The Phospha-Bora-Wittig Reaction

Borys, Andryj M.; Rice, Ella F.; Nichol, Gary S.; Cowley, Michael J.

doi:10.1021/jacs.1c06228

Cited by 23 publications

(29 citation statements)

References 55 publications

(86 reference statements)

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“…In contrast, the heavier BP‐analogues (phosphaborenes) possess a considerably weaker π‐bond, [10] and, consequently, a strong tendency to dimerize [13] . For sterically enriched systems, transient monomeric phosphaborene species can be thermally generated in solution and subsequently reacted with unsaturated organic compounds, including phenylacetylene, aldehydes, ketones, esters, or amides, to produce [2+2] cycloaddition or phosphaalkenes products, respectively [13d, 14] . Also, the monomeric species can be trapped by suppressing the dimerization via coordination to Lewis acids at P or Lewis bases on B terminal [15]…”

Section: Methodsmentioning

confidence: 99%

“…Although a handful of phosphaborenes examples have been reported from the pioneering works of Nöth ( IV ), [15a] Power( V ), [15b,c] and more recently Cowley ( VI and VII ), [13d, 14, 16] and Gilliard ( VIII ), [17] their chemistry remains rather unexplored. In particular, it has not yet been possible to observe a process where the BP‐unit is transferred.…”

Section: Methodsmentioning

confidence: 99%

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Metathesis Reactions of a NHC‐Stabilized Phosphaborene

2022

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The BP unsaturated unit is a very attractive functional group as it provides novel reactivity and unique physical properties. Nonetheless, applications remain limited so far due to the bulky nature of B/Pprotecting groups, required to prevent oligomerization. Herein, we report the synthesis and isolation of a Nheterocyclic carbene (NHC)-stabilized phosphaborene, bearing a trimethylsilyl (TMS) functionality at the Pterminal, as a room-temperature-stable crystalline solid accessible via facile NHC-induced trimethylsilyl chloride (TMSCl) elimination from its phosphinoborane precursor. This phosphaborene compound, bearing a genuine B=P bond, exhibits a remarkable ability for undergoing P-centre metathesis reactions, which allows the isolation of a series of unprecedented phosphaborenes. X-ray crystallographic analysis, UV/Vis spectroscopy, and DFT calculations provide insights into the B=P bonding situation.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Metathesis Reactions of a NHC‐Stabilized Phosphaborene

2022

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“…Phosphaboren‐Spezies thermisch in Lösung generiert werden und dann mit ungesättigten organischen Verbindungen, Phenylacetylene, Aldehyde, Ketone, Ester oder Amide eingeschlossen, umgesetzt werden, um [2+2]‐Cycloadditionen einzugehen oder entsprechende Phosphaalken‐Produkte zu produzieren [13d, 14] . Außerdem kann die monomere Spezies, durch Unterdrückung der Dimerisierung mithilfe von endständiger Koordination von Lewis‐Säuren am P oder Lewis‐Basen am B, abgefangen werden [15]…”

Section: Methodsunclassified

“…Obwohl in den Pionierarbeiten von Nöth ( IV ), [15a] Power( V ), [15b,c] und, aktueller, Cowley ( VI und VII ), [13d, 14, 16] sowie Gilliard ( VIII ) [17] eine Handvoll Phosphaboren‐Beispiele berichtet wurde, verbleibt ihre Chemie recht unerforscht. Insbesondere ist es bisher nicht möglich gewesen, einen Prozess zu beobachten, bei dem die BP‐Einheit tranferiert wird.…”

Section: Methodsunclassified

Metathese Reaktionen eines NHC‐stabilisierten Phosphaborens

2022

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Die ungesättigte BP-Einheit stellt durch ihre neuartige Reaktivität und ihre einzigartigen physikalischen Eigenschaften eine attraktive funktionelle Gruppe dar. Nichtsdestotrotz ist ihre Anwendung begrenzt durch die sperrige Natur der B/P-Schutzgruppen, welche erforderlich sind, um Oligomerisation zu vermeiden. Wir berichten hiermit von der Synthese und Isolation eines N-heterozyklischen Carben-(NHC) stabilisierten Phosphaborens, welches eine Trimethylsilyl-(TMS) Funktionalität am endständigen P trägt, ein bei Raumtemperatur stabiler kristalliner Feststoff, zugänglich durch einfache NHC-induzierte Trimethylsilylchlorid-(TMSCl) Eliminierung des Phosphinoboran-Präkursors. Diese Phosphaborenverbindung, die eine genuine B=P-Bindung enthält, zeigt die außergewöhnliche Fähigkeit, P-zentrierte Metathese Reaktionen einzugehen, was die Isolierung einer Reihe neuartiger Phosphaborene erlaubt. Röntgenkristallographische Analyse, UV/Vis-Spektroskopie und DFT-Rechnungen liefern Einblicke in die B=P Bindungssituation.

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“…An impressive portfolio of Wittig-type reactions has been published to date and the field is still evolving. To mention just a few significant contributions, bora-, [5,6] aza-, [7] phospha-, [8,9] arsa-, [10][11][12] sila-, [13] and most recently phospha-bora [14] Wittig reactions have been described.…”

Section: Introductionmentioning

confidence: 99%

On the ambiphilic character of phosphanylidenephosphoranes and manipulation of phosphinidenoid reactivity with Lewis acids

Dankert

Fischer

Hering‐Junghans

2022

Preprint

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Phosphanylidenephosphoranes of the type R−P(PR’3), also known as phospha-Wittig reagents, can be utilized in a variety of bond activation reactions pursuing their phosphinidenoid reactivity. In here, we thoroughly show that a facile PMe3 for H2O exchange gives access to various primary phosphine oxides of the general formula RP(H)2O (R = Mes*, MesTer, DipTer). The molecular structure of DipTerP(H)2O was determined and provided the first picture of such species in the solid state. However, phosphanylidenephosphoranes are described to be highly nucleophilic as well. We show that the attachment of main group Lewis acids such as GaCl3 and GaI3 to2 R−P(PMe3) yielded highly sensitive, yet stable coordination compounds [RP(GaX3)PMe3] (R = Mes*, DipTer) or [(RPPMe3)2GaCl2]GaCl4 (R = MesTer). In contrast to the free phosphanylidenephosphoranes, these species reacted differently with H2O which was demonstrated for [(Mes*PPMe3)GaI3]. Here the formation of the phosphinophosphonium cation [Mes*P(H)PMe3]+ and different anions was observed with combined NMR spectroscopic and SC-XRD (SC-XRD = single crystal diffraction analysis) studies. This work demonstrates that the ambiphilic character of phosphanylidenephosphoranes can be utilized to manipulate the reactivity of R−P(PMe3) towards water, giving primary phosphine oxides, whereas the Lewis acid adducts [(RPPMe3)GaX3] gave phosphino-phosphonium species.

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The Phospha-Bora-Wittig Reaction

Cited by 23 publications

References 55 publications

Metathesis Reactions of a NHC‐Stabilized Phosphaborene

Metathesis Reactions of a NHC‐Stabilized Phosphaborene

Metathese Reaktionen eines NHC‐stabilisierten Phosphaborens

On the ambiphilic character of phosphanylidenephosphoranes and manipulation of phosphinidenoid reactivity with Lewis acids

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