銠及釕金屬催化碳—氫鍵活化與環化反應之研究

Rhodium and Ruthenium-Catalyzed C−H Bond Activation and Cyclization Reactions

莫瑞克(Krishnamoorthy Muralirajan)

指導教授 ： 鄭建鴻

國立清華大學/理學院/化學系/博士(2013年)

https://doi.org/10.6843/NTHU.2013.00381

摘要

無中文摘要

關鍵字

銠 ； 碳-氫鍵活化 ； 碳-氮鍵生成 ； 環化反應

並列摘要

ABSTRACT

Transition-metal-catalyzed direct conversions of unreactive, less polar CH bonds into numerous organic functional groups by uniting commercially available π-components, which brought a revolution recently in synthetic methodologies for the production of pharmaceuticals, natural products and for opening new routes to organic reactions. Because it can introduce simple conversions, consumes low catalyst loading, inexpensive, readily available starting materials and environmentally friendly conditions. A large variety of metal catalysts, especially rhodium, palladium and ruthenium catalysts are now useful for the efficient catalytic conversion of CH bonds. The uses of rhodium and ruthenium complexes for CH activation via insertion of unsaturated substrates to generate new CC bonds are considerable interest in organic synthesis.
In this regard, this thesis describes seven new reactions that focus on the various directing groups with various alkynes and alkenes by rhodium and ruthenium catalyzed CH activations. The CH functionalization reaction affords various functionalized heterocyclic compounds and yields out new five membered and six membered rings. On the other hand carbocyclization, annulation, and insertion reactions of
ketone, aldehyde, azo, hydrazine hydrochloride and pyridine containing arenes with simple alkynes and alkenes afforded biologically active indenols, isocoumarins, cinnolinium salts, indoles and amide derivatives in one-pot manner. For better perceptive, I divided this thesis into six chapters. The first four chapters describe about rhodium(III)-catalyzed CH bond activation of aryl ketones, aryl aldehydes, azobenzenes, and aryl hydrazine hydrochlorides with internal alkynes. The fifth chapter describes about rhodium(III)-catalyzed ortho alkenation and cyclization of azobenzenes with alkenes. The final chapter deals with ruthenium-catalyzed amidation of 2-arylpyrindes with isocyanates by CH activation.
 Chapter 1 describes a regioselective synthesis of indenols by rhodium-catalyzed CH activation and carbocyclization of aryl ketones and alkynes. The catalytic system proceeds via CH activation followed by regioselective insertion of alkynes to give biologically useful, substituted indenols in excellent yields.

 Chapter 2 deals about a synthesis of highly substituted isocoumarin derivatives from aryl aldehydes and alkynes via C−H activation as a result of rhodium catalyst. This methodology shows in-situ oxidation of aldehydes affords acid and ortho CH activation. This simple method offers an alternative and less expensive way to the synthesis of isocoumarins.

 Chapter 3 illustrates the rhodium (III)-catalyzed synthesis of cinnolinium salts starting with azobenzenes and alkynes: application to the synthesis of indoles and cinnolines. The reaction path way appears to be the first example employing rhodium catalyzed CH activation and annulation to the synthesis of cinnolinium salts. In addition, the cinnolinium salt products have been successfully applied to the synthesis of three important classes of bioactive compounds and advanced materials namely indole, indoloindole and cinnoline derivatives.

 Chapter 4 elaborates an efficient regioselective synthesis of indoles from aryl hydrazine hydrochlorides and alkynes via CH activation. This reaction proceeds through the hydrazone group directed selective ortho CH bond activation and insertion of NN bond gave indoles in highly regioselective manner.

 Chapter 5 reveals a new insertion and aromatization of azobenzenes with alkenes via RhCp*-catalyzed CH activation. The present rhodium catalyzed CH activation reaction is successfully applied to various acrylates and acrylamides to synthesize aminoindole-2-carboxylates and 2-carboxyindoles.

 Chapter 6 shows a Ru(II)-catalyzed amidation of 2-arylpyridines with isocyanates via CH activation. This method provides an opportunity for the synthesis of various amidated 2-arylpyridines using less expensive ruthenium catalyst under mild reaction condition.

並列關鍵字

rhodium ； C-H activation ； C-N bond formation ； annulation

參考文獻

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