19:56:09Z"}