{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/145029"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/145029","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Organophosphorus-Catalyzed Reductive Functionalization of Nitrocompounds via P(III)/P(V) Redox Couple","abstract":"Nitro compounds are widely available synthetic building blocks which present a strategical opportunity to serve as direct precursors for the construction of nitrogen-containing molecules with increasing complexity and value. With the utilization of geometric-distorted organophosphetanes as catalysts and hydrosilanes as terminal reductants, nitro compounds (nitroarenes, nitromethane and nitroalkanes) undergo reductive O-atom transfer reactions involving the conversion of P(III)/P(V)=O. With that, boronic acids were employed as coupling partners to intercept the nitrene reactivity of nitro compounds derived oxazaphosphorane intermediates for direct reductive C–N coupling. This organophosphorus-catalyzed nitro deoxygenative platform was further developed to a tandem C–N coupling/cyclization sequence, yielding a variety N-functionalized azaheterocycles (oxindoles, indoles, quinoxalinediones, and benzimidazoles). Besides boronic acids, anilines were also introduced as an exogenous coupling partner for novel cross-selective intermolecular N–N bond forming reactivity in the formation of various hydrazines with excellent chemoselectivities and functional group tolerance. These works herein not only expand the reactivity of low-cost and environment-benign organophosphorus compounds as platforms for catalytic reductive O-atom transfer, but also details the P(III)/P(V)=O redox couple catalyzed reaction mechanism, providing further precedents for the catalytic potential of organophosphorus compounds in reaction classes heretofore dominated by transition-metal catalysis and suggesting potential opportunities for organophosphorus catalyst optimization.","abstract_html":"Nitro compounds are widely available synthetic building blocks which present a strategical opportunity to serve as direct precursors for the construction of nitrogen-containing molecules with increasing complexity and value. With the utilization of geometric-distorted organophosphetanes as catalysts and hydrosilanes as terminal reductants, nitro compounds (nitroarenes, nitromethane and nitroalkanes) undergo reductive O-atom transfer reactions involving the conversion of P(III)/P(V)=O. With that, boronic acids were employed as coupling partners to intercept the nitrene reactivity of nitro compounds derived oxazaphosphorane intermediates for direct reductive C–N coupling. This organophosphorus-catalyzed nitro deoxygenative platform was further developed to a tandem C–N coupling/cyclization sequence, yielding a variety N-functionalized azaheterocycles (oxindoles, indoles, quinoxalinediones, and benzimidazoles). Besides boronic acids, anilines were also introduced as an exogenous coupling partner for novel cross-selective intermolecular N–N bond forming reactivity in the formation of various hydrazines with excellent chemoselectivities and functional group tolerance. These works herein not only expand the reactivity of low-cost and environment-benign organophosphorus compounds as platforms for catalytic reductive O-atom transfer, but also details the P(III)/P(V)=O redox couple catalyzed reaction mechanism, providing further precedents for the catalytic potential of organophosphorus compounds in reaction classes heretofore dominated by transition-metal catalysis and suggesting potential opportunities for organophosphorus catalyst optimization.","abstract_has_math":false,"creators":["Li, Gen"],"institution":"Massachusetts Institute of Technology","degree_name":"Doctoral","degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Department of Chemistry","school":null,"contributors":[],"advisors":["Radosevich, Alexander T."],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-05","date_published":"2022-05","updated_at":"2026-07-22T22:21:07Z","subjects":[],"languages":[],"rights":["In Copyright - Educational Use Permitted","Copyright MIT"],"rights_urls":["http://rightsstatements.org/page/InC-EDU/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1721.1/145029","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Radosevich, Alexander T."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. 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With the utilization of geometric-distorted organophosphetanes as catalysts and hydrosilanes as terminal reductants, nitro compounds (nitroarenes, nitromethane and nitroalkanes) undergo reductive O-atom transfer reactions involving the conversion of P(III)/P(V)=O. With that, boronic acids were employed as coupling partners to intercept the nitrene reactivity of nitro compounds derived oxazaphosphorane intermediates for direct reductive C–N coupling. This organophosphorus-catalyzed nitro deoxygenative platform was further developed to a tandem C–N coupling/cyclization sequence, yielding a variety N-functionalized azaheterocycles (oxindoles, indoles, quinoxalinediones, and benzimidazoles). Besides boronic acids, anilines were also introduced as an exogenous coupling partner for novel cross-selective intermolecular N–N bond forming reactivity in the formation of various hydrazines with excellent chemoselectivities and functional group tolerance. These works herein not only expand the reactivity of low-cost and environment-benign organophosphorus compounds as platforms for catalytic reductive O-atom transfer, but also details the P(III)/P(V)=O redox couple catalyzed reaction mechanism, providing further precedents for the catalytic potential of organophosphorus compounds in reaction classes heretofore dominated by transition-metal catalysis and suggesting potential opportunities for organophosphorus catalyst optimization."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["Organophosphorus-Catalyzed Reductive Functionalization of Nitrocompounds via P(III)/P(V) Redox Couple"]}]}],"canonical_facts":{"dc:contributor.advisor":["Radosevich, Alexander T."],"dc:contributor.department":["Massachusetts Institute of Technology. Department of Chemistry"],"dc:creator":["Li, Gen"],"dc:date.accessioned":["2022-08-29T16:28:17Z"],"dc:date.available":["2022-08-29T16:28:17Z"],"dc:date.issued":["2022-05"],"dc:description.abstract":["Nitro compounds are widely available synthetic building blocks which present a strategical opportunity to serve as direct precursors for the construction of nitrogen-containing molecules with increasing complexity and value. With the utilization of geometric-distorted organophosphetanes as catalysts and hydrosilanes as terminal reductants, nitro compounds (nitroarenes, nitromethane and nitroalkanes) undergo reductive O-atom transfer reactions involving the conversion of P(III)/P(V)=O. With that, boronic acids were employed as coupling partners to intercept the nitrene reactivity of nitro compounds derived oxazaphosphorane intermediates for direct reductive C–N coupling. This organophosphorus-catalyzed nitro deoxygenative platform was further developed to a tandem C–N coupling/cyclization sequence, yielding a variety N-functionalized azaheterocycles (oxindoles, indoles, quinoxalinediones, and benzimidazoles). Besides boronic acids, anilines were also introduced as an exogenous coupling partner for novel cross-selective intermolecular N–N bond forming reactivity in the formation of various hydrazines with excellent chemoselectivities and functional group tolerance. These works herein not only expand the reactivity of low-cost and environment-benign organophosphorus compounds as platforms for catalytic reductive O-atom transfer, but also details the P(III)/P(V)=O redox couple catalyzed reaction mechanism, providing further precedents for the catalytic potential of organophosphorus compounds in reaction classes heretofore dominated by transition-metal catalysis and suggesting potential opportunities for organophosphorus catalyst optimization."],"dc:description.degree":["Ph.D."],"dc:identifier.uri":["https://hdl.handle.net/1721.1/145029"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["In Copyright - Educational Use Permitted","Copyright MIT"],"dc:rights.uri":["http://rightsstatements.org/page/InC-EDU/1.0/"],"dc:title":["Organophosphorus-Catalyzed Reductive Functionalization of Nitrocompounds via P(III)/P(V) Redox Couple"],"dc:type":["Thesis"],"thesis:degree_name":["Doctoral","Doctor of Philosophy"]},"updated_at":"2026-07-22T22:21:07Z"}