Ruthenium- and Manganese-Catalyzed C−O and C−C Formation via C−H Activation

by Weiping Liu
Doctoral thesis
Date of Examination:2016-06-06
Date of issue:2016-06-08
Advisor:Prof. Dr. Lutz Ackermann
Referee:Prof. Dr. Lutz Ackermann
Referee:Prof. Dr. Dietmar Stalke
Persistent Address: http://dx.doi.org/10.53846/goediss-5685

 

 

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Abstract

English

In the past several decades, transition metal-catalyzed cross-coupling reactions have been proved to be one of the most useful and reliable tools for C−C bond formation. However, the prefunctionalized organometallic substrates are often sensitive to air and water, relatively expensive and generate stoichiometric byproducts, all of which remain major disadvantages and limit their applications. According to the guideline of the twelve principles of green chemistry, direct C−H activations are emerging as potential alternatives to conventional cross-coupling reactions due to their atom- and step-economy, which compares favorably to traditional organic synthesis. Indeed, C−H activation has been identified to be a powerful tool for constructing complicated molecules from simple precursors. First, an unprecedented ruthenium(II)-catalyzed C–H cyanation on arenes by using bench stable, readily accessible and user-friendly N-cyano-N-phenyl-p-toluenesulfonamide (NCTS, 13) as the cyanation reagent was accomplished. Second, an ortho- and para-selective ruthenium-catalyzed C(sp2)–H oxygenation of phenol derivatives was developed, which provides a new strategy for the synthesis of phenol derivatives. Third, a novel type of manganese-catalyzed annulation of acrylates by imines via organometallic C–H bond activation was developed, which provided a new approach to valuable carbocyclic β-amino acid derivatives. Fourth, the first manganese-catalyzed C–H aminocarbonylation with good yields, highly functional group tolerance and broad substrate scope was developed. Fifth, a versatile manganese(I)-catalyzed allylation of inert C–H bond with allyl carbonates by C–O bond cleavage has been developed.
Keywords: C-H Activation; Ruthenium; Manganese; Homogenous Catalysis
 
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