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磷乙炔醇盐阴离子与稳定碳正离子的反应性：机理研究与合成应用。

Reactivity of the phosphaethynolate anion with stabilized carbocations: mechanistic studies and synthetic applications.

作者信息

Nguyen Thi Hong Van, Chelli Saloua, Mallet-Ladeira Sonia, Breugst Martin, Lakhdar Sami

机构信息

CNRS, Université Paul Sabatier, Laboratoire Hetérochimie Fondamentale et Appliquée (LHFA, UMR5069) 118 Route de Narbonne 31062 Cedex 09 Toulouse France

Institut de Chimie de Toulouse (FR 2599) 118 Route de Narbonne 31062 Cedex 09 Toulouse France.

出版信息

Chem Sci. 2024 Aug 8;15(35):14406-14. doi: 10.1039/d4sc03518f.

DOI:10.1039/d4sc03518f
PMID:39165734
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11331332/
Abstract

The reactivity of sodium phosphaethynolate Na(OCP) towards various Mayr's reference electrophiles was investigated using conventional UV-visible and laser-flash photolysis techniques. The kinetic data, along with density functional theory (DFT) calculations, enabled the first experimental quantification of the phosphorus nucleophilicity of [OCP]. Product studies of these reactions demonstrate the formation of secondary as well as tertiary phosphines. The mechanism of this unprecedented phosphorus-atom transfer reaction is thoroughly discussed, with key intermediates successfully isolated and characterized. Importantly, some bulky secondary phosphine oxides synthesized using this approach, have demonstrated high efficiency as ligands in the Suzuki coupling reaction.

摘要

采用传统紫外可见光谱和激光闪光光解技术研究了磷乙炔醇钠Na（OCP）与各种迈尔参考亲电试剂的反应活性。动力学数据以及密度泛函理论（DFT）计算，实现了对[OCP]磷亲核性的首次实验量化。这些反应的产物研究表明形成了仲膦和叔膦。对这种前所未有的磷原子转移反应的机理进行了深入讨论，成功分离并表征了关键中间体。重要的是，用这种方法合成的一些大体积仲膦氧化物在铃木偶联反应中作为配体表现出了高效率。

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本文引用的文献

1
Deciphering the Differences in Ambident Reactivity between the Cyanate, Thiocyanate Ions, and their P- and As-Containing Analogues.解析氰酸根、硫氰酸根离子及其 P 和 As 同系物的两性反应活性差异。
Chemistry. 2023 Jul 3;29(37):e202300611. doi: 10.1002/chem.202300611. Epub 2023 May 10.
2
Photocatalytic stannylation of white phosphorus.白磷的光催化锡化反应
Chem Commun (Camb). 2022 Aug 9;58(64):8986-8989. doi: 10.1039/d2cc03474c.
3
Recent Breakthroughs in P Chemistry: Towards Practical, Direct Transformations into P Compounds.
磷化学的最新突破：迈向磷化合物的实用直接转化
Angew Chem Int Ed Engl. 2022 Jul 11;61(28):e202205019. doi: 10.1002/anie.202205019. Epub 2022 May 25.
4
Phosphorus-Atom Transfer from Phosphaethynolate to an Alkylidyne.磷原子从磷乙炔醇盐向次烷基的转移。
Angew Chem Int Ed Engl. 2021 Nov 8;60(46):24411-24417. doi: 10.1002/anie.202107475. Epub 2021 Oct 7.
5
A Primary Acyl Phosphine Stabilized by a Phosphonium Ylide.一种由鏻叶立德稳定的伯酰基膦。
Angew Chem Int Ed Engl. 2021 Aug 16;60(34):18547-18551. doi: 10.1002/anie.202106846. Epub 2021 Jul 13.
6
Synthesis of monophosphines directly from white phosphorus.直接从白磷合成单膦。
Nat Chem. 2021 May;13(5):458-464. doi: 10.1038/s41557-021-00657-7. Epub 2021 Apr 5.
7
From Carbodiimides to Carbon Dioxide: Quantification of the Electrophilic Reactivities of Heteroallenes.从碳二亚胺到二氧化碳：杂联烯亲电反应活性的定量分析
J Am Chem Soc. 2020 May 6;142(18):8383-8402. doi: 10.1021/jacs.0c01960. Epub 2020 Apr 27.
8
Avenue to phosphaalkenes from PhGePCO.从 PhGePCO 到膦烯炔的途径。
Dalton Trans. 2020 Jan 21;49(3):885-890. doi: 10.1039/c9dt04590b.
9
Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer.通过磷烯转移实现酰基（氯）膦的合成。
Chem Sci. 2019 Feb 7;10(12):3627-3631. doi: 10.1039/c8sc05657a. eCollection 2019 Mar 28.
10
Uranium and thorium complexes of the phosphaethynolate ion.磷乙炔醇根离子的铀和钍配合物。
Chem Sci. 2015 Nov 1;6(11):6379-6384. doi: 10.1039/c5sc02150b. Epub 2015 Jul 20.