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Silane, trichloro - | Cl3HSi or Cl3Si ..

Some phenomenological and mechanistic aspects of the use of copper as catalyst in trichlorosilane synthesis

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and Protective Action Distances for Trichlorosilane ..

This thesis consists of two subprojects, dealing with the design, synthesis and application of novel (1) pyridinyl-oxazoline ligands and (2) prolyl-oxazoline ligands.
In Project 1 eleven novel pyridinyl-oxazoline ligands were synthesized. Metal complexes of these ligands have been applied to transition-metal catalysed reactions, including asymmetric cyclopropanation reaction, asymmetric allylic alkylation reaction and asymmetric reduction of a conjugated ketone. The copper complexes of these ligands gave good conversions (up to 73%) but low enantiomeric excesses (up to 14%) in the cyclopropanation reaction. In the allylic alkylation reaction, the palladium complexes of these ligands showed excellent activities (up to 96% conversion) and modest selectivities (up to 28% ee). In the asymmetric reduction of a conjugated ketone, up to 99% conversions and 20% ee were achieved using the cobalt complexes of these ligands..
The ligands were also applied to the organo-catalytic reactions, including the trichlorosilane-assisted hydrosilylation of acetophenone and an imine, and the allyltrichlorosilane-assisted allylation of benzaldehyde. In the hydrosilylation the ligands showed outstanding catalytic activities giving over 90% conversions in 13 out of the 17 test reactions. In the hydrosilylation of an imine the ligands gave up to 28% ee and in the hydrosilylation of acetophenone the ligands offered up to 70% ee, the highest seen in our work in this reaction. In the allylation of benzaldehyde the ligands were not as efficient, giving up to 11% conversion and 25% ee.
In Project 2, we designed and developed two pathways for the synthesis of a prolyl oxazoline ligand. We then attempted the synthesis of a phosphine- oxazoline ligand from this prolyl oxazoline base. Although the synthesis was not completed, due to time constraints, it demonstrated the potential of synthesizing a novel phosphine-oxazoline ligand in a flexible manner via two synthetic routes.
Chapter One deals with the introduction of general concepts of asymmetric synthesis, oxazoline ligands and their applications to different catalytic reactions. Chapter Two discusses the synthesis of novel mono-oxazoline ligands and the application of these ligands, or the metal complexes of these ligands, to the asymmetric catalytic reactions. Chapter Three contains the full experimental details for the project, including spectral and analytical data.

The invention discloses equipment for preparing trichlorosilane

This telescoped synthesis gave the final product in 45% overall yield and required less than 2 h as a total reaction time, representing the shortest existing route for the manufacture of efavirenz.

Acker 2008 Journal of Organometallic Chemistry | …

Acker 2008 Journal of Organometallic ..

This thesis consists of two subprojects, dealing with the design, synthesis and application of novel (1) pyridinyl-oxazoline ligands and (2) prolyl-oxazoline ligands.
In Project 1 eleven novel pyridinyl-oxazoline ligands were synthesized. Metal complexes of these ligands have been applied to transition-metal catalysed reactions, including asymmetric cyclopropanation reaction, asymmetric allylic alkylation reaction and asymmetric reduction of a conjugated ketone. The copper complexes of these ligands gave good conversions (up to 73%) but low enantiomeric excesses (up to 14%) in the cyclopropanation reaction. In the allylic alkylation reaction, the palladium complexes of these ligands showed excellent activities (up to 96% conversion) and modest selectivities (up to 28% ee). In the asymmetric reduction of a conjugated ketone, up to 99% conversions and 20% ee were achieved using the cobalt complexes of these ligands..
The ligands were also applied to the organo-catalytic reactions, including the trichlorosilane-assisted hydrosilylation of acetophenone and an imine, and the allyltrichlorosilane-assisted allylation of benzaldehyde. In the hydrosilylation the ligands showed outstanding catalytic activities giving over 90% conversions in 13 out of the 17 test reactions. In the hydrosilylation of an imine the ligands gave up to 28% ee and in the hydrosilylation of acetophenone the ligands offered up to 70% ee, the highest seen in our work in this reaction. In the allylation of benzaldehyde the ligands were not as efficient, giving up to 11% conversion and 25% ee.
In Project 2, we designed and developed two pathways for the synthesis of a prolyl oxazoline ligand. We then attempted the synthesis of a phosphine- oxazoline ligand from this prolyl oxazoline base. Although the synthesis was not completed, due to time constraints, it demonstrated the potential of synthesizing a novel phosphine-oxazoline ligand in a flexible manner via two synthetic routes.
Chapter One deals with the introduction of general concepts of asymmetric synthesis, oxazoline ligands and their applications to different catalytic reactions. Chapter Two discusses the synthesis of novel mono-oxazoline ligands and the application of these ligands, or the metal complexes of these ligands, to the asymmetric catalytic reactions. Chapter Three contains the full experimental details for the project, including spectral and analytical data.

With the optimized conditions in hand, we set out to explore the scope of the reaction (). A diverse set of commercially available and generated Grignard reagents were used to synthesize a variety of sulfoxides. We were pleased to find that aromatic Grignard reagents bearing electron-donating, -neutral, and -withdrawing groups could be combined, to afford unsymmetrical diaryl sulfoxides in good yields (5ad). The initial addition of an aryl Grignard reagent could be partnered effectively with primary (5e), secondary (5f,g), and tertiary alkyl Grignard reagents (5h) to deliver mixed arylalkyl sulfoxides.

To Acker 2008 Journal of Organometallic Chemistry.

Thermodynamic assessment of the copper catalyzed direct synthesis of ..

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    本发明针对合成三氯硅烷的系统和方法。 The system and method of the present invention for the synthesis of trichlorosilane.

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