Chelating diphosphite complexes of nickel(0) and platinum(0): their remarkable stability and hydrocyanation activity

Baker, Michael J.; Harrison, Karl N.; Orpen, A. Guy; Pringle, Paul G.; Shaw, G.

doi:10.1039/c39910000803

Cited by 86 publications

(47 citation statements)

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“…[113] Recently, chiral aryl diphosphite ligands derived from 2,2'-binaphthol are found to be useful for the Ni 0 -catalyzed enantioselective hydrocyanation of styrenes (up to 94 % regioselectivity; up to 65 % ee) and vinyl acetate (83 % regioselectivity; 73 % ee) by using acetone cyanohydrine as the cyanating agent (Scheme 30). [114] Again, the branched nitriles are formed due to the thermodynamically stabilized branched benzyl nickel complex.…”

Section: Scheme 28 Nickel Catalyzed Hydrocyanation Of Styrenementioning

confidence: 99%

Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

et al. 2004

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The regioselective functionalization of terminal alkenes and alkynes is of utmost importance for the synthesis of a wide variety of organic products. Based on the original observation by Vladimir Markovnikov-the pioneer of this field of research-in the 19th century, the possible regioisomeric products are classified as Markovnikov or anti-Markovnikov products. Contrary to traditional belief, it is nowadays possible to control the regiochemistry of various additions of nucleophiles to alkenes and alkynes by applying different transition-metal catalysts. Recent developments in this area of selective functionalization of alkenes and alkynes are reviewed.

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Section: Scheme 28 Nickel Catalyzed Hydrocyanation Of Styrenementioning

confidence: 99%

Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

et al. 2004

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“…The 5 ligands coordinate in a bidentate fashion, as monodentate coordination would form the complex (L)Ni(CO) 3 , which would give an IR CO vibration at~2085 cm À1 . [12] Furthermore, nickel bis-chelates have been identified as inactive systems in hydrocyanation reactions; [7,9,14,15] the formation of bis-chelates is likely to be dependent on the steric bulk of the ligand. NMR experiments were carried out in which 1 and 3 equivalents of ligand L1-L5 were mixed with NiA C H T U N G T R E N N U N G (cod) 2 at 25 8C (Table 4).…”

Section: Electronic and Steric Effectsmentioning

confidence: 99%

Binaphthol‐Based Diphosphite Ligands in Asymmetric Nickel‐Catalyzed Hydrocyanation of Styrene and 1,3‐Cyclohexadiene: Influence of Steric Properties

et al. 2007

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A series of chiral (R)-binaphthol-based diphosphite ligands with different substituents was prepared and applied in the asymmetric nickel-catalyzed hydrocyanation of styrene and 1,3-cyclohexadiene to investigate the influence of their steric properties. The optimum steric properties for the hydrocyanation reaction lie within a narrow window. With the optimized ligand, hydrocyanation of styrene gave full conversion (Subs/Ni = 100) with 49 % ee, the TON was determined to be 600. Hydrocyanation of 1,3-cyclohexadiene gave 50 % conversion (Subs/Ni = 500) with an excellent ee of 86 %. This demonstrates that high ees are not only accessible for vinylarenes but also for conjugated dienes in the asymmetric nickelcatalyzed hydrocyanation.

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“…Entsprechende σ 3 P-Verbindungen wurden bereits untersucht [12,14]. Entsprechende σ 3 P-Verbindungen wurden bereits untersucht [12,14].…”

Section: Schemaunclassified

Zur Reaktion von Dihydroxybiphenylen mit Phosphorpentachlorid - Phosphepine mit Phosphonium- und Phosphoranstruktur

Gloede¹,

Habicher

Schneider

2002

Z. anorg. allg. Chem.

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Bei der Redaktion eingegangen am 23. Juli 2001.Inhaltsübersicht. Die 2,2Ј-Dihydroxybiphenylderivate 1d-f reagieren mit Phosphorpentachlorid zu den Dioxaphosphepinium-hexachlorophosphaten 3a, 3b und 17. Als Zwischenstufen werden die Trichloro-dioxaphosphepine 8a, 8b und 21 diskutiert, deren Existenz durch Chlorierung der 6-Chloro-dioxaphosphepine 7a, 7b und 20 Abstract. The 2,2Ј-dihydroxybiphenyl derivatives 1d-f react with phosphorus pentachloride to give the dioxaphosphepinium hexachlorophosphates 3a, 3b, and 17. The trichloro-dioxaphosphepins 8a, 8b, and 21 were discussed as intermediates, which were obtained by chlorination of the 6-chloro-dioxaphosphepins 7a, 7b, and 20. The hydrolysis of the dioxaphosphepins leads to the stable, cyclic Einleitung Bei den Reaktionen von Dihydroxyaromaten mit Phosphorpentachlorid werden Trichlorodioxyphosphorane erhalten. So reagieren Brenzcatechinderivate (1a) zu 5-gliedrigen cyclischen Phosphoranen vom Typ 2a und Bis(o-hydroxyphenyl)-methanderivate (1b) zu 8-gliedrigen cyclischen Phosphoranen vom Typ 2b [1Ϫ4]. Die entsprechenden 7-gliedrigen cyclischen Derivate vom Typ 2c sind bisher noch nicht beschrieben. Die unsubstituierte Verbindung 2c (Y ϭ H) wurde als Zwischenprodukt bei der Umsetzung von 2,2Ј-Dihydroxybiphenyl (1d) mit PCl 5 (Molverhältnis: 3:1) vermutet, aber eine Isolierung oder Charakterisierung erfolgte nicht [3].Wir berichten hier über das Verhalten der unterschiedlich substituierten 2,2Ј-Dihydroxy-biphenylderivate 1d-1f gegenüber PCl 5 . bewiesen werden konnte. Die Hydrolyse der Dioxaphosphepinderivate führt zu den stabilen, cyclische Phosphorsäurederivaten 4a, 4b, 9a, 9b, 11a, 11b,19a und 19b. Vom Dioxaphosphepin 4a ist die Kristallstruktur bestimmt worden; in der asymmetrischen Einheit befinden sich zwei unterschiedliche Moleküle.phosphates 4a, 4b, 9a, 9b, 11a, 11b, 19a, and 19b. The crystal structure of 4a was determined; two different molecules was observed in the asymmetric unit. Ergebnisse und DiskussionReaktion von 2,2Ј-Dihydroxybiphenyl (1d) und 2,2Ј-Dihydroxybinaphthyl (1e) mit Phosphorpentachlorid Die Umsetzung des Diols 1d mit PCl 5 in Chloroform verläuft unter HCl-Entwicklung. Im 31 P-NMR-Spektrum der Reaktionslösung werden zwei Signale mit den δ-Werten von 8,6 und Ϫ298 beobachtet. Sie sprechen für das Vorliegen eines cyclischen Tetraoxyphosphonium-hexachlorophos-

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Chelating diphosphite complexes of nickel(0) and platinum(0): their remarkable stability and hydrocyanation activity

Abstract: The synthesis, stability and hydrocyanation catalytic activity of nickel(0) complexes of the diphosphite 1 derived from 2,2'-biphenol are described; the X-ray crystal structures of the ligand 1 and its platinum(0) complex 2b are reported.

Cited by 86 publications

References 1 publication

Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

Binaphthol‐Based Diphosphite Ligands in Asymmetric Nickel‐Catalyzed Hydrocyanation of Styrene and 1,3‐Cyclohexadiene: Influence of Steric Properties

Zur Reaktion von Dihydroxybiphenylen mit Phosphorpentachlorid - Phosphepine mit Phosphonium- und Phosphoranstruktur

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