{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/147250"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/147250","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Synthesis and Reactivity of Phosphorus-Containing Heterocycles and Tetrahedranes","abstract":"3,5-Diphenyl-2-phosphafuran (DPF) was synthesized by treating trans-chalcone with dibenzo-7𝜆³ -phosphanorbornadiene EtOPA (A = C₁₄H₁₀, anthracene), a source of ethoxyphosphinidene, followed by formal elimination of ethanol. DPF is a potent diene and readily reacts with dienophiles at room temperature. Mild heating of the corresponding ethylene adduct results in the retro-Diels-Alder reaction. MesN₂PA (Mes = mesityl), a synthon of mesitylphosphaazide (MesN₂P) and anthracene, was synthesized by treating [Ph3BPA][Na(OEt₂)₂] with [MesN₂]OTf (OTf = CF₃SO₃ −). MesN₂PA reacts with alkynes and phosphaalkynes to form the corresponding [3+2] phosphaazide-(phospha)alkyne cycloadducts and anthracene. Mesitylphosphaazide transfer likely proceeds via a 1,3-dipolar cycloaddition reaction, followed by anthracene elimination. cis-Macrocyclic diphosphine (PhPA)₂ was prepared by treating [EtOP₂A₂]AlCl₄ with phenylmagnesium chloride (2 equiv). X-ray diffraction analysis of the the corresponding nickel dichloride complex shows the rigid, bowl-shaped cavity of (PhPA)₂. Tri-tert-butylphosphatetrahedrane (ᵗBuC)₃P was prepared via the dehydrohalogenation of fluorophosphine (ᵗBuC)₃P(F)H. The phosphatetrahedrane core was confirmed spectroscopically and by X-ray diffraction analysis. Hydrogen-hydrogen bonding interactions between neighboring tert-butyl groups of (ᵗBuC)₃P were computationally investigated and contribute approximately −6 kcal/mol of stabilization. Synthetically useful quantities of (ᵗBuC)₃P were obtained using an improved synthesis based on fluoride-induced trimethylsilyl chloride elimination from chloro(trimethylsilyl)phosphine (ᵗBuC)₃P(TMS)Cl. Despite the incorporation of phosphorus, (ᵗBuC)₃P remains highly reactive and cage-opens to the corresponding cyclobutadiene when treated with catalytic triphenylborane. The proposed reactive intermediate was trapped by styrene and ethylene to form [4+2]-cycloadducts. (ᵗBuC)₃P also functions as a spring-loaded phosphinidene synthon for nickelcatalyzed group transfer to unactivated alkenes, leading to phosphiranes, three-membered rings that contain a phosphorus atom. Deprotection of the corresponding phosphiranes was achieved by the addition of triflic acid to form a P−H bond and [ᵗBu₃C₃]OTf, demonstrating that (ᵗBuC)₃P can also be viewed as a ‘PH’ synthon. Tetrahydrofuran (THF) solutions of triphosphatetrahedrane HCP₃ were generated by combining [Na(THF)₃][P₃Nb(ODipp)₃] (Dipp = 2,6-diisopropylphenyl), bromodichloromethane, and INb(ODipp)₃(THF). Removal of solvent under reduced pressure led to a black material that corresponds to a polymerized form of HCP₃. X-ray diffraction analysis of a cationic iron complex of HCP₃ confirmed the tetrahedral nature of the CP₃ core. Computational studies suggest that triphosphatetrahedrane is the least strained tetrahedrane with as mixed carbon-phosphorus core.","abstract_html":"3,5-Diphenyl-2-phosphafuran (DPF) was synthesized by treating trans-chalcone with dibenzo-7𝜆³ -phosphanorbornadiene EtOPA (A = C₁₄H₁₀, anthracene), a source of ethoxyphosphinidene, followed by formal elimination of ethanol. DPF is a potent diene and readily reacts with dienophiles at room temperature. Mild heating of the corresponding ethylene adduct results in the retro-Diels-Alder reaction. MesN₂PA (Mes = mesityl), a synthon of mesitylphosphaazide (MesN₂P) and anthracene, was synthesized by treating [Ph3BPA][Na(OEt₂)₂] with [MesN₂]OTf (OTf = CF₃SO₃ −). MesN₂PA reacts with alkynes and phosphaalkynes to form the corresponding [3+2] phosphaazide-(phospha)alkyne cycloadducts and anthracene. Mesitylphosphaazide transfer likely proceeds via a 1,3-dipolar cycloaddition reaction, followed by anthracene elimination. cis-Macrocyclic diphosphine (PhPA)₂ was prepared by treating [EtOP₂A₂]AlCl₄ with phenylmagnesium chloride (2 equiv). X-ray diffraction analysis of the the corresponding nickel dichloride complex shows the rigid, bowl-shaped cavity of (PhPA)₂. Tri-tert-butylphosphatetrahedrane (ᵗBuC)₃P was prepared via the dehydrohalogenation of fluorophosphine (ᵗBuC)₃P(F)H. The phosphatetrahedrane core was confirmed spectroscopically and by X-ray diffraction analysis. Hydrogen-hydrogen bonding interactions between neighboring tert-butyl groups of (ᵗBuC)₃P were computationally investigated and contribute approximately −6 kcal/mol of stabilization. Synthetically useful quantities of (ᵗBuC)₃P were obtained using an improved synthesis based on fluoride-induced trimethylsilyl chloride elimination from chloro(trimethylsilyl)phosphine (ᵗBuC)₃P(TMS)Cl. Despite the incorporation of phosphorus, (ᵗBuC)₃P remains highly reactive and cage-opens to the corresponding cyclobutadiene when treated with catalytic triphenylborane. The proposed reactive intermediate was trapped by styrene and ethylene to form [4+2]-cycloadducts. (ᵗBuC)₃P also functions as a spring-loaded phosphinidene synthon for nickelcatalyzed group transfer to unactivated alkenes, leading to phosphiranes, three-membered rings that contain a phosphorus atom. Deprotection of the corresponding phosphiranes was achieved by the addition of triflic acid to form a P−H bond and [ᵗBu₃C₃]OTf, demonstrating that (ᵗBuC)₃P can also be viewed as a ‘PH’ synthon. Tetrahydrofuran (THF) solutions of triphosphatetrahedrane HCP₃ were generated by combining [Na(THF)₃][P₃Nb(ODipp)₃] (Dipp = 2,6-diisopropylphenyl), bromodichloromethane, and INb(ODipp)₃(THF). Removal of solvent under reduced pressure led to a black material that corresponds to a polymerized form of HCP₃. X-ray diffraction analysis of a cationic iron complex of HCP₃ confirmed the tetrahedral nature of the CP₃ core. Computational studies suggest that triphosphatetrahedrane is the least strained tetrahedrane with as mixed carbon-phosphorus core.","abstract_has_math":false,"creators":["Riu, Martin-Louis Y."],"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":["Cummins, Christopher C."],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-09","date_published":"2022-09","updated_at":"2026-07-22T22:21:45Z","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/1721.1/147250","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Cummins, Christopher C."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. Department of Chemistry"]},{"key":"dc:creator","label":"Author","values":["Riu, Martin-Louis Y."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2023-01-19T18:40:20Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2023-01-19T18:40:20Z"]},{"key":"dc:date.issued","label":"Date","values":["2022-09"]},{"key":"dc:publisher","label":"Institution","values":["Massachusetts Institute of Technology"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctoral","Doctor of Philosophy"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["In Copyright - Educational Use Permitted","Copyright MIT"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/page/InC-EDU/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/1721.1/147250"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["3,5-Diphenyl-2-phosphafuran (DPF) was synthesized by treating trans-chalcone with dibenzo-7𝜆³ -phosphanorbornadiene EtOPA (A = C₁₄H₁₀, anthracene), a source of ethoxyphosphinidene, followed by formal elimination of ethanol. DPF is a potent diene and readily reacts with dienophiles at room temperature. Mild heating of the corresponding ethylene adduct results in the retro-Diels-Alder reaction. MesN₂PA (Mes = mesityl), a synthon of mesitylphosphaazide (MesN₂P) and anthracene, was synthesized by treating [Ph3BPA][Na(OEt₂)₂] with [MesN₂]OTf (OTf = CF₃SO₃ −). MesN₂PA reacts with alkynes and phosphaalkynes to form the corresponding [3+2] phosphaazide-(phospha)alkyne cycloadducts and anthracene. Mesitylphosphaazide transfer likely proceeds via a 1,3-dipolar cycloaddition reaction, followed by anthracene elimination. cis-Macrocyclic diphosphine (PhPA)₂ was prepared by treating [EtOP₂A₂]AlCl₄ with phenylmagnesium chloride (2 equiv). X-ray diffraction analysis of the the corresponding nickel dichloride complex shows the rigid, bowl-shaped cavity of (PhPA)₂. Tri-tert-butylphosphatetrahedrane (ᵗBuC)₃P was prepared via the dehydrohalogenation of fluorophosphine (ᵗBuC)₃P(F)H. The phosphatetrahedrane core was confirmed spectroscopically and by X-ray diffraction analysis. Hydrogen-hydrogen bonding interactions between neighboring tert-butyl groups of (ᵗBuC)₃P were computationally investigated and contribute approximately −6 kcal/mol of stabilization. Synthetically useful quantities of (ᵗBuC)₃P were obtained using an improved synthesis based on fluoride-induced trimethylsilyl chloride elimination from chloro(trimethylsilyl)phosphine (ᵗBuC)₃P(TMS)Cl. Despite the incorporation of phosphorus, (ᵗBuC)₃P remains highly reactive and cage-opens to the corresponding cyclobutadiene when treated with catalytic triphenylborane. The proposed reactive intermediate was trapped by styrene and ethylene to form [4+2]-cycloadducts. (ᵗBuC)₃P also functions as a spring-loaded phosphinidene synthon for nickelcatalyzed group transfer to unactivated alkenes, leading to phosphiranes, three-membered rings that contain a phosphorus atom. Deprotection of the corresponding phosphiranes was achieved by the addition of triflic acid to form a P−H bond and [ᵗBu₃C₃]OTf, demonstrating that (ᵗBuC)₃P can also be viewed as a ‘PH’ synthon. Tetrahydrofuran (THF) solutions of triphosphatetrahedrane HCP₃ were generated by combining [Na(THF)₃][P₃Nb(ODipp)₃] (Dipp = 2,6-diisopropylphenyl), bromodichloromethane, and INb(ODipp)₃(THF). Removal of solvent under reduced pressure led to a black material that corresponds to a polymerized form of HCP₃. X-ray diffraction analysis of a cationic iron complex of HCP₃ confirmed the tetrahedral nature of the CP₃ core. Computational studies suggest that triphosphatetrahedrane is the least strained tetrahedrane with as mixed carbon-phosphorus core."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["Synthesis and Reactivity of Phosphorus-Containing Heterocycles and Tetrahedranes"]}]}],"canonical_facts":{"dc:contributor.advisor":["Cummins, Christopher C."],"dc:contributor.department":["Massachusetts Institute of Technology. Department of Chemistry"],"dc:creator":["Riu, Martin-Louis Y."],"dc:date.accessioned":["2023-01-19T18:40:20Z"],"dc:date.available":["2023-01-19T18:40:20Z"],"dc:date.issued":["2022-09"],"dc:description.abstract":["3,5-Diphenyl-2-phosphafuran (DPF) was synthesized by treating trans-chalcone with dibenzo-7𝜆³ -phosphanorbornadiene EtOPA (A = C₁₄H₁₀, anthracene), a source of ethoxyphosphinidene, followed by formal elimination of ethanol. DPF is a potent diene and readily reacts with dienophiles at room temperature. Mild heating of the corresponding ethylene adduct results in the retro-Diels-Alder reaction. MesN₂PA (Mes = mesityl), a synthon of mesitylphosphaazide (MesN₂P) and anthracene, was synthesized by treating [Ph3BPA][Na(OEt₂)₂] with [MesN₂]OTf (OTf = CF₃SO₃ −). MesN₂PA reacts with alkynes and phosphaalkynes to form the corresponding [3+2] phosphaazide-(phospha)alkyne cycloadducts and anthracene. Mesitylphosphaazide transfer likely proceeds via a 1,3-dipolar cycloaddition reaction, followed by anthracene elimination. cis-Macrocyclic diphosphine (PhPA)₂ was prepared by treating [EtOP₂A₂]AlCl₄ with phenylmagnesium chloride (2 equiv). X-ray diffraction analysis of the the corresponding nickel dichloride complex shows the rigid, bowl-shaped cavity of (PhPA)₂. Tri-tert-butylphosphatetrahedrane (ᵗBuC)₃P was prepared via the dehydrohalogenation of fluorophosphine (ᵗBuC)₃P(F)H. The phosphatetrahedrane core was confirmed spectroscopically and by X-ray diffraction analysis. Hydrogen-hydrogen bonding interactions between neighboring tert-butyl groups of (ᵗBuC)₃P were computationally investigated and contribute approximately −6 kcal/mol of stabilization. Synthetically useful quantities of (ᵗBuC)₃P were obtained using an improved synthesis based on fluoride-induced trimethylsilyl chloride elimination from chloro(trimethylsilyl)phosphine (ᵗBuC)₃P(TMS)Cl. Despite the incorporation of phosphorus, (ᵗBuC)₃P remains highly reactive and cage-opens to the corresponding cyclobutadiene when treated with catalytic triphenylborane. The proposed reactive intermediate was trapped by styrene and ethylene to form [4+2]-cycloadducts. (ᵗBuC)₃P also functions as a spring-loaded phosphinidene synthon for nickelcatalyzed group transfer to unactivated alkenes, leading to phosphiranes, three-membered rings that contain a phosphorus atom. Deprotection of the corresponding phosphiranes was achieved by the addition of triflic acid to form a P−H bond and [ᵗBu₃C₃]OTf, demonstrating that (ᵗBuC)₃P can also be viewed as a ‘PH’ synthon. Tetrahydrofuran (THF) solutions of triphosphatetrahedrane HCP₃ were generated by combining [Na(THF)₃][P₃Nb(ODipp)₃] (Dipp = 2,6-diisopropylphenyl), bromodichloromethane, and INb(ODipp)₃(THF). Removal of solvent under reduced pressure led to a black material that corresponds to a polymerized form of HCP₃. X-ray diffraction analysis of a cationic iron complex of HCP₃ confirmed the tetrahedral nature of the CP₃ core. Computational studies suggest that triphosphatetrahedrane is the least strained tetrahedrane with as mixed carbon-phosphorus core."],"dc:description.degree":["Ph.D."],"dc:identifier.uri":["https://hdl.handle.net/1721.1/147250"],"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":["Synthesis and Reactivity of Phosphorus-Containing Heterocycles and Tetrahedranes"],"dc:type":["Thesis"],"thesis:degree_name":["Doctoral","Doctor of Philosophy"]},"updated_at":"2026-07-22T22:21:45Z"}