Toward the catalytic synthesis of phosphiranes. A computational study

Goumans, T. P. M.; Ehlers, Andreas W.; Lammertsma, Koop

doi:10.1016/j.jorganchem.2005.05.040

Cited by 11 publications

(8 citation statements)

References 86 publications

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“…[57] Lammertsma and co-workers showed that the rate of the reaction of phosphinidenes 10 (M = Co (10 c), Rh (10 d), Ir (10 a)) with dihalomethanes to afford phosphaalkene 76 d (Scheme 23 a) depends on the halogen atom of the substrate, the oxo-and halophilicity of the transition metal, and the electronic properties of the ancillary ligand.…”

Section: Angewandte Chemiementioning

confidence: 99%

Nucleophilic Phosphinidene Complexes: Access and Applicability

2010

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Syntheses, properties, and reactivities of nucleophilic phosphinidene complexes [L(n)M=P-R] are reviewed. Emphasis is placed on the electronic tuning of this emerging class of phosphorus reagents, using different ancillary ligands and coordinatively unsaturated transition-metal moieties. The difference in applicability of the established stable 18-electron and transient 16-electron phosphinidenes is addressed.

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Section: Angewandte Chemiementioning

confidence: 99%

Nucleophilic Phosphinidene Complexes: Access and Applicability

2010

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“…4 Only a handful of transition metal-promoted phosphirane syntheses have been reported, 5−8 and catalytic phosphiranation to give unprotected λ 3 -phosphiranes remains unknown despite decades of interest. 6,7,9−11…”

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confidence: 99%

“…In contrast, the phosphorus analog (“phosphiranation”) remains in its infancy, despite the documented utility of phosphiranes as catalyst ligands, polymer precursors, and synthetic intermediates . Only a handful of transition metal-promoted phosphirane syntheses have been reported, − and catalytic phosphiranation to give unprotected λ 3 -phosphiranes remains unknown despite decades of interest. ,,− …”

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confidence: 99%

Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes

2019

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Catalytic phosphiranation has been achieved, allowing preparation of trans -1-R-2-phenylphosphiranes (R = t -Bu: 1 - t -Bu; i -Pr: 1 - i -Pr) from the corresponding dibenzo-7-(R)-7-phospha-norbornadiene (RP A , A = C 14 H 10 , anthracene) and styrene in 73% and 57% isolated yields, respectively. The cocatalyst system requires tetramethylammonium fluoride (TMAF) and [Fp(THF)][BF 4 ] (Fp = Fe(η 5 -C 5 H 5 )(CO) 2 ). In the case of the t -Bu derivative, the reaction mechanism was probed using stoichiometric reaction studies, a Hammett analysis, and a deuterium labeling experiment. Together, these suggest the intermediacy of iron-phosphido FpP(F)( t -Bu) ( 2 ), generated independently from the stoichiometric reaction of [Fp( t -BuP A )][BF 4 ] with TMAF. Two other plausible reaction intermediates, [Fp( t -BuP A )][BF 4 ] and [Fp( 1 - t -Bu)][BF 4 ], were prepared independently and structurally characterized.

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“…Dieser Ansatz wurde erfolgreich auf die Synthese des Phosphirens 80 , des Phospholans 81 und des substituierten Phosphirans 82 erweitert (Schema ) 20b. Der Bildungmechanismus des Phosphirans 80 aus dem Zr‐Phosphiniden 4 und 1,2‐Dichlorethan unter Beteiligung des 16‐Elektronen‐Komplexes [Cp 2 ZrPMes*] wurde auch in theoretischen Studien untersucht 57…”

Section: Reaktivität Nucleophiler Phosphinidenkomplexeunclassified

Nucleophile Phosphinidenkomplexe: Synthese und Anwendungen

2010

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Dieser Kurzaufsatz gibt einen Überblick über die Synthese, Eigenschaften und Reaktivitäten nucleophiler Phosphinidenkomplexe, [LnMPR]. Ein Schwerpunkt liegt auf Methoden zur Feinabstimmung der elektronischen Eigenschaften dieser neuen Klasse von Phosphorreagentien mithilfe verschiedener Hilfsliganden und koordinativ ungesättigter Übergangsmetallfragmente. Zudem richten wir unser Augenmerk auf die charakteristischen Unterschiede in der Anwendbarkeit der stabilen 18‐Elektronen‐Phosphinidene und der kurzlebigen 16‐Elektronen‐Phosphinidene.

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Toward the catalytic synthesis of phosphiranes. A computational study

Cited by 11 publications

References 86 publications

Nucleophilic Phosphinidene Complexes: Access and Applicability

Nucleophilic Phosphinidene Complexes: Access and Applicability

Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes

Nucleophile Phosphinidenkomplexe: Synthese und Anwendungen

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