Benjamin E. Fener, Philipp Schüler, Felix E. Pröhl, Helmar Görls, Phil Liebing and Matthias Westerhausen*,
{"title":"s-嵌段金属碱催化合成乙烷-1,2-二基双(二苯基氧化膦)(dppeO2)的立体包被衍生物","authors":"Benjamin E. Fener, Philipp Schüler, Felix E. Pröhl, Helmar Görls, Phil Liebing and Matthias Westerhausen*, ","doi":"10.1021/acs.organomet.4c00052","DOIUrl":null,"url":null,"abstract":"<p >The synthesis of ethane-1,2-diyl-bis(diarylphosphane oxides) and -phosphanes, containing bulky <i>ortho</i>-substituted P-bound aryl groups, poses severe challenges, such as drastic reaction conditions and low yields. A potassium base-mediated hydrophosphorylation of phenylacetylene with dimesitylphosphane oxide (Mes<sub>2</sub>P(O)H) yields an <i>E</i>/<i>Z</i> mixture of alkenyl-dimesitylphosphane oxide. The bulky mesityl group hampers the addition of a second diarylphosphane oxide. Contrary to this expected addition of a phosphane oxide across an alkyne yielding an alkenylphosphane oxide, the potassium base-mediated reaction of trimethylsilyl acetylene with Mes<sub>2</sub>P(O)H yields ethane-1,2-diyl-bis(dimesitylphosphane oxide) (<b>2b</b>); surprisingly, the TMS group is substituted by a hydrogen atom via a rather complex reaction mechanism. Excess TMS-C≡CH (5 equiv), ethereal solvents, soft alkali metal catalysts, and large catalyst loadings of 30 mol % are highly beneficial. Furthermore, at least one <i>ortho</i>-position must be alkylated, whereas very bulky aryl groups pose no obstacle. Di(<i>n</i>-alkyl)phosphane oxides and diphenylphosphane oxide do not show the described conversion but react completely different. Alternatively, ethane-1,2-diyl-bis(diarylphosphane oxides) are accessible via a metathetical approach of calcium acetylide CaC<sub>2</sub> with diarylphosphane oxide in a superbasic solvent. Reduction of these phosphane oxides (<b>2</b>) to phosphanes (<b>3</b>) offers a library of bulky bidentate ligands for coordination chemistry at hard (e.g., Y<sup>3+</sup>) and soft metal ions (e.g., Pd<sup>2+</sup>).</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00052","citationCount":"0","resultStr":"{\"title\":\"s-Block Metal Base-Catalyzed Synthesis of Sterically Encumbered Derivatives of Ethane-1,2-diyl-bis(diphenylphosphane oxide) (dppeO2)\",\"authors\":\"Benjamin E. Fener, Philipp Schüler, Felix E. Pröhl, Helmar Görls, Phil Liebing and Matthias Westerhausen*, \",\"doi\":\"10.1021/acs.organomet.4c00052\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The synthesis of ethane-1,2-diyl-bis(diarylphosphane oxides) and -phosphanes, containing bulky <i>ortho</i>-substituted P-bound aryl groups, poses severe challenges, such as drastic reaction conditions and low yields. A potassium base-mediated hydrophosphorylation of phenylacetylene with dimesitylphosphane oxide (Mes<sub>2</sub>P(O)H) yields an <i>E</i>/<i>Z</i> mixture of alkenyl-dimesitylphosphane oxide. The bulky mesityl group hampers the addition of a second diarylphosphane oxide. Contrary to this expected addition of a phosphane oxide across an alkyne yielding an alkenylphosphane oxide, the potassium base-mediated reaction of trimethylsilyl acetylene with Mes<sub>2</sub>P(O)H yields ethane-1,2-diyl-bis(dimesitylphosphane oxide) (<b>2b</b>); surprisingly, the TMS group is substituted by a hydrogen atom via a rather complex reaction mechanism. Excess TMS-C≡CH (5 equiv), ethereal solvents, soft alkali metal catalysts, and large catalyst loadings of 30 mol % are highly beneficial. Furthermore, at least one <i>ortho</i>-position must be alkylated, whereas very bulky aryl groups pose no obstacle. Di(<i>n</i>-alkyl)phosphane oxides and diphenylphosphane oxide do not show the described conversion but react completely different. Alternatively, ethane-1,2-diyl-bis(diarylphosphane oxides) are accessible via a metathetical approach of calcium acetylide CaC<sub>2</sub> with diarylphosphane oxide in a superbasic solvent. 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s-Block Metal Base-Catalyzed Synthesis of Sterically Encumbered Derivatives of Ethane-1,2-diyl-bis(diphenylphosphane oxide) (dppeO2)
The synthesis of ethane-1,2-diyl-bis(diarylphosphane oxides) and -phosphanes, containing bulky ortho-substituted P-bound aryl groups, poses severe challenges, such as drastic reaction conditions and low yields. A potassium base-mediated hydrophosphorylation of phenylacetylene with dimesitylphosphane oxide (Mes2P(O)H) yields an E/Z mixture of alkenyl-dimesitylphosphane oxide. The bulky mesityl group hampers the addition of a second diarylphosphane oxide. Contrary to this expected addition of a phosphane oxide across an alkyne yielding an alkenylphosphane oxide, the potassium base-mediated reaction of trimethylsilyl acetylene with Mes2P(O)H yields ethane-1,2-diyl-bis(dimesitylphosphane oxide) (2b); surprisingly, the TMS group is substituted by a hydrogen atom via a rather complex reaction mechanism. Excess TMS-C≡CH (5 equiv), ethereal solvents, soft alkali metal catalysts, and large catalyst loadings of 30 mol % are highly beneficial. Furthermore, at least one ortho-position must be alkylated, whereas very bulky aryl groups pose no obstacle. Di(n-alkyl)phosphane oxides and diphenylphosphane oxide do not show the described conversion but react completely different. Alternatively, ethane-1,2-diyl-bis(diarylphosphane oxides) are accessible via a metathetical approach of calcium acetylide CaC2 with diarylphosphane oxide in a superbasic solvent. Reduction of these phosphane oxides (2) to phosphanes (3) offers a library of bulky bidentate ligands for coordination chemistry at hard (e.g., Y3+) and soft metal ions (e.g., Pd2+).
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.