ChemInform Abstract: Stereospecific Reduction of Diastereomerically Pure Menthyl Phosphinates: A New Route to Optically Active Phosphine Oxides.
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Stereospecificity
The phosphine dissociation characteristics of a range of bis-phosphine ruthenium(II)−arene complexes, [Ru(PPh3)(PR3)(η6-arene)]PF6 (arene = p-cymene: PR3 = PPhMe2, PPh3, P(p-tol)3, PPh2iPr; arene = PhMe: PR3 = PPhMe2, PPh3), [Ru(PPh3)(η2-PPh2(C6H4O))(η6-p-cymene)]PF6, and [RuCl(PPh3)(η7-PPh2(CH2)3Ph)]PF6, have been investigated by a combination of ligand exchange kinetics (with P(p-tol)3 in THF) and tandem electrospray ionization mass spectrometry (ESI-MS/MS). Trends in reactivity established from these studies were rationalized in terms of steric bulk, on the arene or phosphine, and conformational freedom of the phosphine ligands. A good correlation is found between these trends, especially from the ESI-MS/MS data, and activity of the complexes as catalyst precursors for the hydrogenation of styrene to ethyl benzene (in THF). The most active catalyst precursors show good activity under comparatively mild conditions (e.g., TOF ≥ 2000 h-1 for styrene hydrogenation in THF at 50 °C under 50 bar of H2). The X-ray structures of [RuCl(PPh3)(PPhMe2)(η6-p-cymene)]PF6, [RuCl(PPh3)(PPh2iPr)(η6-p-cymene)]PF6, [RuCl(PPh3)(P(p-tol)3)(η6-p-cymene)]PF6, and [RuCl(η2-PPh2(C6H4O))(η6-p-cymene)] are also reported.
Reactivity
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The phenyldimethylsilyl-cuprate reagent reacts with secondary allyl acetates stereospecifically anti, and with secondary and tertiary allyl urethanes stereospecifically syn; these reactions can be used to synthesise either enantiomer of an optically active allylsilane from a single enantiomer of an optically active allyl alcohol.
Stereospecificity
Allyl alcohol
Enantiomeric excess
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Abstract Bei der Einwirkung von Alkylmercaptanen (II) auf Alkylphenyl‐chlorarsine (I) in Anwesenheit der optisch‐aktiven Verbindung (III) läßt sich eine asymmetrische Synthese der Alkylester der Alkylphenyl‐thioarsinigsäure (IV) durchführen.
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Treatment of sulphinamides with alcohols in the presence of strong acids results in the formation of sulphinates in good yields; this reaction has been shown to proceed with inversion of configuration at the sulphinyl centre and high stereospecificity which is dependent on the structure of the alcohol used.
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Abstract Der aus S‐Milchsäure hergestellte Ester (I) wird mit den Aryl‐Grignard‐Verbindungen (II) in die Diole (III) übergeführt, aus denen stereospezifisch die Epoxide (IV) hergestellt werden (opt.
Stereospecificity
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Stereospecificity
Diastereomer
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Stereospecificity
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An efficient method for the synthesis of optically active N -alkyl aziridines has been realized for the first time by stereospecific reductive cyclization of optically active α-mesylated acetamides. A series of optically active N -alkyl aziridines are prepared in moderate to good yields and excellent ees.
Stereospecificity
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Abstract Optisch aktive Übergangsmetall‐Komplexe.
Stereospecificity
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Reaction of optically active π-allylpalladium complexes with Cl3SiSiMe3 or Cl2PhSiSiMe3 in the presence of triphenylphosphine was found to proceed with retention of configuration to give optically active allylsilanes in high yields.
Stereospecificity
Walden inversion
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