Photoinduced synthesis of C2-linked phosphine oxides <i>via</i> radical difunctionalization of acetylene

Li, Kangkui; Deng, Jiazhen; Long, Xianyang; Zhu, Shifa

doi:10.1039/d3gc02794e

Green Chem.

2023

DOI: 10.1039/d3gc02794e

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Photoinduced synthesis of C2-linked phosphine oxides via radical difunctionalization of acetylene

Kangkui Li¹,

Jiazhen Deng²,

Xianyang Long³

et al.

Abstract: Herein, we report a photocatalyzed radical difunctionalization of acetylene for the rapid synthesis of C2-linked phosphine compounds. The reaction was initiated by addition of a phosphinoyl radical and follwed by...

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2024

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Cited by 4 publications

References 82 publications

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Radical Difunctionalization of Unsaturated Hydrocarbons Employing the Same Functional Reagent

Tian,

Dai,

et al. 2024

Adv Synth Catal

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The radical difunctionalization of unsaturated hydrocarbons serves as an efficient means to rapidly construct molecular skeletons and synthesize‐highly valuable compounds. In this transformational process, diverse positions within unsaturated hydrocarbons are sequentially functionalized by a single radical precursor reagent, thereby achieving highly efficient and selective transformations that promote atom economy. Furthermore, this approach minimizes the generation of numerous byproducts stemming from cross‐coupling reactions between reactants, owing to the reduction of the number of participating components. Therefore, this review provides an in‐depth analysis of the radical difunctionalization of unsaturated hydrocarbons utilizing a single functional reagent in recent decades. The discussion is based on eight different radical classes (carbon‐, nitrogen‐, phosphine‐, oxygen‐, sulfur‐, selenium‐, tellurium‐, and chlorine‐centered radicals), emphasizing the mechanism of specific radical difunctionalization. It also analyzes in detail the regulation of key factors such as regional selectivity, and provides unique insights into reaction transformations.

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Radical Difunctionalization of Unsaturated Hydrocarbons Employing the Same Functional Reagent

Tian,

Dai,

et al. 2024

Adv Synth Catal

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Bifunctional two-carbon reagent made from acetylene via 1,2-difunctionalization and its applications

Yang,

Li,

Wang

et al. 2024

Sci. China Chem.

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s-Block Metal Base-Catalyzed Synthesis of Sterically Encumbered Derivatives of Ethane-1,2-diyl-bis(diphenylphosphane oxide) (dppeO₂)

Fener,

Schüler,

Pröhl

et al. 2024

Organometallics

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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 (Mes 2 P(O)H) yields an E/Z mixture of alkenyldimesitylphosphane 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 2 P(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(nalkyl)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 2 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., Y 3+ ) and soft metal ions (e.g., Pd 2+ ).

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Photoinduced synthesis of C2-linked phosphine oxides via radical difunctionalization of acetylene

Abstract: Herein, we report a photocatalyzed radical difunctionalization of acetylene for the rapid synthesis of C2-linked phosphine compounds. The reaction was initiated by addition of a phosphinoyl radical and follwed by...

Cited by 4 publications

References 82 publications

Radical Difunctionalization of Unsaturated Hydrocarbons Employing the Same Functional Reagent

Radical Difunctionalization of Unsaturated Hydrocarbons Employing the Same Functional Reagent

Bifunctional two-carbon reagent made from acetylene via 1,2-difunctionalization and its applications

s-Block Metal Base-Catalyzed Synthesis of Sterically Encumbered Derivatives of Ethane-1,2-diyl-bis(diphenylphosphane oxide) (dppeO₂)

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Photoinduced synthesis of C2-linked phosphine oxides via radical difunctionalization of acetylene

Abstract: Herein, we report a photocatalyzed radical difunctionalization of acetylene for the rapid synthesis of C2-linked phosphine compounds. The reaction was initiated by addition of a phosphinoyl radical and follwed by...

Cited by 4 publications

References 82 publications

Radical Difunctionalization of Unsaturated Hydrocarbons Employing the Same Functional Reagent

Radical Difunctionalization of Unsaturated Hydrocarbons Employing the Same Functional Reagent

Bifunctional two-carbon reagent made from acetylene via 1,2-difunctionalization and its applications

s-Block Metal Base-Catalyzed Synthesis of Sterically Encumbered Derivatives of Ethane-1,2-diyl-bis(diphenylphosphane oxide) (dppeO2)

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Product

Resources

About

s-Block Metal Base-Catalyzed Synthesis of Sterically Encumbered Derivatives of Ethane-1,2-diyl-bis(diphenylphosphane oxide) (dppeO₂)