Reaction of secondary phosphine oxides with acylacetylenes

Dvorko, Marina Yu.; Glotova, T. E.; Ushakov, Igor А.; Гусарова, Н. К.

doi:10.1134/s1070428010040056

Cited by 13 publications

(5 citation statements)

References 24 publications

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“…Of these compounds, only 7 a resulting from 1O and acetone could be isolated in pure form. The more sterically congested compound 7 b was in equilibrium with the starting materials, [13] which precluded its isolation by chromatography or crystallization because 1O and Ph 2 CO were partly regenerated during the purification. Lastly, in the reaction of the phosphane oxide 1O with phenyl isocyanate [14] and isothiocyanate, the respective phosphabiurets 8 a and 8 b were formed in good yields [15] .…”

Section: Methodsmentioning

confidence: 99%

A Stable Primary Phosphane Oxide and Its Heavier Congeners

Horký

Cı́sařová

Štěpnička

2020

Chemistry A European J

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(Ferrocenylmethyl)phosphane (1)o xidation with hydrogen peroxide, elemental sulfur and grey selenium produced (ferrocenylmethyl)phosphane oxide 1O,s ulfide 1S and selenide 1Se,r espectively,a st he first isolable primary phosphane chalcogenides lacking stericp rotection. At elevated temperatures, compound 1O disproportionated into 1 and (ferrocenylmethyl)phosphinic acid.I nr eactions with [(h 6-mes)RuCl 2 ] 2 , 1O underwent tautomerization into ap hosphanec omplex [(h 6-mes)RuCl 2 {FcCH 2 PH(OH)-kP}],w hereas 1S and 1Se lost their P-bound chalcogen atoms, giving rise to the phosphane complex [(h 6-mes)-RuCl 2 (FcCH 2 PH 2-kP)] (Fc = ferrocenyl, mes = mesitylene). No tautomerization was observed in the reactiono f1O with B(C 6 F 5) 3 ,w hich insteadp roduced aL ewis pair FcCH 2 P(O)H 2-B(C 6 F 5) 3 .P hosphane oxide 1O added to C=O bonds of aldehydes and ketonesa nd even to cumulenes PhNCE (E = Oa nd S). However,b oth PH hydrogens were only employed in the reactions with aldehydes and cyanates. Scheme1.Synthesis of P-chalcogenides 1E.

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Section: Methodsmentioning

confidence: 99%

A Stable Primary Phosphane Oxide and Its Heavier Congeners

Horký

Cı́sařová

Štěpnička

2020

Chemistry A European J

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“…Similarly to FcCH 2 P(O)H 2 , compounds 6 and 7 reacted with acetone at slightly elevated temperature (40 °C; the reaction proceeds even at room temperature but only slowly), providing the corresponding addition products 8 and 9 in good yields. Phosphine oxides 6 – 9 were stable under ambient conditions (we noted, however, that compounds 8 and 9 slowly and partly regenerated 6 and 7 , respectively, in a dichloromethane solution , ).…”

Section: Resultsmentioning

confidence: 60%

Synthesis, Reactivity, and Coordination of Semihomologous dppf Congeners Bearing Primary Phosphine and Primary Phosphine Oxide Groups

2021

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This contribution reports the synthesis of two phosphinoferrocene ligands desymmetrized by an inserted methylene spacer, viz., a bis-phosphine combining primary and tertiary phosphine moieties in its structure, Ph2PfcCH2PH2 (2), and a structurally unique, stable phosphine-primary phosphine oxide Ph2PfcCH2P(O)H2 (7; fc = ferrocene-1,1′-diyl). Compounds 2 and 7, together with 1,1′-bis(diphenylphosphino)ferrocene (dppf), the bis-tertiary phosphine Ph2PfcCH2PPh2, and the adduct Ph2P(BH3)fcCH2PH2 (6), were studied as ligands in Ru(II) complexes bearing auxiliary η6-arene ligands and both free ligands and the isolated complexes were structurally authenticated, using spectroscopic methods and X-ray crystallography, and further investigated by cyclic voltammetry. The results suggest that distinct donor moieties in the unsymmetric ligands differentiate the otherwise identical coordinated metal centers and that the phosphine moiety in phosphine-phosphine oxide ligand 7 is preferably coordinated to Ru(II), before the phosphine oxide group, which must tautomerize into the hydroxyphosphine form prior to coordination.

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“…Vicinal bis-addition of P(O)H compounds to alkynes can be catalyzed by organometallic catalysts, for example, palladium, [5] nickel [6] and rhodium in the microwave irradiation. [7] Other methods of the double addition of P(O)H compounds to alkynes require the use of strong bases (KOH, [8] t-BuOLi, [9] t-BuOK [10] ).…”

Section: Introductionmentioning

confidence: 99%

Phosphine‐Catalyzed α‐ and Vicinal Bis‐Addition of P(O)H Compounds to Alkynoates

et al. 2023

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The efficient route to phosphine‐catalyzed preparation of α‐phosphoryl acrylates and vicinal bis‐phosphoryl propanoates was developed. The products of diarylphosphine oxide monoaddition and dibenzyl‐H‐phosphonate vicinal bis‐addition to ethylphenylpropiolate were obtained by using previously data on the reactivity and prototropic tautomerism of various classes of P(O)H compounds. In previous works devoted to the phosphine‐catalyzed addition of P(O)H compounds to this activated alkyne, the use of secondary phosphine oxides gave only vicinal bisphosphine oxides, while the addition of H‐phosphonates led only to α‐products. On the basis of this work and our previous studies, a series of the reactivity increase of P(O)H compounds in the phosphine‐catalyzed β‐addition reaction can be assumed: (AlkO)2P(O)H≤Ph(EtO)P(O)H<(BnO)2P(O)H<(m‐(CH3)2C6H3)2P(O)H

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Reaction of secondary phosphine oxides with acylacetylenes

Cited by 13 publications

References 24 publications

A Stable Primary Phosphane Oxide and Its Heavier Congeners

A Stable Primary Phosphane Oxide and Its Heavier Congeners

Synthesis, Reactivity, and Coordination of Semihomologous dppf Congeners Bearing Primary Phosphine and Primary Phosphine Oxide Groups

Phosphine‐Catalyzed α‐ and Vicinal Bis‐Addition of P(O)H Compounds to Alkynoates

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