Synthesis and Application of New Chiral Ligands for Enantioselectivity Tuning in Transition Metal Catalysis

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A set of five new C3-symmetric phosphites were synthesized and tested in palladium-catalyzed asymmetric Suzuki coupling. The observed reactivity and selectivity were dependent upon several factors. One of the phosphites was able to achieve some of the highest levels of enantioselectivity in asymmetric Suzuki couplings with specific substrates. Different hypotheses have been made for understanding the ligand effects and reaction selectivities, and those hypotheses were tested via various methods including DOSY NMR experiments, X-ray crystallography, and correlation of catalyst selectivity with Tolman cone angles. Although only modest enantioselectivities were observed in most reactions, the ability to synthesis these phosphites in ... continued below

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Kong, Fanji August 2017.

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  • Kong, Fanji

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A set of five new C3-symmetric phosphites were synthesized and tested in palladium-catalyzed asymmetric Suzuki coupling. The observed reactivity and selectivity were dependent upon several factors. One of the phosphites was able to achieve some of the highest levels of enantioselectivity in asymmetric Suzuki couplings with specific substrates. Different hypotheses have been made for understanding the ligand effects and reaction selectivities, and those hypotheses were tested via various methods including DOSY NMR experiments, X-ray crystallography, and correlation of catalyst selectivity with Tolman cone angles. Although only modest enantioselectivities were observed in most reactions, the ability to synthesis these phosphites in only three steps on gram scales and to readily tune their properties by simple modification of the binaphthyl 2´-substituents makes them promising candidates for determining structure-selectivity relationships in asymmetric transition metal catalysis, in which phosphites have been previously shown to be successful. A series of novel chiral oxazoline-based carbodicarbene ligands was targeted for synthesis. Unfortunately, the chosen synthetic route could not be completed due to unwanted reactivity of the oxazoline ring. However, a new and efficient route for Pd-catalyzed direct amination of aryl halides with oxazoline amine was developed and optimized during these studies. Chiral binaphthyl based Pd(II) ADC complexes with different substituent groups have been synthesized and tested in asymmetric Suzuki coupling reactions. Although only low enantioselectivities were observed in Suzuki coupling, this represents a new class of chiral metal-ADC catalysts that could be tested in further catalytic.

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  • August 2017

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  • Oct. 9, 2017, 11:44 a.m.

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Kong, Fanji. Synthesis and Application of New Chiral Ligands for Enantioselectivity Tuning in Transition Metal Catalysis, thesis, August 2017; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc1011774/: accessed August 14, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .