Phospha-alkynes - Useful Building Blocks in Organic Chemistry<sup>1</sup>

Regitz, Manfred; Rösch, Wolfgang; Allspach, T.; Annen, U.; Blatter, Karsten; Fink, Jürgen; Hermesdorf, M.; Heydt, H.; Vogelbacher, Uwe‐Josef; Wagner, O.

doi:10.1080/03086648708080624

Cited by 27 publications

(7 citation statements)

References 6 publications

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“…It has been found advantageous not to perform the reaction 12 -* 3 in solution, as originally reported,23 but rather to work at temperatures of 120-200 °C in the absence of a solvent. 24,48,49 Using this variation, it was possible to prepare not only phosphaalkynes with tertiary carbon substituents (3a,d-g,j) but also those with secondary carbon substituents (see . In addition, tetrabutylammonium fluoride on silica gel (12h -3h)52 and diiron nonacarbonyl (CE/Z-12a -* 3a)50 are also able to bring about the elimination reactions; in the cases of 3i53 and 3k54 no auxiliary reagents are necessary.…”

Section: Of Hexamethyldisiloxanementioning

confidence: 99%

Phosphaalkynes: new building blocks in synthetic chemistry

Regitz¹

1990

Chem. Rev.

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320

117

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Section: Of Hexamethyldisiloxanementioning

confidence: 99%

Phosphaalkynes: new building blocks in synthetic chemistry

Regitz¹

1990

Chem. Rev.

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320

117

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“…[18][19][20] Here we want to report on the activation of a phosphaalkyne, P≡C-t Bu, [21][22][23][24] its rearrangement reaction to a [2.1.1]heterobicycles (2, Scheme 2) and its application in gold(I) complexation reactions (Scheme 3). As shown in Scheme 2, the facile addition of phosphaalkyne P≡C-t Bu onto the singlet biradicaloid 1 is complete within minutes and cage compound 2 is formed in quantitative yield.…”

Section: Resultsmentioning

confidence: 99%

“…The reactivity of [P(m-NTer)] 2 (1) (Ter = 2,6-dimesityl-phenyl) has been utilized widely to activate small molecules such as alkenes and alkynes leading to bicycle and cage compounds. [18][19][20] Here we want to report on the activation of a phosphaalkyne, PRC-t Bu, [21][22][23][24] its rearrangement reaction to [2.1.1]heterobicycles (2, Scheme 2) and its application in gold(I) complexation reactions (Scheme 3).…”

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P–P σ-bond activation by gold(I) coordination

2015

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Bond activation by gold is of imminent interest with respect to catalytic activity. By coordination of an AuCl fragment onto the P-P σ-bond of an azadiphosphiridine, the P-P bond is cleaved to give a PNP type of ligand in the gold(I) complex. Another equivalent of the gold precursor selectively binds on a P lone pair. The bonding situation was further studied by means of computation, indicating the existence of a 3-center-2-electron bond.

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“…M elting points are uncorrected (heating rate 2°/m in). N [23], 4b [24], 4d,e [25,26], 5a,b [27,28], 21a [29], 21b [30] and 15a [31] w ere p rep ared by p u b lished m ethods.…”

Section: Methodsmentioning

confidence: 99%

Organophosphorus Compounds, Part 146* Imidovanadium(V) Complexes as Reaction Partners for Kinetically Stabilized Phosphaalkynes. Synthesis and Reactivity of 3-Aza-l,2,4,6-tetraphospha-quadricyclanes

Peters

Tabellion

Nachbauer

et al. 2001

Zeitschrift Für Naturforschung B

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The Lewis base adducts of imidovanadium(V) compounds 5a,b undergo chemoselective cyclooligomerization reactions with the kinetically stabilized phosphaalkynes 4a-e to furnish the azatetraphosphaquadricyclanes 6a-f with incorporation of the imido fragment. The reac tivity of this novel class of heteropolycyclic compounds has been examined exemplarily for compound 6a. Complexation of one and two phosphorus atoms was achieved by reaction with nonacarbonyldiiron or the tungsten pentacarbonyl-THF complex resulting in the forma tion of the transition metal compounds 17-20. Reactions of 6a with the sulfonyl azides 21ac furnished the Staudinger products 22a-c. The reaction of 6a with two equivalents of tosyl azide gave a surprising result. No double complexation leading to a symmetrical product was achieved, and compound 23 was obtained instead in which the two phosphorus atoms of one diphosphirane ring are functionalized. Oxidative cleavage of a P/P bond in 6a to furnish product 24 is observed in the reaction of 6a with the Lewis base-free imidovanadium(V) species 15a. Intro d u ctio nCage com pounds, som e of which have highly sym m etrical skeletons, have always been of great in terest to chemists. T heir often tedious, m ulti stage syntheses have p resented a challenge to ex p erim ental tech n iq u es and the unusual bonding relationships have gen erated new im pulses for theoretical considerations.Thus, it is n o t surprising that th e construction of phosphoru s-carb o n cage com pounds has devel oped into an im p o rta n t field in th e chem istry of kinetically stabilized phosphaalkynes. In contrast to their all-carbon analogues, how ever, access to the phosp h o ru s-carb o n cage system s has only b e com e possible in th e past ten years w ith the ph o s phaalkynes being indispensable starting com pounds. * Part 145: S. G. Ruf, U. Bergsträsser, M. Regitz, Eur. J. Org. Chem. 2000, 2219. M ajor b reakthroughs in this developm ent in clude the syntheses of the tetrap h o sp h acu b an e 1 [1 ], the tetrap hosphabishom oprism ane 2 [2 ], and the h ex aphosphapentaprism ane 3 [3] (Schem e 1).The cubane 1 was of p articular in terest on account of its high sym m etry and its at first inexplicable spectral properties. A ccordingly, the rem arkably stable cubane 1 has, on th e one hand, b een the subject of num erous th eo retical bonding studies [4 -6 ] and, on the o th er hand, the starting point for m any functionalization reactions at the ph o s phorus atom s [7 -9 ]. A lthough the first syntheses of the phosphaalkyne te tra m ers 1 and 2 w ere based on the therm olysis of the fe/t-butylphosphaalkyne 4a, m any novel synthetic strategies have since been developed for the specific con struction of polycyclic phosphorus-carbon systems. These now provide selective and high-yield access to the cage com pounds 1 and 2. The synthetic p rin ciples em ployed include transition m etal-(-> 1 [10,11]), base-(-»• 2 [12]), and Lewis acid-m ediated processes (-* ■ 3 [3]).

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Phospha-alkynes - Useful Building Blocks in Organic Chemistry¹

Cited by 27 publications

References 6 publications

Phosphaalkynes: new building blocks in synthetic chemistry

Phosphaalkynes: new building blocks in synthetic chemistry

P–P σ-bond activation by gold(I) coordination

Organophosphorus Compounds, Part 146* Imidovanadium(V) Complexes as Reaction Partners for Kinetically Stabilized Phosphaalkynes. Synthesis and Reactivity of 3-Aza-l,2,4,6-tetraphospha-quadricyclanes

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Phospha-alkynes - Useful Building Blocks in Organic Chemistry1

Cited by 27 publications

References 6 publications

Phosphaalkynes: new building blocks in synthetic chemistry

Phosphaalkynes: new building blocks in synthetic chemistry

P–P σ-bond activation by gold(I) coordination

Organophosphorus Compounds, Part 146* Imidovanadium(V) Complexes as Reaction Partners for Kinetically Stabilized Phosphaalkynes. Synthesis and Reactivity of 3-Aza-l,2,4,6-tetraphospha-quadricyclanes

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Phospha-alkynes - Useful Building Blocks in Organic Chemistry¹